EPA/AA/CTAB/PA/81-11
MOBILE SOURCE EMISSIONS OF FORMALDEHYDE AND OTHER ALDEHYDES
by
Penny M. Carey
May 1981
NOTICE
Technical reports do not necessarily represent final EPA decisions
or positions. They are intended to present technical analyses of
issues using data which are currently available. .The purpose in
the release of such reports is to facilitate the exchange of
technical information and to inform the public of technical
developments which may form the basis for a final EPA decision,
position or regulatory action.
Control Technology Assessment and Characterization Branch
Emission Control Technology Division
Office of Mobile Source Air Pollution Control
U.S. Environmental Protection Agency
2565 Plymouth Road
Ann Arbor, Michigan 48105
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Mobile Source Emissions of Formaldehyde and Other Aldehydes
I. Introduction
Aldehydes are a class of partially oxidized hydrocarbons emitted from many
sources, including mobile sources. Vehicular aldehyde emissions are
currently unregulated; however, preliminary results of a 24-month inhalation
study indicate that formaldehyde, the most prevalent aldehyde in vehicular
emissions, is a carcinogen in rats. The results of this study may serve as
an impetus for future regulatory action and possible classification of
formaldehyde as a human carcinogen.. Consequently, there has been an
increasing number of studies examining the potential health risks and
relative contribution of the aldehydes as exhaust pollutants. Topics
covered in these studies include aldehyde emission factors for unmodified
and malfunction vehicle engine configurations, effects of mileage accu-
mulation, fuel and temperature variations and aldehyde emissions from
Diesel-equipped vehicles equipped with prototype light-duty Diesel oxidation
catalysts. The purpose of this document is to summarize these studies and
formulate formaldehyde and total aldehyde emission factors for each vehicle
class.
II. Summary
The available vehicular aldehyde studies were summarized in an attempt to
characterize aldehyde emissions from motor vehicles. Topics covered in these
studies include aldehyde emission factors for unmodified and malfunction
vehicle engine configurations, effects of fuel, mileage accumulation and
temperature variations and aldehyde emissions from Diesel-equipped vehicles
equipped with prototype light-duty Diesel oxidation catalysts. Thus, it was
possible to obtain aldehyde data for standard conditions and for a variety
of operating conditions. The Federal test procedure (FTP) was used for the
light-duty vehicles and the 13-mode test procedure for the heavy-duty
engines. The 2, 4 dinitrophenylhydrazine (DNPH) procedure was used for the
sampling and analysis of the aldehydes. This procedure is discussed in the
Appendix. In addition to aldehydes, the DNPH procedure detects two ketones,
methylethylketone and acetone. Methylethylketone measurements are not
included in this report. However, acetone and two aldehydes, acrolein and
propionaldehyde are reported together as acetone since they are not resolved
from each other under normal gas chromatographic operating conditions. The
term "total aldehydes", as used in this report, includes the acetone
measurements.
Based on the studies summarized, the following generalizations can be made:
1. For the light-duty vehicles, highest average total aldehyde emissions
occurred with the gasoline fueled non-catalyst-equipped vehicles (88.
mg/km) followed by the Diesel engine-equipped vehicles (37 mg/km) and
the gasoline fueled catalyst-equipped vehicles (2 mg/km). Formaldehyde
emissions showed a similar trend. On the same basis (mg/km), the
heavy-duty vehicles, in turn, emitted more formaldehyde and total
aldehydes than the light-duty vehicles.
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2. Results for the malfunction configuration studies involving light-duty
gasoline fueled vehicles indicate that, for the non-catalyst-equipped
vehicles and vehicles equipped with oxidation catalysts, aldehyde
emissions tend to increase most during 12 percent misfire (by factors of
9 and 13, respectively compared to the unmodified configuration).
Aldehyde emissions for these vehicles also increase slightly during rich
best idle and disabled EGR malfunction configurations. The results for
the three-way catalyst-equipped vehicles were not as conclusive. The
greatest number of three-way catalyst-equipped vehicles for which the
emissions increased occurred during a disabled 02 sensor malfunction.
The catalyst-equipped vehicles appear to be more effective in con-
trolling THC, formaldehyde and total aldehyde emissions than non-
catalyst-equipped vehicles, even under malfunction conditions.
3. A Diesel fuel study was conducted with light-duty vehicles and
heavy-duty engines. For the light-duty vehicles, total aldehyde and
formaldehyde emissions were generally the lowest when "Jet A" No. 1 fuel
was used and highest when the Minimum Quality No. 2 fuel was used.
Minimum and maximum total aldehyde emissions differed by as much as a
factor of 4. THC emissions behaved similarly. There was more
variability for the heavy-duty engines, compared to the light-duty
vehicles, and few trends were apparent.
4. The results of a temperature study were variable, but in general
aldehyde emissions tend to increase as the temperature decreases. The
total range for the aldehyde emissions varied from 19 mg/km for a 1980
Buick prototype (soaked and tested at 80°F with the air conditioner
operating) to 285 mg/km for a 1977 Honda Civic without a catalyst
(soaked and tested at 20°F).
5. A 1979 Oldsmobile Diesel Delta 88 was used to evaluate emissions from
prototype catalytic converters for Diesel exhaust supplied by two
manufacturers, Englehard and UOP, Inc. A total of three catalysts were
evaluated; one fresh Engelhard catalyst, one fresh UOP catalyst and an
aged UOP counterpart (subjected by UOP to 81,000 km of road aging on a
similar vehicle before delivery to the test site). The vehicle was also
tested without a catalyst. The fresh catalysts were found to be
effective in decreasing the amount of aldehydes and THC in the exhaust;
however, the fresh UOP catalyst exhibited substantially greater activity
for reducing THC and aldehydes than the aged UOP counterpart. Average
total aldehyde emissions for the fresh Engelhard catalyst were 2.5 mg/km
compared to 6.2 mg/km for the non-catalyst baseline. Average total
aldehyde emissions for the fresh UOP catalyst were 4.3 mg/km compared to
5.7 mg/km for the aged counterpart. Average THC emissions for the fresh
Engelhard catalyst, fresh UOP catalyst, aged UOP catalyst and
non-catalyst baseline were 90, 85, 195 and 245 mg/km respectively.
6. The effect of mileage accumulation on aldehyde emissions from gasoline
fueled catalyst-equipped vehicles has not been extensively studied.
General Motors has conducted tests on four high mileage vehicles
equipped with oxidation catalysts. Odometer readings ranged from 69,417
to 76,099 miles. Aldehyde emissions from these high mileage vehicles
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averaged 18.05 mg/km in comparison to 12.4 mg/km for low mileage
catalyst-equipped vehicles and 87 mg/km for non-catalyst-equipped
vehicles (all tested by GM).
In an EPA sponsored study, aldehyde emissions from four new three-way
catalyst-equipped vehicles were evaluated initially and at three mileage
accumulation points (5000 mile increments). While some of the vehicles
did not show a continuous increase in aldehyde emissions with mileage,
they all showed an increase in individual and total aldehydes from the
initial to the final mileage tesf point. In an attempt to determine if
this trend continues as mileage increases, the data from this study were
extrapolated to higher mileages (50,000 + miles) using linear
regression. Deterioration factors were then calculated at selected high
mileage points and used with low mileage aldehyde data from oxidation
catalyst-equipped vehicles to project aldehyde emissions from high
mileage oxidation catalyst-equipped vehicles. These projected emissions
were then compared to the actual high mileage aldehyde data generated by
GM. The projected values for aldehydes and THC exceeded the values
obtained by GM. It appears that aldehyde and THC emissions do not
increase at a constant rate with increasing mileage; however, it is not
certain whether, 1) these emissions level off at some point, or 2)
continue to increase with mileage but at a slower rate than indicated by
the study. In either case, the projected high mileage aldehyde
emissions from catalyst-equipped vehicles were less than aldehyde
emissions found from non-catalyst-equipped vehicles. An EPA sponsored
study is presently underway to investigate aldehyde emissions from high
mileage catalyst-equipped vehicles.
III. Definition/Sources
Aldehydes are a chemical class of partially oxidized hydrocarbons. A
partially oxidized hydrocarbon is a hydrocarbon containing one or more
oxygen molecules in addition to hydrogen and carbon. The partially oxidized
hydrocarbon with the chemical formula ECHO is known as formaldehyde and its
structure is shown below.
H - C = 0
formaldehyde
In general, aldehydes are a chemical class of partially oxidized
hydrocarbons that contain the group -CHO. Table 1, at the end of the text,
contains a list of a few of the aldehydes, including those measured in motor
vehicle exhaust, along with their corresponding chemical structures.
Formaldehyde is one of the primary aldehydes of importance in industrial use.
Several billion pounds of formaldehyde are produced each year in the United
States. Partially because of formaldehyde's antiseptic properties, it is
used in the medical, brewing, and agricultural industries. It is also
widely used in the manufacture of phenolic, urea, and melamine resins.
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Under certain conditions, formaldehyde can be released into the environment
over a prolonged period from resinous products. These products include
ureafonnaldehyde foam insulation, particle board, and even some plywoods.
Additional sources of formaldehyde include automotive exhaust, smog formed
in the ambient air, cigarette smoke and incinerators. Aldehydes and
formaldehyde are often formed by the incomplete combustion of hydrocarbons.
Aldehydes in mobile source exhaust are formed by the incomplete combustion
(partial oxidation) of the fuel.
IV. Health Effects
This section summarizes some of the available health information on alde-
hydes. The aldehydes have a characteristically pungent odor, are flammable,
are photochemically reactive, can cause respiratory problems and are eye
irritants. The two major aldehydes of interest from a human health per-
spective appear to be formaldehyde and acrolein. Both are severe eye
irritants. In addition, exposure to formaldehyde causes upper respiratory
tract irritation, headaches, gastrointestinal problems and skin irritation.
Formaldehyde is known to be a component of photochemical smog formation.
Photochemical smog is a form of air pollution which arises from the re-
actions of oxides of nitrogen and hydrocarbon compounds in the presence of
sunlight. Formaldehyde can be photooxidized with a nitrogen oxide mixture
in air to yield ozone, which is also toxic. Smog often results in eye and
throat irritation, odor, plant damage and decreased visibility. Form-
aldehyde may account for a large fraction of the eye irritation associated
with photochemical air pollution.
