EPA/AA/CTAB/PA/81-18
Summary of Current Status of
EPA Office of Mobile Source Air Pollution Control
Characterization Projects
Thomas M. Baines
August, 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.
U.S. Environmental Protection Agency
Office of Air, Noise and Radiation
Office of Mobile Source Air Pollution Control
Emission Control Technology Division
Control Technology Assessment and Characterization Branch
2565 Plymouth Road
Ann Arbor, Michigan 48105
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Table of Contents
Page
I. Overview 3
II. Summary and Conclusions 6
III.Recommendations for Future Work 12
IV. Characterization Results 15
A. Heavy Duty Diesels ' 15
1. Normal Operation 15
2. Malfunction Conditions 21
B. Light Duty Diesels 23
C. Light Duty Gasoline Vehicles 23
D. Fuels 31
1. Fuels Variables 31
2. Alternate Fuels 36
a. Middle Distillates Derived From Alternate Sources 36
b. Gasoline Derived From Alternate Sources ... 40
c. Alcohol Fuels 40
E. Nitrosamines 43
F. Identification of Types of Compounds Responsible
for Ames Test Activity in Diesel Particulates 45
G. Development of Method to Collect/Characterize
Gas-phase Hydrocarbons 45
H. Ames Testing 47
V. References 54
VI. Appendixes 58
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I. Overview
The Characterization Program of ECTD has focused on .expanding the knowledge
of pollutants as they are emitted from various mobile sources. This work
has been done within ECTD, by in-house and extramural programs, as well as
monitoring the characterization efforts performed by other organizations
both within EPA and by industry and others. Some of the principal guiding
objectives of the ECTD characterization program can be summarized by the
following points.
1. The characterization of pollutants not normally tested and that may
represent a human health concern.
Currently, and in the past, a large amount of effort has been expended
by industry and EPA characterizing the hydrocarbon, carbon monoxide and
oxides of nitrogen emissions from a variety of engines and vehiclesi
However, there may be other compounds being emitted by vehicles that may
be hazardous. Especially of interest would be those compounds that may
have a deleterious effect on human health. Some of these compounds
would be emitted in varying amounts from uncontrolled as well as
controlled engines. Other compounds (such as catalyst attrition
products) could be emitted mostly from vehicles which have emission
control systems designed to lower HC, CO and NOx. Various systems to
improve both emissions and fuel economy could have a large impact on
unregulated emissions. Since motor vehicle technology is changing so
rapidly now in response to the need for improved emissions and fuel
economy, it is critical that ECTD characterize new systems for
unregulated pollutants. Consequently, the ECTD program has been focused
on characterizing a broad range of compounds from present and future
engine and vehicle "technologies.
2. Testing for a variety of pollutants under malfunction conditions.
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Much, if not most, of the testing performed by EPA and other
laboratories has been done with the engines tuned to manufacturers'
recommended specifications. However, many vehicles that are in use
today operate under conditions of tune that do not meet the
manufacturers' recommended specifications. This could result in
increased emissions of a variety of both regulated and unregulated
pollutants, some of which could have negative human health effects. As
a consequence, ECTD has tested a variety of engines/vehicles for
pollutants of concern under malfunction conditions to estimate the
impact that such vehicles/conditions would have on the environmental
loading of pollutants.
3. Fuel parameters.
The fuel