\
There are no published data to indicate that formaldehyde is a confirmed
carcinogen in humans. However, preliminary results of a 24-month inhalation
study sponsored by the Chemical Industry Institute of Toxicology (CUT) in
Research Triangle Park, North Carolina indicate that formaldehyde is a car-
cinogen in rats. After 16 months, three male rats exposed to a formaldehyde
level of 15 ppm for six hours per day, five days per week were found to have
squamous cell carcinoma of the nasal passages. The frequency of nasal
tumors through the 18 month sacrifice was reported by Swenberg et al. (1)*.
These results provided evidence that formaldehyde might represent a
carcinogenic risk to humans.
In April, 1980, a panel of scientists from within the Federal Government was
formed under the guidance of the National Toxicology Program and coordinated
by the Consumer Product Safety Commission. The panel members reviewed and
evaluated the available published and unpublished information on the adverse
health effects from repeated exposure to formaldehyde. Acute toxic effects
and hypersensitivity were not considered by the panel since they had
recently been assessed by the Committee on Toxicology of the National
Academy of Sciences (2). The Panel released their report in November, 1980
(3). The Panel concluded that definitive experiments exist which demon-
strate the mutagenicity and carcinogenicity of formaldehyde under laboratory
conditions. The Panel also concluded that formaldehyde should be presumed
to pose a carcinogenic risk to humans.
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V. Methods of Measurement
Two major methods have been used for the sampling and analysis of aldehydes
in vehicle exhaust, the 3-methyl-2-benzothiazolone hydrazone (MBTH) method
(4) and the 2, 4 dinitrophenylhydrazine (DNPH) procedure (5). The MBTH
method detects total aliphatic aldehydes and is not capable of separating
individual components. The MBTH method has been found to give generally low
results due to a positive interference of oxides of sulfur on the absorption
readings. Previous data from an EPA-DOE program at Bartlesville (6)
indicate that the DNPH method gave, on the average, 44 percent higher
response than the MBTH method. Unlike the MBTH method, the DNPH method
detects individual aldehydes and ketones. The individual aldehydes and
ketones that are included in this analysis are: formaldehyde, acetaldehyde,
acetone, acrolein, propionaldehyde, isobutyraldehyde, methylethylketone,
crotonaldehyde, hexanaldehyde and benzaldehyde. A summary of the DNPH
procedure can be found in the Appendix. Phthalates and
di-2-ethylhexyladipate were found by mass spectroscopy to be interferences
in the procedure (5). Many phthalate esters are found in lubricants and
plastics, and di-2-ethylhexyladipate is used as a fuel stabilizer. The
crotonaldehyde and benzaldehyde values can be affected by these
interferences. The DNPH procedure is also labor intensive but is capable of
at least a 98 percent collection efficiency.
The emission factor data reported here were found using the DNPH method
(with gas chromatograph/flame ionization detector analysis) unless otherwise
stated. Mention should be made of the two ketones detected with this
procedure, methylethylketone and acetone. Methylethylketone measurements
are not included in this report. However, acetone and two aldehydes,
acrolein and propionaldehyde are reported together as acetone since they are
not resolved from each other under normal gas chromatographic operating
conditions. The term "total aldehydes", as used in this report, includes
the acetone measurements. It should be noted that work is currently being
performed to improve both the MBTH (7) and DNPH (8,9) procedures.
VI. Summaries of Aldehyde Studies and Emission Factor Data
A. Manufacturers' Status Reports
At the request of the EPA, the manufacturers submit status reports sum-
marizing their emission control development and testing programs. Many of
the manufacturers have measured unregulated emissions as part* of their
testing program. The following is a summary of some of the manufacturers'
research with regard to the collection and measurement of aldehydes in
vehicle exhaust (10).
GM has presented data on total aldehyde emissions using the MBTH method and
1975 FTP for two Diesel-equipped vehicles, a 1976 Mercedes 300D and a 1976
Peugeot 504D. The results were 13.7 ing/km and 37.3 mg/km respectively.
^Numbers in parentheses designate references at end of paper.
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The MBTH method and 1975 FTP were used to measure total aldehyde emissions
for two cars as part of an evaluation of alcohol-based motor fuels. The
first car was a Brazilian Chevrolet Opala with no emission controls operated
on gasoline/ethanol blends. The HC, CO and NOx emissions were 4.8, 74.5 and
0.8 g/km respectively. The aldehyde emissions were 33.6 mg/km on gasoline,
42.3 mg/km on 52 ethanol, 59 mg/km on 10% ethanol and 75.8 mg/km on 20%
ethanol. The second car was a 1974 Chevelle operated on pure methanol. The
aldehyde emissions were 181.5 mg/km at one spark carburetor setting and
121.8 mg/km at another. The car was not tested on gasoline.
Other data on GM aldehyde work was found in a Feb. 1, 1978 letter from T. M.
Fisher (GM) to Dr. James N. Pitts (University of California). These data,
according to GM, show that aldehydes are reduced in automotive exhaust by
catalysts even under adverse oxidation conditions and after the normal
decrease in hydrocarbon oxidation efficiency has occurred with mileage. The
results of GM tests conducted on four high mileage vehicles equipped with
oxidation catalysts are shown in Table 2. Also shown as part of Table 2 is
a comparison of the range of the aldehyde emissions for
non-catalyst-equipped vehicles, low and high mileage catalyst-equipped
vehicles and Diesel-equipped vehicles. Aldehyde emissions from
non-catalyst-equipped vehicles averaged 87 mg/km in comparison to 12.4 mg/km
for low mileage catalyst-equipped vehicles, 18.05 mg/km for high mileage
catalyst-equipped vehicles and 24.85 mg/km for Diesel-equipped vehicles (all
tested by GM). Table 2 also includes exhaust aldehyde emissions of special
cars (11). GM concludes that the catalyst is generally more effective in
controlling aldehyde emissions than it is for total hydrocarbons.
Ford focused its attention on evaluation of aldehyde measurement pro-
cedures. A revised MBTH method was evaluated for the determination of low
concentrations of total aliphatic aldehydes in exhaust. The revised pro-
cedure is not subject to interferences encountered in earlier MBTH methods.
Ford has experimented with the DNPH method for determination of total alde-
hydes and developed an oxime technique for determination of airborne alde-
hydes. In addition, a gas analysis system composed of a Fourier Transform
Infra-Red (FTIB.) spectrometer, a quadrupole mass spectrometer and a total
hydrocarbon analyzer has been developed. Both regulated and unregulated
emissions, including individual aldehydes, can be measured with this gas
analysis system.
Ford has measured ethanol and total aliphatic aldehyde emissions from a 100%
ethanol fueled Corcel II vehicle. Samples were taken from undiluted raw
exhaust and exhaust diluted in the constant volume sampling (CVS) test.
Runs were conducted with and without a copper alumina oxidation catalyst.
Over the duration of the CVS test, aldehyde emissions were about 25% higher
with the catalyst than without it. Similar results were found for the
undiluted raw exhaust; the average aldehyde emission increase was less than
8% with the catalyst. It is possible that the unhurried ethanol in the
exhaust was only partially oxidized by the catalyst, resulting in increased
aldehyde emissions.
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Leyland used the MBTH method to report total aldehyde emission rates for
three Triumphs. They were 6.8 mg/km (over hot LA-4) for a 1977 Triumph
TA7-2V (Federal emission standards), 4.8 mg/km (over cold LA-4) for a 1977
Triumph TA7-2V (California emission standard) and 4.0 mg/km (over hot LA-4)
for a 1978 Triumph Spitfire 1500 (Federal emission standards).
Honda reported total aldehyde emissions for a CVCC engine (19.6 mg/km) and a
conventional engine (30.2 mg/km) at 25 MFH steady state using the DNPH
method. Honda is also conducting studies using a high performance liquid
chromatograph for measurement of individual aldehydes.
Toyo Kogyo (Mazda) measured aldehyde emissions from a 1978 Mazda RX-3
equipped with a thermal reactor and a 1978 GLC equipped with an oxidation
catalyst. The tests used were FTP, 0-2 min (choke was pulled out fully when
starting, pushed in to a half setting in 5 seconds and pushed in fully in
another 2 minutes), 2-10 min (after cold starting) and idle (after suf-
ficient idling). The test results indicated lover emission rates for the
1978 GLC with an oxidation catalyst regardless of the test used.
In a later study, Toyo Kogyo measured aldehyde emissions from four gasoline
vehicles equipped with catalysts. The maximum emission rates found for five
individual aldehydes were compared to an exposure level and an evaluation
standard determined for each individual aldehyde. The exposure levels for
each aldehyde were the 24-hour exposure levels on a highway assuming that
all vehicles emit the maximum emission rates of each aldehyde. The
evaluation-standard exposure levels at roadside locations of a city were set
at one-hundredth of the ACGIH-TLV* for each aldehyde, in consideration of
infirm persons, children, etc. and also because people are exposed to the
pollutants- for a long time. The exposure levels of the aldehydes were
greatly lower than the evaluation-standard levels in spite of the severe
conditions assumed.
VW presented total aldehyde data for eight gasoline VW vehicles, five
equipped with catalysts. The MBTH method was used. These data, shown in
Table 3,. generally indicate a substantial decrease in aldehyde emissions of
catalyst-equipped vehicles over the non-catalyst-equipped vehicles. VW also
measured total aldehyde emissions from a naturally aspirated 50 hp, a turbo-
charged 70 hp and a naturally aspirated 66 hp Diesel. The aldehyde emission
levels for the Diesel and gasoline vehicles were comparable.
Nissan is presently using the MBTH method but plans to use the DNPH method
in the future. Nissan has measured aldehyde emissions from both gasoline
and Diesel-equipped vehicles. A synopsis of this research follows.
Diesel testing was conducted to determine the effect the presence or absence
of EGR had on unregulated emissions. When NOx levels are lowered using EGR,
the emission levels of aldehydes rise markedly, according to Nissan. When
*American Conference of Governmental Industrial Hygienists-Threshold Limit
Value
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emissions from gasoline and Diesel-equipped vehicles were compared, Nissan
found that aldehyde emissions from Diesel-equipped vehicles are the same as
aldehyde emissions from gasoline vehicles without catalytic converters but
are a factor of 10 greater than gasoline vehicles equipped with catalytic
converters.
Nissan has examined the effect of mileage accumulation on unregulated
emissions using vehicles equipped with catalysts which had been put through
an AMA 50,000 mile durability run. Components such as aldehydes and hydro-
carbons that are originally present in the exhaust and are reduced by the
catalyst show a tendency to increase after the mileage accumulation.
Methanol (15 vol. %) was blended into the gasoline to investigate the effect
of an alternate fuel on aldehyde emissions. With the methanol blend, the
aldehyde emissions increase from two to five times in comparison with
gasoline. In an AMA 30,000 mile durability test using this blend, there was
no particular change in the aldehyde emissions.
Nissan has also investigated how various malfunctions (air-fuel ratio,
secondary air induction system and EGR) would affect the unregulated
emissions from a vehicle equipped with an oxidation catalyst. When the
air-fuel ratio is on the rich side, aldehydes decrease since they are the
product of an oxidizing atmosphere. When the air-fuel ratio deviates on the
lean side, the aldehydes do not show any significant change. A secondary
air induction system (EAI) malfunction results in a reducing atmosphere;
consequently, aldehyde emissions decrease. The aldehydes did not appear to
be affected by an EGR system malfunction.
In general, emissions of aldehydes have been shown to decrease when a
catalyst is used for emission control. Control of HC and CO emissions
brings about a corresponding reduction in aldehyde emissions for most
emission control systems.
B. Light-Duty Vehicle Aldehyde Emissions
1. Light-Duty Gasoline
The aldehyde emission factors for a few light-duty catalyst-equipped and
non-catalyst-equipped gasoline vehicles are shown in Tables 4 and 5, respec-
tively. Data for the catalyst-equipped vehicles come from work performed by
Southwest Research Institute under four contracts to the Environmental
Protection Agency (12, 13, 14, 15). Data for the non-catalyst-equipped
vehicles were taken from two EPA sponsored contracts (6, 16).
The aldehyde emissions for all light-duty vehicles were measured by the DNPH
method. Values for crotonaldehyde and benzaldehyde are not included in the
tables due to the aforementioned interferences with the DNPH procedure. The
light-duty Federal Test Procedure (FTP) was used.
For the catalyst-equipped vehicles, total aldehyde values ranged from 0.375
rag/km (1978 Saab 99) to 6.80 mg/km (1977 Olds Cutlass) with an average
emission factor of 2.36 mg/km. The average formaldehyde emission factor is
1.26 mg/km. On a mass basis, total aldehyde emissions are roughly 1.3
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percent of the total hydrocarbon (THC) emissions for the catalyst-equipped
vehicles. These averages have been computed using vehicles equipped with
oxidation catalysts, three-way catalysts and three-way plus oxidation
catalysts. The three-way catalysts appear to be the most effective for
controlling formaldehyde and total aldehyde emissions. The addition of an
oxidation catalyst to a three-way catalyst system, however, results in
increased formaldehyde and total aldehyde emissions, approaching levels
characteristic of operation with an oxidation catalyst alone. Average
emission factors are presented in Table 4 computed with and without the
inclusion of three-way and three-way plus oxidation catalyst-equipped
vehicles. The average emission factors for the aldehydes and THC decrease
when the three-way and three-way plus oxidation catalyst-equipped vehicles
are included. It should be noted when reviewing these data that the
catalyst-equipped vehicles used for this analysis were low mileage vehicles
tuned to manufacturers' specifications.
Table 5 presents data for the non-catalyst-equipped vehicles. As seen in
Table 5, individual aldehyde data are not available for 10 of the vehicles.
These vehicles were part of a program designed to characterize aldehyde and
reactive organic emissions from 1970 through 1973 model vehicles. Odometer
readings varied froom 2288 to 68,779 miles. Unfortunately, since the
aldehyde distribution in the exhaust of these vehicles is unknown, it is not
possible to determine if some of the unusually high values for total
aldehydes (e.g. 205 mg/km for the 1970 Pontiac) are due to interferences
with the sampling procedure. Individual aldehyde data are available for
four 1970 vehicles. These vehicles are part of a recent effort to determine
unregulated exhaust emissions from non-catalyst baseline vehicles. The
vehicles were 10 years old upon receipt and were tuned to manufacturers'
specifications prior to testing.
The total aldehyde average emission factor for the non-catalyst-equipped
vehicles was 88 mg/km, much higher than the catalyst-equipped vehicles but
not unexpected. The formaldehyde average emission factor was 32.31 mg/km,
over 20 times that of the catalyst-equipped vehicles. (This figure is based
on four vehicles.) On a mass basis, total aldehyde emissions are roughly
4.2 percent of the THC emissions for the non-catalyst-equipped vehicles.
2. Light-Duty Diesel
The aldehyde emission factors for some light-duty Diesel-equipped vehicles
can be found in Table 6. The data in Table 6 were generated in two EPA
sponsored studies (12, 17). Total aldehyde emission values ranged from 8.75
mg/km (1975 Mercedes 240D) to 76.50 mg/km (1976 Cutlass Diesel) with an
average of 36.70 mg/km. The average formaldehyde emission rate for the
light-duty Diesels is 13.07 mg/km, falling between the values given for the
catalyst-equipped vehicles (1.26 mg/km) and the non-catalyst-equipped
vehicles (32.31 mg/km). Total aldehyde emissions are roughly 11.5 percent
of the THC emissions.
3. Summary - Light-Duty Vehicles
The light-duty gasoline catalyst-equipped vehicles had the lowest average
formaldehyde and total aldehyde emission rates. These values may be
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11
especially low due to the inclusion of three-way catalyst-equipped vehicles.
Cars equipped with dual or three-way catalyst systems have lower aldehyde
emissions (see Tables 2 and 4). The non-catalyst-equipped gasoline vehicles
produced the highest average formaldehyde, and total aldehyde emission
rates; however, the light-duty Diesel-equipped vehicles produced the largest
percentage of aldehydes in the total hydrocarbon exhaust. It is evident
that aldehyde emissions could constitute an appreciable fraction of the
photochemical oxidant potential of Diesel exhaust.
C. Heavy-Duty Engine Aldehyde Emissions
Aldehyde emission factors for three heavy-duty engines are listed in Table
7. The data reported here come from work performed by Southwest Research
Institute under contract to EPA (12). The DNFH method was used to measure
the heavy-duty engine aldehyde emissions. The 13-mode FTP (steady state)
test procedure was selected. Two Diesel heavy-duty engines were tested, a
Mack ETAY(B)673A and a Caterpillar 3208/EGR. The Chevrolet 366 engine was
chosen to represent the gasoline heavy-duty engine. Both the Mack and the
Caterpillar used No. 2 Diesel fuel, representative of "national average"
properties. The Chevrolet engine used leaded gasoline. The aldehyde
emissions are listed in units of g/kw-hr, g/kg fuel and g/km. The work
specific rates (g/kw-hr) and fuel specific emission, rates (g/kg fuel) were
taken from the EPA contract project (12). The emission factors (g/km) were
derived using the fuel specific emission rates and information taken from
the article "Heavy-Duty Diesel Particulate Emission Factors" (18). The
emission factors derived are crude approximations and are included as a
means of comparison with other vehicle types. The conditions used in
formulating these emission factors included half load and combined
city-highway driving. The emission factors used were the average of the New
York City and Los Angeles derived emission factors. These conditions
represent an estimate of the general population1s exposure to aldehyde
emissions from heavy-duty vehicles.
On a brake specific basis, the Chevrolet 366 gasoline engine emitted more
aldehydes overall. Formaldehyde emissions were substantially higher.
Crotonaldehyde and benzaldehyde emissions given in the original report were
extremely high and are probably the result of artifacts in the sampling pro-
cedure; therefore,they were not included in Table 7. Total aldehyde
emissions are roughly 5.9 percent of the THC emissions for the gasoline
engine versus roughly 7.8 percent for the Diesel-equipped heavy-duty
engines.
An overall summary of the aldehyde and hydrocarbon emissions for the
light-duty vehicles and heavy-duty engines can be found in Table 3. It
should be noted that the vehicles/engines used for this analysis were all
tuned to manufacturer specifications.
D. Malfunction Configuration Studies - LD Gasoline Vehicles
Three malfunction configuration studies will be summarized here (13, 14,
15). A total of nine gasoline vehicles were tested in the unmodified con-
figuration and in four engine and/or emission control system malfunction
configurations; the results for six of the vehicles will be reported here.
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The DNPH method and four cycle FTP testing procedures were used in each
study. The specific malfunction configurations varied somewhat from vehicle
to vehicle. One vehicle tested, a 1977 AMC Pacer, had no catalyst. Of the
remaining five catalyst vehicles, one had an oxidation catalyst, two had
three-way catalysts and two had three-way plus oxidation catalysts. The
results are listed in Tables 9 and 10. The non-catalyst AMC Pacer produced
the highest levels of formaldehyde and aldehydes in both the unmodified and
malfunction configurations. The highest levels occurred at the 12 percent
misfire condition (12 percent misfire was estimated to be the limit at which
driveability remained reasonably acceptable to some people). Similar
results have been obtained in a study using four 1970 non-catalyst-equipped
vehicles (16). The Chevrolet Malibu behaved similarly with the highest
levels of formaldehyde and total aldehydes occurring during the 12 percent
misfire condition. The high oil consumption condition increased
formaldehyde and total aldehyde levels for the non-catalyst-equipped
vehicles but exhibited an inverse effect for the catalyst-equipped
vehicles. The disabled EGR condition increased aldehyde emissions for both
the catalyst-equipped and non-catalyst-equipped vehicles. The rich best
idle increased the aldehyde emissions slightly for both vehicles tested.
The 1978 Saab 99 had the lowest unmodified aldehyde emissions of all the
vehicles tested. Highest. values for the Saab 99 occurred during the
disabled 02 sensor and rich best idle configurations. In general, the
catalyst-equipped vehicles appear to be more effective in controlling THC,
formaldehyde and total aldehyde emissions than non-catalyst-equipped
vehicles, even under malfunction conditions.
The results listed in Tables 9 and 10 are average values. The unmodified
values were obtained by averaging four runs while the malfunction
configuration values were obtained by averaging two runs. The emission
rates varied quite substantially in some cases from run to run. By
averaging the runs the variability was reduced but the maximum values were
lost.
E. Effects of Fuel Composition on Aldehydes
EPA has run several programs with various types of Diesel fuels. These data
give an indication of how Diesel fuel composition affects aldehyde emissions.
The aldehyde emission factors for two light-duty and two heavy-duty Diesel
equipped engines operated on five different fuels can be found in Table 11.
The test fuel descriptions are as follows:
EM-238-F: 2D Emissions - "wide boiling range" fuel
EM-239-F: National Average No. 2
EM-240-F: "Jet A" No. 1
EM-241-F: Minimum Quality No. 2 - a low-cetane (e.g. 42)
high-aromatic Diesel fuel
EM-242-F: Premium No. 2 - a high-cetane (e.g. 52) high
paraffin Diesel fuel
-------
13
The two light-duty Diesel-equipped vehicles tested were a Mercedes 240D and
a VW Rabbit Diesel (19). The two heavy-duty Diesel-equipped engines tested
were a Detroit Diesel Allison 6V-71 and a Caterpillar 3208 (20).
The VW Rabbit Diesel produced somewhat higher total aldehydes than the
Mercedes 240D. Few trends seem to be evident regarding fuel effects. In
both cases, however, the highest formaldehyde and total aldehyde values
occurred when the Minimum Quality No. 2 fuel was used. Maximum and minimum
total aldehyde emissions for the VW Rabbit differed by a factor of 2; for
the Mercedes 240D by a factor of 4. THC emissions behaved similarly for
both vehicles.
More variability is apparent in the heavy-duty 6V-71 data than in the 3208
data. The variability, according to the study, may be due to lubricating
oil in the exhaust that created an interference with the analysis.
F. Temperature Study
It is known that emissions vary with ambient temperature. EPA has conducted
some emission studies at various ambient temperatures. The composite
aldehyde results of an ambient temperature study are shown in Table 12
(21). Fourteen vehicles were tested; three non-catalyst, three 49 state
approved, five California approved and three prototype vehicles. Odometer
readings ranged from 2774 miles (1978 Buick Regal) to 65,212 miles (1972
Chevrolet Impala). A modification of the DNPH method with colorimetric
detection was used for determination of total aldehydes.
The 1974 Chevrolet Impala and 1977 Honda Civic, non-catalyst-equipped cars,
showed the greatest aldehyde emissions. Air conditioning generally showed
greater aldehyde emissions at 80 and 110°F (27 and 43°C) but less at
90°F (32°C). The total range for the values varied from 19 mg/km in the
1980 Buick prototype (soaked and tested at 80°F with air conditioning) to
285 mg/km in the Honda (soaked and tested at 20°F).
G. Prototype LD Diesel Catalyst Study
A preliminary investigation of prototype light-duty Diesel oxidation
catalysts was performed (22). A 1979 Oldsmobile Diesel Delta 88 was used to
evaluate emissions from prototype Diesel catalytic converters supplied by
two manufacturers, Engelhard and UOP, Inc. The vehicle's exhaust system was
modified twice* in order to accomodate each of the manufacturer's systems.
The vehicle was tested with and without a converter. A total of three
catalytic converters were evaluated, two fresh and one aged. The Engelhard
converter was a fresh monolithic oxidation catalyst and identified as
PTX-516. There were two UOP monolithic oxidation catalysts identified as
UOP-99 and UOP-103. Both were identical with the exception that UOP-99 was
subjected to 81,000 km (50,342 miles) of road aging on a similar vehicle
before delivery to the test site. The aldehydes were measured using the
DNPH method. The Federal Test Procedure (FTP) results are shown in Table 13.
The reduction of the total amount of aldehydes for the Englehard catalyst
was approximately 55 percent. Formaldehyde reduction was no greater than
-------
14
the other aldehydes. Total hydrocarbons were reduced by approximately 60
percent.
The aldehyde and formaldehyde emissions for both UOP fresh and aged
catalysts did not change appreciably from the non-catalyst baseline.
However, the fresh catalyst exhibited substantially greater activity for
reducing total hydrocarbons than its aged counterpart. The fresh UOP
catalyst (UOP-103) reduced total hydrocarbons by approximately 50 percent.
The aged UOP catalyst (UOP-99) reduced hydrocarbons approximately 30
percent.
H. Mileage Accumulation Study
A study was undertaken to characterize regulated and unregulated exhaust
emissions at various mileages from three-way catalyst-equipped gasoline
automobiles (23). In this study, four new three-way, catalyst-equipped
automobiles were tuned to the manufacturer's specifications, and the
emissions were evaluated over four test cycles with three unleaded gasolines
initially and at three mileage accumulation points (5000 mile increments).
The three fuels were: fuel 1, a low sulfur content fuel (less than 0.003
weight percent sulfur); fuel 2, fuel 1 blended to 0.03 weight percent
sulfur, and fuel 3, a commercial grade fuel blended to 0.03 weight percent
sulfur. A total of eight aldehydes and ketones were measured; however, the
emission rate of two of the aldehydes, crotonaldehyde and benzaldehyde,
could not be measured accurately due to interferences in the analysis
procedure. Two other aldehydes and ketones, acetone and methylethylketone
were found in only a small fraction of the samples analyzed. The FTP
average emission rates for the remaining four aldehydes, formaldehyde,
acetaldehyde, isobutyraldehyde and hexanaldehyde at each 5000 mile
accumulation point are listed in Table 14. Each value in the table
represents an average of 6 tests (2 duplications x 3 fuels).
While some of the vehicles do not show a continuous increase in aldehyde
emissions with mileage, they all show an increase in individual and total
aldehyde emissions from the initial to the final mileage test point. It is
interesting to note that, of the vehicles tested, the Mercury Marquis had
the highest aldehyde emissions; yet these aldehyde emissions were the least
affected by mileage. Total aldehyde emissions for the Mercury Marquis, from
the initial to the final test point, increased by roughly a factor of 2 as
compared to a factor of 30 for the Ford Pinto. In general, THC emissions
also increased with mileage but not to the same extent. In all cases, there
was less than a two fold increase in THC emissions. The results are shown
graphically in Figure 1.
These results give an indication of how aldehyde emissions vary during the
first 15,000 miles. An important issue that remains is how the aldehyde
emissions behave after extended mileage (i.e. 50,000 + miles). Does the
trend apparent during the first 15,000 miles continue over the life of the
vehicle with aldehyde emissions continually increasing with mileage? In an
attempt to determine this, the data in Table 14 were extrapolated to higher
mileages (50,000, 72,866 and 100,000 miles). This was done by performing a
linear regression with each vehicle using the three 5000 mile accumulation
points. Since certification data are collected at 4000 miles, the initial
-------
15
point was not used. The linear regression parameters and extrapolated high
mileage emissions can be found in Table 15. Deterioration factors were also
determined with the available data and with each extrapolated high mileage
point. The deterioration factors can be found in Table 16. The
deterioration factors can be used with low mileage aldehyde data to project
aldehyde emissions at high mileages. These projected emissions can then be
compared to actual high mileage aldehyde emissions. Available high mileage
aldehyde data are limited to that generated by GM. These data are presented
in Table 2. The high mileage vehicles used by GM were equipped with
oxidation catalysts; the average odometer reading was 72,866 miles. Using
Table 4, the average total aldehyde emissions from low mileage vehicles
equipped with oxidation catalysts are 3.26 mg/km. This number, multiplied
by the deterioration factor calculated for 72,866 miles will give the
projected aldehyde emissions at 72,866 miles. This can then be compared to
the actual aldehyde emissions found by GM. The projected value is 39 mg/km,
compared to the actual maximum value of 25 mg/km found by GM; however, GM
used the MBTH method to generate their data. GM estimates that the MBTH
aldehyde values for auto exhaust range from 10 to 50% low and average about
25Z low (11). Taking this into consideration and adjusting the actual
maximum value by 25% gives 31 mg/km, still lower than the projected value.
If the average low mileage value generated by GM (12.4 mg/km) is multiplied
by the same deterioration factor, the projected high mileage value then
becomes 148 mg/km, much higher than the actual high mileage factor of 25
mg/km. Using the three-way catalyst-equipped vehicle data in Table 15, the
average extrapolated aldehyde levels at 50,000 and 100,000 miles are 18.32
and 36.20 mg/km, respectively. These levels far exceed those found for low
mileage three-way catalyst-equipped vehicles under malfunction conditions.
It appears that aldehyde emissions from catalyst-equipped vehicles do not
increase at a constant rate with increasing mileage; it is not certain with
the available data whether the aldehyde emissions, 1) level off at some
point, or 2) continue to increase with mileage but at a slower rate than
indicated by the study. In either case, the projected high mileage aldehyde
emissions from 'catalyst-equipped vehicles are generally less than aldehyde
emissions found from non-catalyst-equipped vehicles.
The same type of analysis can be performed with THC emissions. Average THC
emissions for the GM high mileage vehicles are 396 mg/km. From Table 4, the
average THC emissions from low mileage vehicles equipped with oxidation
catalysts are 255 mg/km. The projected THC emissions at 72,866 miles are
663 mg/km, much higher than the actual THC emissions of 396 mg/km at that
mileage. These results are similar to those found for the aldehydes. It
should be noted that an EPA sponsored study is presently underway to
investigate aldehyde emissions from high mileage catalyst-equipped vehicles.
-------
16
References
1. J.A. Swenberg, W.D. Kerns, R.I. Mitchell, E.J, Gralla, and K.L. Pavkov,
"Induction of Squamous Cell Carcinomas of the Rat Nasal Cavity by
Inhalation Exposure to Formaldehyde Vapor", Cancer Res. 40, 3398-3402
(1980). ~
2. "Formaldehyde - An Assessment of Its Health Effects", prepared for the
Consumer Product Safety Commission by the Committee on Toxicology of the
National Academy of Sciences, March 1980.
3. "Report of the Federal Panel on Formaldehyde", prepared for the Consumer
Product Safety Commission by a Federal Panel under the auspices of the
National Toxicology Program, November 1980.
4. E. Sawicki, T.R. Uauser, T.W. Stanley and W. Elbert, "The 3-Methyl
2-Benzothiazolone Hydrazone Test", Anal. Chem., 33, 93 (1961).
5. H.E. Dietzmann, et al., "Analytical Procedures for Characterizing Un-
regulated Pollutant Emissions from Motor Vehicles", EPA Report
600/2-79-017, February 1979.
6. "Aldehyde and Reactive Organic Emissions From Motor Vehicles, Part II,
Characterization of Emissions from 1970 through 1973 Model Vehicles,
Final Report", prepared for EPA by the U.S. Bureau of Mines,
Bartlesville Energy Research Center, Publication No. APTD-1586, March
1973.
7. G.J. Nebel, (General Motors Research Laboratories), "A Modified MBTH
Method for the Determination of Total Aliphatic Aldehydes in Gasoline
and Diesel Exhaust", presented at the Chemical Characterization of
Diesel Exhaust Emissions Workshop organized by CRC CAPI-1-64 Panel,
Hyatt Regency, Dearborn, Michigan, March 2-4, 1981.
8. T. Tanaka, et al., (Toyota Motor Industry Co., Ltd.), "Measurement of
Aldehydes in Automotive Exhaust Using a High Performance Liquid
Chromatograph", presented at the Chemical Characterization of Diesel
Exhaust Emissions Workshop organized by CRC CAPI-1-64 Panel, Hyatt
Regency, Dearborn, Michigan, March 2-4, 1981.
9. F. Lipari and S.J. Swarin, (General Motors Research Laboratories)
"Determination of Formaldehyde and Other Carbonyl Compounds by High
Performance Liquid Chromatography", presented at the Chemical Char-
acterization of Diesel Exhaust Emissions Workshop organized by CRC
CAPI-1-64 Panel, Hyatt Regency, Dearborn, Michigan, March 2-4, 1981.
10. Data were taken from the 1977 and 1981 manufacturers status reports.
Data for the following manufacturers were taken from the 1977 status
reports: GM, Leyland, Honda, Toyo Kogyo and VW. Data for the following
manufacturers were taken from the 1981 status reports: GM, Ford, Honda,
Toyo Kogyo and Nissan.
-------
17
11. S.H. Cadle, G.J. Nebel, and R.L. Williams, "Measurements of Unregulated
Emissions from General Motors' Light-Duty Vehicles", SAE Paper 790694,
June 1979.
12. K.J. Springer, "Characterization of Sulfates, Odor, Smoke, POM and
Particulates From Light and Heavy Duty Engines-Part IX",
EPA-460/3-79-007, June 1979.
13. C. Urban, "Regulated and Unregulated Exhaust Emissions from Mal-
functioning Non-Catalyst and Oxidation Catalyst Gasoline Automobiles",
EPA-460/3-80-003, January 1980.
14. C. Urban, "Regulated and Unregulated Exhaust Emissions from Mal-
functioning Three-Way Catalyst Gasoline Automobiles", EPA-460/3-80-004,
January 1980.
15. C. Urban, "Regulated and Unregulated Exhaust Emissions from a Mal-
functioning Three-Way Catalyst Gasoline Automobile", EPA-460/3-80-005,
January 1980.
16. C. Urban, "Unregulated Exhaust Emissions from Non-Catalyst Baseline Cars
Under Malfunction Conditions", EPA Contract No. 68-03-2884, 1981.
17. K.J. Springer, "Investigation of Diesel-Powered Vehicle Emissions-Part
VII", EPA-460/3-76-034, February 1977.
18. T.M. Baines, J.H. Somers, and C.A. Harvey, "Heavy-Duty Diesel Par-
ticulate Emission Factors", Journal of the Air Pollution Control Assoc-
iation, Vol. 29, No. 6, June 1979.
19. C.T. Hare, "Characterization of Gaseous and Particulate Emissions from
Light-Duty Diesels Operated on Various Fuels", EPA-460/3-79-008, July
1979.
20. C.T. Hare, "Characterization of Diesel Gaseous and Particulate
Emissions", EPA Contract No. 68-02-1777, 1977.
21. R.S. Spindt, et al., "Effect of Ambient Temperature on Vehicle Emissions
and Performance Factors", EPA-460/3-79-006A, September 1979.
22. B.B. Bykowski, "Preliminary Investigation of Light-Duty Diesel
Catalysts", EPA-460/3-80-002, January 1980.
23. L.R. Smith and F.M. Black, "Characterization of Exhaust Emissions from
Passenger Cars Equipped with Three-Way Catalyst Control Systems", SAE
Paper 800822 presented at the Passenger Car Meeting, Hyatt Regency,
Dearborn, June 9-13, 1980.
-------
18
Appendix
The following is a summary of the DNPH procedure used to collect and measure
mobile source emissions of aldehydes and ketones. A more complete
description can be found in the EPA report, "Analytical Procedures for
Characterizing Unregulated Pollutant Emissions From Motor Vehicles" by Harry
E. Dietzmann, et al. (5).
The collection of aldehydes (formaldehyde, acetaldehyde, isobutyraldehyde
and hexanaldehyde) and ketones (acetone and methylethylketone) is
accomplished by bubbling CVS diluted exhaust through glass impingers
containing 2, 4-dinitrophenylhydrazine (DNPH) in dilute hydrochloric acid.
The aldehydes and ketones (also known as carbonyl compounds) react with the
DNPH to form their respective phenylhydrazone derivatives. These
derivatives are insoluble or only slightly soluble in the DNPH/HC1 solution
and are removed by filtration followed by pentane extractions. The filtered
precipitate and the pentane extracts are combined and then the pentane is
evaporated in a vacuum oven. The remaining dried extract contains the
phenylhydrazone derivatives. The extract is dissolved in a quantitative
volume of toluene containing a known amount of anthracene as an internal
standard. A portion of this dissolved extract is injected into a gas
chromatograph and analyzed using a flame ionization detector. Acetone,
acrolein and propionaldehyde are not resolved from each other under normal
gas chromatographic operating conditions and all three are reported together
as acetone.
-------
-w
FIGURE 1
EFFECTS OF MILEAGE ACCUMULATION
TOTAL
ALDEHYDE 4
EMISSIONS
OUJ/Km
me FORD PINTO •
inSPONTIACSlMBlRD A
me SAAB ^ o
MERCURV MARQUIS i
1
INITIAL
5000 MILE
ACCUM
10000 MILE
ACCUM
15000 MIUE.
ACtUM
MILEAGE
-------
20
ALDEHYDE
TABLE I
CHEMICAL STRUCTURES OF THE ALDEHYDES
STRUCTURE
FORMALDEHYDE
H - C - 0
ACETALDEHYDE
9
CH3C
0
ACROLEIN
CH2-CH- C - 0
PROPIONALDEHYDE
ISOBUTYRALDEHYDE
H H
CH3-C - C - 0
CH3
CROTONALDEHYDE
CH3 —
f
CH » CH-C » 0
HEXANALDEHYDB
CH3 -
H
-C-0
BENZALDEHYDE
-------
21
Vehicle*
No.
14
15
17
18
Odometer
71,319
74,629
76,099
69,417
TABLE 2
GM MILEAGE DATA
FTP HC Emissions
mg/km
360
547
273
404
Aldehyde Emissions
(3 tests)
mg/km Range
14.3 11.2 - 15.5
23.6 21.1 - 26.7
9.3 7.5 - 11.8
24.9 21.1 - 28.6
*1973 Oldsmobiles equipped with 1975 emission control systems
Type of Vehicle
Non-Catalyst
Low-Mileage w/catalyst
High-Mileage w/catalyst
(69,417-76,099 miles)
Diesel
Mileage Effects
Model Year Range of Aldehyde Emissions
mg/km
1970-1974 49.7 - 124.3
1975 6.2 - 18.6
1975* 7.5 - 28.6
12.4 - 37.3
*1975 emission control systems on 1973 Oldsmobile
Exhaust Aldehyde Emissions of Special Cars
Category '
No. of cars
Aldehyde min
max
avg.
Total Aldehydes - mg/km*
Oxidation
Catalyst
110,000km
4
9.3
24.9
18.02
Dual and
3 -way
Catalysts
5
3.1
4.4
3.1
Stratified-
Charge
Engine
5
23.0
74.0
55.9
Diesel
Engine
5
13.7
37.3
21.13
Rotary
Engine**
2
59.04
315.10
187.07
*Driving cycle 1975 FTP
**Also equipped with thermal reactor
-------
22
Vehicle
1972 Beetle
1975 Beetle
1975 Dasher
1975 Dasher
1975 Beetle
1975 Scirocco
1976 Beetle
1976 Rabbit
Table 3
VW Aldehyde Data
Catalyst Secondary Air
No No
No Yes
No Yes
Yes Yes
Yes No
Yes Yes
Yes No
Yes Yes
Average Aldehyde Emission Factor
Catalyst: 7.33 ing/km
Non-Catalyst: 45.16 mg/km
Total Aldehydes
mg/km
-------
TABLE 4
FTP ALDEHYDE EMISSIONS (rag/km)
LIGHT DUTY CATALYST-EQUIPPED GASOLINE VEHICLES
FORM- ACET-
ALDEIIYDE ALDEHYDE
1 77 Olds Cutlaasb
'77 VVJ Rabbi lb
'78 Ciniv. Malibuc
1 78 Kuril Crmiaila0
' 7tt turd Hii3tangllc
1 78 Ford Pinto11
3-u.iy » OX Catalyst
1 7rt Font. biinbirdj
J-way Catalyst
1 7d Saab 9T1
J-way Cit.'ily.st
1 79 Mure. Maryijs0
3-way + OX Catalyst
Emission Factor
K.-III,;U 0
Avi-r:i|',i! Emission
Ka, lor w/p 3-way
A vi -i. !,•,<• Kini ii!ii|H)
Factor with J-way
2.60
0.40
i.io
2. 01
1.58
0.79
0.35
0.085
2;41
.Utti-2.60
1.54
1.26
0.40
0.305
0.14
0.63
0.00
O.Q6
0.29
0.11
•
0.00-U.63 0.
0.37
0.24
ACETONE*
~_—
0.05
0.05
0.15
0.035
0.03
0.00
0,01
00-0.15 0.
o.oa
0.05
ISOBUTYH-
AtDEHYDE
3.80
2.60
0.00
0.00
0.03
0.00
0.00
0.00
p. 08
00-3.80
1.29
P. 72
CBOTON- HEXAN-
ALDBHYDE ALDEHYDE
___ _ —
0.11
0.15
0.18
0.09
0.11
0.00
0.00
0.00-0.18
0.15
0.09
BENZ- TOTAL
ALDEHYDE ALDEHYDES
— * 6.80
3.00
1.565
2.35
2.57
0.915
0.55
0.375
2.61
0.375-6.80 67.5-307
3.26
2.36
TOTAL AS
THC Z
240
140
307.5
265
323
67.5
155.0
100.0
127.5
.5 0.35-2.
255
192
OF THC
2.8
2.1
0.5
0.9
0.8
1.4
0.35
0.30
2.0
8
1.3
1.2
_ tlo Vnliil Oijta Av
°. iiic lii'I'.'S ucroliMii a i iU propanal.
b Data (rum "CliarncttM" izat i on ol Sull.itcs, Odor, Smoke, POM and Parttculatec fro* Light and Heavy Duty Engines-Part IX,"
9-007 , June 1979, pg. 196.
N>
CJ
cl)ata fruni "lu-t;u I al.>>! an. I llnri',;.i I atc-d Kxbaust Emissions from Malfunctioning Nop-Catalyst and Oxidation Catalyst Gasoline Autojppbijes",
EI>A-4t.O/J-ao-OOJ, Janiuny 1980, Appendix C.
d U.i l a Irum "Ki-'^nl ;iti>d ami Unregulated txli^uat Eiqisaions from Malfunctioning Three-Uay Catalyst Gasoline Automobiles",
tl'A-460/3-HO-004, January 1980, Appendix C.
eData from "KcgnlatoJ and Unrcgulutcd Exhaust Emissions from a Malfunctioning Three-Way Catalyst Gssoline Automobile",
Et'A-460/3-80-005, Jnniiary 1980.
-------
TABLE 5
FTP ALDEHYDE EMISSIONS (ag/kn)
LIGHT-DUTY NON-CATALYST GASOLINE VEHICLES
VEHICLE FORM- ACET- ISOBUTYR- CROTON-
ALDEHYDE ALDEHYDE ACETONE* ALDEHYDE ALDEHYDE
1972b
Olds 98
X97QD
Volkswagen
1971b .
Ford Galaxie
Plymouth Furylll
Ford Torino
197Ub
Chev . Impala
Pontiac
197 lb
Chev. Vega
Ford Torino
1973b — r
Chev. Impala
1970 Oldsc 31.87 4.46 0.71
Delta 88
1970C 9.31 3.45 0.00 ,
Dodge Challenger
1970 Chevyc 66.77 6.74 0.00 — -
Monte Carlo
1970 Fordc 21.29 1.42 0.23
Fairlane
Emission 9.31-66.77 142-6.74 0.00-0.71
Factor Range
Average 32.31 4.02 0.24
Emission
Factor
HEXAN- BENZ- TOTAL
ALDEHYDE ALDEHYDE ALDEHYDES
111.9
59.7
105.7
111.9
62.1
93.2
205.1
74.6
111.9
149.2
0.00 37.04
0.00 12.76
0.00 73.51
0.00 22.94
. 12.76-205.1
0.00 87.97
THC
1069
1187
3456
2200
1423
2449
3679
3381
1666
1318
1430
1710
2050
2350
TOTAL AS
t OF THC
10.5
5.0
3.1
5.1.
4.4
3.8
5.6
2.2
6.7
11.3
2.6
0.7
3.6
1.0
1069-3679 0.7-10.5
2098
4.2
No Data Available
Includes acrolein and propanal
b Data from "Aldehyde and Reactive Organic Emissions from Motor Vehicles. Part II". APTD-1568b, March 1973.
c Da£Snfract"IJoreSB-85-^8fiihall|filEaii*8ion8 *r°a Non"c-t*lyat Baseline Car* Under Malfunction Conditions",
-------
TABLE 6
FTP ALDEHYDE EMISSIONS (nig/tun)
LIGHT-DUTY DIESEL VEHICLES
FORM- ' ACET-
1 ALDEHYDE ALDEHYDE ACETONEa
'74 Perkins^
6-247
'74 Peugotj,
204D
' 75 Mercedes},
2201) Cumprex
' 75 Mercedesi,
240D
1 75 Mercedes},
30UD
'76 Cutla88c
Dieael
'77 Rabbitc
Diesel
Emission factor
Range 2.
Average Emission
Factor
38.17
11.25
2.52
3.96
3.80
15.80
16.00
52-38.17
13.07
10.50
4.28
1.00
1.13
1.11
6.50
5.00
1.00-10.50
4.22
5.31
3.01
8.37
1.47
9.41
35.70
2.60
1.47-35.70
9.41
ISOBUTYB- CROTON- HEXAN-
ALDEHYDE ALDEHYDE ALDEHYDE
13.00
8.75
11.08
2.19
0.00
18.50
16.00
0.00-18.50
9.93
0.00
0.00
0.47
0.00
0.00
__• — — —
_«•. • !--•
_^_ 0.00-0.47
0.07
BENZ- TOTAL TOTAL AS
ALDEHYDE ALDEHYDES THC 1 OK TUG
66.98
0.00 27.29
0.00 23.44
0.00 8.75
14.32
76.50
39.60
8. 75-76". 50
36.70
450.
690.
110.
180.
100.
470.
230.
100-690 4
381.6
14.9
4.0
21.3 - .-. K
4.9
14.3
*16.3
17. Z
.0-21.3
11.5
No Valid Data Available
"Includes Acrolein and Propansl
bUuta from "Investigation of Diesel-Powered Vehicle Emissions VII". EPA-460 /3-76-034. Feb. 1977, Pg. 172.
cData from "Characterization of Sulfates, Odor, Smoke, POM, and Participates from Light and Heavy Duty Engines-Part IX",
EPA-460/3-79-007, June 1979.
-------
TABLE 7
ALDEHYDE EMISSIONS
HEAVY-DUTY VEHICLES* •>>
Chevrolet mg/kw-hr
Gasoline mg/kg fuel
mg/kme 92.
Avg. mg/km
Hack mg/kw-hr
ETAY(B)673A mg/kg fuel
Diesel oig/kme 31.
Avg. mg/km
Caterpillar mg/kw-hr
3208/EGR mg/kg fuel
Diesel rag/kme 104
Avg. mg/km
DIESEL AVG.
mg/kw-hr
DIESEL AVG.
mg/km
FORM-
ALDEHYDE
104.75
228.88
82-59.11
75.97
16.59
166.84
17-19.85
25.51
49.90
223.76
.35-66.46
85.41
33.25
55.46
ACET-
ALDEHYDE
18.09
39.53
16.03-10.21
13.12
0.94
3.78
1.76-1.12
1.44
21.85
97.98
45.69-29.10
37.40
11.40
19.42
ACETONE6
18.40
40.20
16.30-10.38
13.34
12.55
56.28
26.25-16.72
21.49
6.27
10.75
ISQBUTYB-
ALDEIIYDE
13.79
30.13
12.22-7.78
10.00
31.79
128.12
59.75-38.05
48.90
3.18
14.24
6.64-4.23
5.43
17.48
27.17
CROTON- HEXAN-
ALDEHYDE ALDEHYDE
42.83
93.58
37.95-24.17
31.06
20.18
83.87
39.11-24.91
— - 32.01
13.98
62.70
29.24-18.62
23.93
17.08
27.97
BENZ- TOTAL
ALDEHYDE ALDEHYDES THC
197.86 " 3340°
432.32
175.32-111.65
143.49
69.50 638
282.61
131.79-83.93
107.86
101.46 1559
454.96
212.17-135.13
173.66
85.48 1099
—- 140.77
TOTAL AS
I OF THC
5.9
10,9
6.5
7.8
N>
a\
New York City-Los Angeles
Usage Usage
No Valid Data Available
"Bused on Weighting Factors Derived form 13-Hode FTP.
bData from Characterisation of Sulfatea, Odor, Smoke, POM and Particulates From Light-«nd Heavy-Duty Engine* Part IX.
EPA-460/3-79-007, June 1979.
clncludea Acrolcin and Propanal
dBased on 23-Mode FTP
^Emission Factor Data Derived using T.M. Bainea, et «!., "Heavy-Duty Diesel Particulate Emission Factors",
Journal of the Air Pollution Control Association, Volume 29, No. 6; Juno 1979.
-------
27
TABLE 8
SUMMARY OF VEHICULAR ALDEHYDE AND HYDROCARBON EMISSIONS
HC
mg/km
LD Gasoline
Non-Catalyst 2098
LD Gasoline-
Catalsyt
including
3-way catalyst
vehicles 192
excluding
3-way catalyst
vehicles 255
LD Diesel 319
HD Diesela 1099
«M^
HD Gasoline* 3340
••^•^v
Aldehydes
mg/km
88
2
3
37
86
141
198
143
Form-
Aldehyde Ald/HCZ
mg/km
32b 4
1 2
2 2
13 12
33 8
55
105 6
76
No. of Cars
Engines Tested
14
9
5
7
2
2
1
1
amg/kw-hr
Abased on four vehicles
-------
Table 9
MALFUNCTION CONFIGURATION
ALDEHYDE EMISSIONS
AVERAGE EMISSION RATE, tag/km
•77 AMC
PACER
b
W/0
Catalyst
'78 Chev
Malibu
b
'78 Ford
Pinto
c
3-Way+OX
Catalyst
Formaldehyde
Acetaldehyde
Acetone0
Isobutyraldehyde.
Crotona Idchyde
Hexana Idehyde
Benzaldchyde
Total Aldehydes
TIIC
Total as Z of
THC
Formaldehyde
Acetaldehyde
Acetone*
Isobutyraldehyde
Crotena Idehyde
llexanaldehyde
Benzaldchyde
Total Aldehydes
TIIC
Total as I of
TIIC
Formaldehyde
Acetaldehyde
Acetone*
Isobutyraldhyde
Crotonaldehyde
Hexanaldehyde
Bcnziildehydti
Total Aldehydes
TIIC
Total an * of
TIIC
UNMODIFIED
FTP
9.71
2.345
0.765
0.00
0.19
— — T
13.01
725.0
1.8
1.10
0.305
0.05
0.00
0.11
1.57
307.5
0.51
0.79
0.00
0.035
0.00
— -
0.09
0.92
67.5
1.4
12 PERCENT
MISFIRE
75.24
31.04
10.00
0.00
1.915
118.20
10820.
1.1
2.29
2.115
0.295
0.00
0.10
4.8
1780
0.27
0.00
0.0
0.00
0.00
0.00
0.00
380
0.00
DISABLED
ECR
11.055
2.205
1.01
0.00
0.165
14.44
785.0
1.8
2.22
0.88
0.265
0.00
0.105
3.47
335
1.04
__—
— —
.
__ ._
RICH BEST
IDLE
12.62
2.23
0.075
0.00
0.08
15.01
805.0
1.9
1.305
0.405
0.00
0.03
0.04
1.78
1080
0.16
__..
—
___
HIGH OIL
CONSUMPTION
21.725
7.23
1.27
0.00
—
0.435
30.66
1115.
2.7
0.165
0.20
0.09
0.03
0.095
0.58
570
0.10
_ __
—
-»_-
___
DISABLED
02 SENSOR
___
0.00
•0.015
0.135
0.00
0.255
0.41
95
0.43
DISABLED
ECR AND 02
. .
_
0.475
0.00
0.00
0.00
0.00
U.4B
115
0.42
DISABLED 02 SENSOR
AND AIH PUMP
__~
0.315
0.615
0.00
0.09
0.00
l.u*
1160
0.09
No Valid Data Available not measured
•Includes Acrolein and Propanal
''Data from "Regulated and Unregulated Exhaust Emissions From Malfunctioning Non-Catalyst and Oxidation Catalyst Gasoline Automobiles",
EPA-460/3-80-003, January 1980. Appendix C.
cData from "Regulated and Unregulated Exhaust Emissions From Malfunctions Three-way Catalsyt Gasoline Automobiles",
EPA-460/3-80-004, January I960, Appendix C.
N)
CD
-------
TABLE 10
MALFUNCTION CONFIGURATION ALDEHYDE EMISSIONS
(CONT.)
AVERAGE EMISSIONS RATE, mg/km
UNMODIFIED
FTP
Formaldehyde 0.35
Acetaldehyde 0.06
'78 Pontiac Acetone* 0.03
Sunbirdblsobutyraldehydc 6.00
Crotonaldehyde
3-WAY Hexanaldehyde 0.11
Catalyst Benzaldehyde
Total Aldehydes 0.55
TIIC 155
Total As Z of TIIC0.35
Formaldehyde 0.085
Acetaldehyde 0.29
Acetonca 0.00
'78 Saab
99° Isobutyraldehyde 0.00
12 PERCENT
MISFIRE
0.39
0.76
0.045
0.00
0.00
.
1.20
1050
0.11
0.00
0.00
0.00
0.00
DISABLED 02
DISABLED DISABLED HIGH OIL SENSOR AND
02 SENSOR EGR AND 02 CONSUMPTION RICH BEST IDLE
0.74
2.005
0.40
0.00
0.355
3.50
1470
0.24
0.00 '
0.00
O.i3
0.17
1.675
4.695
0.00
0.00
O.OQ
6.37
1400
0.46
— -.*
««_
0.18
0.00
0.025
0.00
0.00
0.21
240
0.09
0.01
0.29
0.00
0.02 .
— -
0.27
2.47
0.075
0.00
12 PERCENT
MISFIRE AND AIR
TO BYPASS
T
___
DISCONNECTED
CTS
— -
..
Crotonaldehyde '
3-Way Hexanaldehyde 0.00
0.00
0.00
0.00
0.00
Catalyst Benzaldehyde — -
Total Aldehydes 0.38
TIIC JOO
Total As Z of THC0.38
Formaldehyde 2.41
Acetaldehyde 0.11
Acetone8 0.01
'79 Mercury Isobutyraldehyde 0.08
0.00
2150
0.00
0.40
710
0.06
0.00
0.12
0.00
0.13
1,265
0.41
0.145
1.095
0.32
130
0.25
2.82
815
0.35
0.91
0.655
0.00
0.275
• .
0.22
1.17
1.095
0.00
Marquis1- Grot onn Idt-hyde — — -
3-WAY Hoxanaldchydn 0.00
0.00
0.00
0.00
0.00
Catalyst Benzaldehyde •
Total Aldehydes 2.61
TIIC 127.5
Total As Z of TIIC 2.05
•
0.25
105
0.24
2.92
1485
0.20
1.85
1725
0.11
2.49
1795
0.14
No Valid Data Available Not Measured
^Includes Acrolcin and Propanal
Data From "Regulated and Unregulated Exhaust Emissions From Malfunctioning Three-Way Catalyst Gasoline Automobiles",
EPA-460/3-80-004. January I960, Appendix C, ' . . ' .
cData from "Regulated and Unregulated Exhaust Emissions From a Malfunctioning Three-Way Catalyst Gasoline Automobile",
EPA-460/3-80-OOS, January 1980, Appendix C.
to
-------
TABLE 11
FUEL VARIATION ALDEHYDE EMISSIONS
FUEL
FORM- ACET- IS08UTYL- CROTON-
ALDEHYDE ALDEHYDE ACETONE* ALDEHYDE ALDEHYDE
HEXAN- BENZ- TOTAL TOTAL AS
ALDEUYD& ALDEHYDE ALDEHYDES THC ^ OF THC
MERCEDES 240DD«°
EM-238-F
. EM-239-F
EM-240-F
EM-241-F
EM-242-F
VU RABBIT
DIESELb.d
EM-238-F
EM-239-F
EM-240-F
4.70
3.00
2.50
7.00
5.4
6.00
5.10
4.00
1.00
0.69
0.087
1.30
0.57
1.20
0.39
0.41
3.60
3.10
6.31
2.60
1.20
5.50
1.10
A. 46
0.
0.
2.
I.
4.
0.
1.
1.
56
60
90
20
20
73
30
20
0
1
< i
2
2
3
0
2
.75
.20
.30
.10
.20
.90
.84
.90
10
0.00 10
7
14
13
17
8
8
.61
.59
.10
.20
.57
.33
.73
.97
120
190
90
200
120
180
200
170
8.8
5.6
7.9
7.1
11.3
9.6
4.4
5.3
DETROIT DIESEL
ALLISON 6V-71c-e
CATERPILLAR
3208c«e
EM-241-F
EM-242-F
EM-238-F
EM-239-F
EM-240-F
EM-241-F
EM-242-F
EM-23B-F
EM-239-F
EM-240-F
EM-241-F
EM-242-F
19.00
6.20
137.53
72.49
47.68
94.78
63.35
100.55
92.89
126.54
166.18
67.39
4.81
0.86
81.40
0.70
24.56
23.69
7.44
38.21
14.60
39.37
42.54
27.23
8.40
1.60
182.44
5.16
28.89
85.02
12.67
24.49
35.83
70.30
35.89
25.87
2.
1.
322.
0.
96.
76.
28.
52.
35.
140.
53.
25.
30
80
78
00
79
66
92
28
17
60
18
87
3.90
1.00
11.23
22.31
7.22
41.81
• 13.08
16.09
23.89
11.25
9.31
4.83
0.00
0.00
0.00
0.00
—
•
38.40
11.46
735. 3B
100.66
205.14
321.96
125.46
236.62
202.38
388.06
307.10
151.19
710
200
500
710
990
850
690
1240
1110
1620
1880
1100
5.4
5.7
147.1
14.2
20.7
37.9
18.2
19.1
18.2
24.0
16.3
13.7
"Includes Acetone, Acrolein and Propanal
^Emission Factors, ing/km
cAldehyde Emission Factors, ng/hp hr at 10l.3kPA and 21*C, THC Emission Factors, nig/hp hr
dbata from "Characterization of Gaseous and Particulate Emissions from Light-Duty Diesels Operated on Various Fuels",
EPA 460/3-79-008, July 1979.
eData from "Characterization of Diesel Caseous and Particulate Emissions", Contract No. 68-02-1777,
Sept. 1977 (unpublished)
-------
TABLE 12
TEMPBKATUU VARIATION ALDEHYDE EMISSIONS
(•g/km)
TEMPERATURE F
(C>
1972 Chev. lipala
U/0 Catalyat
Ave
1974 Chev. Inpala
U/0 Catalyst
Ave
1977 Honda Civic
49 State
U/O Catalyst Ave
1977 Ford LTD
49 State
Ave
1977 Plymouth Fury
49 State
Ave
1978 buick V6
Turbocharged
Ave
1977 Plymouth Fury
Calif.
Ave
1978 Chevy. St.
Calif.
Ave
1978 Ford Pinto
Calif.-} Way
Ave
1978 VU Babbit
Calif. FUINJ
Ave
1979 Dodge Aapeo
Calif.
Ave
1980 Mercury
Prototype
Ave
J980 Buick Regal
Prototype
Ave
Dataon Prototype
Ave
0
(-18)
91.64
100.41
96. SI
244.21
164.07
•
214.14
277.22
270.85
274.04
149.97
113.36
70.11
111. IS
121.31
108.08
•
114.69
77. 7S
119.52
111.41
102.89
74.91
77.82
•
76.37
69.83
78. 53
73.95
73.14
69.83
85.00
75.99
51.14
60.66
55.90
116.80
79.73
98.26
•
53.02
ta.6*
•
57.84
20
(-7)
103.il
99.84
101.57
206.56
175.04
•
190.80
322.44
247.61
285.03
106.10
84.46
95.63
114.37
•
•
114.37
118.76
111.38
•
115.07
57.53
57.15
•
57^34
63.03
93.15
79.09
57.17
61.14
•
59.16
48.11
76.32
62.22
111.75
71.46
91.61
48.12
52.49
50.31
59.19
40.76
49.97
100.90
49. 91
•
75.38
40
(4)
79. 5S
85.03
82.29
202.87
285.26
•
244.07
192.83
272.30
232.56
99.96
84.50
92.23
102.92
130.41
•
116.66
62.98
64.40
*
63.69
56.85
45.19
»
51.02
64.65
61.59
63.12
68.17
45.40
•
56.79
57.80
57.50
57.65
96.35
72.15
84.25
62.25
•
62.25
52.86
•
52.86
76.32
17.01
80.14
71.39
60
(16)
166.61
90.07
95.44
139.19
260.27
263.36
220.94
276.3d
214.57
245.48
110.31
96.33
103.32
81.47
102.24
65.25
82.99
"146:89 '
60.03
*
103.36
66.81
82.87
•
74.74
49.33
50.74
50.04
63.59
67.9}
•
65.77
97.28
169.48
133.38
7V. 24
yd. 45
86.85
64.75
•
64.75
23.01
•
23.01
57.06
•1.44
t
76.35
70
(21)
169.84
88.19
99.01
142.10
260.16
•
201.23
141.30
235.88
188.59
118. U
111.69
115.32
82.74
92.88
46.86
74.17
171.76
66.36
v»
119.06
69,10
61.15
•
65.12
46.24"
57.35
51.79
50.61
77.29
•
63.95
98.90
58.71
78.81
li.ti
86.40
84.81
59.06
75.67
67.37
41.69
26.83
34.26
45.56
75.18
•
60.47
80
(27)
1(4:60
82.36
99.48
148.10
211.13
•
179,61
170.94
179.38
175.15
91.97
107.41
99.60
82.89
101.21
•
93.05
137.63
70.22
1
103.92
45.14
40.72
•
4,1,03
•44.20
56.68
50.44
33.22
47.07
•
40.15
70.15
66.34
68.25
00. 7*
90.93
85.86
41.49
37.84
39.66
io.n
53.78
51.96
40.17
112.41
•
76.29
80AC
(27)
12). $4
84.41
105.97
95.03
109.25
102.14
•
•
•
138.58
95.60
•
117.09
47.17
45.98
•
44.68
19.12
58.82
48.97
11.92
57.02
•
44.47
•
•
lia.U
89.07
109.10
54.96
•
54.96
19.19
•
19.19
•
•
•
•
90
(12)
124.29
77.15
100.72
158.05
176.41
•
167.23
152.50
175.55
164.03
"70.01
66.77
68.39
88.85
100.42.
•
94.64
136.51
115.13
•
125.82
48.10
47.92
•
47.92
35.21
59.14
47.18
50.37
44.46
29.95
41.59
78.18
53.00
65.59
Ul.li
82.75
111.95
57.73'
•
57.73
42.79
•
42.79
150.27
125.83
•
110.0)
90AC
(32)
lli.12
77.51
97.82
•
•
•
•
•
*
82.17
75.16
78.76
•
•
•
135.71
90.28
•
112.99
44.16
55.84
•
50.01
37.25
63.56
50.40
38.43
31.64
•
35.04
•
•
99.15
101.20
100.17
41.08
•
41.08
51.15
•
51.15
•
•
•
*
110
(43)
114.93
88.30
112.64
198.97
200.34
•
199.66
170.83
195.23
183.03
81. 16
66.94
74.02
62.75
85.99
•
74.37
157.31
93.34
•
125.32
35.37
50.31
•
42.84
30.95
40.81
35.88
42.34
34.56
•
38.45
83.62
53.16
68.39
115.22
113.03
Hi. 12
62.87
39.42
51.14
56.78
39.16
47.97
64.22
28.04
•
46. U
110 AC
(43)
98.40
89.39
93.89
•
•
•
•
•
fit. 76
81.24
81.50
•
•
•
127.56
123.17
•
125.37
46.53
58.01
49.08
51.21
54.99
50.88
52.94
45.67
31.08
81.20
52.65
•
•
105.58
138.13
121. A5
44.93
57.72
51.33
54.36
102.01
78.18
•
*
•
•
-------
TABLE 13
FTP ALDEHYDE EMISSIONS FROM 19/9 OLDSHOBILB
DIESEL.DELTA 88 WITH AMD WITHOUT A CATALYST
(•g/kn)
TEST
NO.
1
3
5
7
9-1
10-1
11-1
12-1
13-1
14-1
1.3.9-1,12-1
5,7
10-1. ll-l
13-1.14-1
CATALYST
NODE
NONE
PTX-516,
PTX-516
None
UOP-103
UOP-103
NONE
OOP- 99
UOP-99
HONE
PTX-516
UOP-103
UOP-99
FORM- ACET- IB08UTYR-
ALDEUYDE ALDEHYDE ACETONE' ALDEHYDE '
3.4
6.1
1.1
2.4
4.2
3.1
2.9
4.9
4.5
5.3
4.7
1.8
3.0
4.9
1.2
0.9
0.6
0.7
0.9
0.7
0.9
0.1
0.0
0.0
0.8
0.7
0.8
0.0
0.1
0.8
0.0
0.0
0.0
0.0
0.4
0.0
0.0
0.0
0.2
0.0
0.2
0.0
2.1
0.0
0.0
0,0
0.0
0.0
0.0
0.0
0.0
1.6
0.5
0.0
0.3
0.8
CBOTON-
ALDEHYDB
0.0
— — -
. o.o
0.0
0.0
0.0
0.0
0.0
^•4
0.0
HEXAN- BENZ-
ALDEHYDE ALDEHYDE
0.0 0.0
0.0
0.0
0.0
0.0
0.0 0.0
0.0 0.0
0.0 0.0
Q.O
0.0
(AVEBACB EMISSIONS. Bg/ka)
0.0 0.0
0.0
0.0
"""• ~
0.0
0.0 0.0
•o.o
TOTAL
ALDEHYDES
6.8
7.8
1.7
3.1
S.I
4.4
4.2
5.0
4.5
6.9
6-2
2.J
4.3
5.7
TOTAL AS
THC 1 Of THC
260
170
90
90
270
130
40
280
210
180
245
90
85
195
2.6
4.6
1-9
3.4
1.9
'•*
10.5
1.8
2.1
3.8
2.5
2.8
5.1
2.9
CO
'include* Acrolein «nd Propanal
-------
Initial
TAJiLE 14
MILEAGE COMPARISONS FOR ALDEHYDES
Average Emission R«c«s, mg/tua
After FiraC After Second
5000 Mile Accum 5000 Mile Accum
After Third
5000 Mile Accum
'78 Ford Pinto
3-waytOX.
'78 Pontiac
Sunbird
3-Way
'78 Saab 99
3-Way
'79 Merc Marquis
3-Hay * OX
Formaldehyde
Acetaldehyde
Isobutyraldehyde
Hexanaldehyde
Total Aldehydes
THQ
Total aft Z of THC
Formaldehyde
Acetaldehyde
Isobutyraldehyde
Hexanaldehyde
Total Aldehydes
TIIC
Total as Z of THC
Formaldehyde
Acetaldehyde
Ispbutyradlehyde
Hexanaldehyde
Total Aldehydes
TIIC
Total as Z of THC
Formaldehyde
Acetaldehyde
laobupyraldehyde
Hexanaldehyde
Total Aldehydes
TIIC
Total as Z of TIIC
0.14
0.09
0.01
ND
0.24
160
0.2
0.22
ND
0.05
ND
0.27
270
0.1 -
0.10
0.55
0.05
0.04
0.74
130
0.6
3.65
0.30
0.04
ND
3.99
140
2.9
1.28
0.14
0.78
HP
2.20
200
1,1
0.88
0.25
1.44
ND
2.57
270
1.0
0.36
0.14
1.16
0.01
1.67
110
1.5
3.23
0.08
0.15
ND
3.46
210
1.6
1.20
0.15
0.91
ND
2.26
260
0.9
0.55
0.58
3.46
0.15
4.74
310
1.5
0.04
0.27
1.99
0.08
2.38
150
1.6
2.82
0.33
1.32
ND
4.47
200
2.2
1.33
0.36
5.18
0.48
7.35
230
3.2
1.05
0.33
1.17
0.31
2.86
380
0.8
0.24
0.64
5.00
0.54
6.42
140
4.6
4.05
0.88
2.20
0.28
7.41
230
3.2
U)
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Table 13
Linear Regression Parameters and Extrapolated High Mileage Emissions
Linear Regression Parameters Extrapolated Emissions, mg/mk
Vehicles
1978 Ford Pinto
Aldehydes
THC
1U78 Pontiac Sunbird •
Aldehydes
THC
1978 Saab 99
Aldehydes
THC
1979 Mercury Marquia
Aldehydes
THC
Slope
0.0005
0.003
• O.OOQ03
0.011
0.0005
0.003
0.0004
0.002
Y-Intercept
-1.213
200.
3.10
210.
-1.26
103.33
1.16
193.33
Correlation
Coefficient
0.871
0.500
0.123
0.988
0.927
0.721
0.962
0.655
50,000 Miles
23.79
350.
4.60
760.
23.74
253.33
21.16
293.33
72,866 Miles
35.22
418.60
5.29
1011.53
35.17
321.93
30.31
339.06
100.000 Milea
48.79
500.
6.10
1310.
48.74
403.33
41.16
393.33
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Tsbl« 16
Deterioration Factors*
Vehicles
Deterioration Factor* Using
Available Data
Deterioration Factors Using
Extrapolated Data
1978
1978
1978
1979
i.
Ford Pinto
Aldehydes
TUG
Pontiac Sunbird
Aldehydes
TIIC
Saab 99
Aldehydes
TIIC
Mercury Marquis
Aldehydes
TIIC
Average
Aldetidyea
TIIC
10,
1
1
1
1
1
1
1
0
1
1
000 Miles 15,000 Miles Average
.03
.30
.84 •
.15
.43
.36
.29
.95
.40
.19
emission factor at
3.34
1.15
1.11
1.41
3.84
1.27
2.14
1.10
2.60
1.23
specified
2.19
1.23
1.47
1,28
2.63
1.32
1.72
1.02
2.00
1.21
mileage( og/ka ' .
50.000 Miles 72,866 Miles
10
1
I
2
14
2
6
1
8
2
.81
.75
.79
.81
.22
.30
.12
.40
.24
.07
16
2
2
3
21
2
8
1
11
2
.01
.09
.06
.75
.06
.93
.76
.61
.97
.60
100,000 Miles
22.
2.
2.
4.
29
3
11.
1.
16
3
18
50
37
85
.19
.67
90
87
.41
.22
OJ
Cn
^Deterioration Factor-emission factor at 5000 miles,
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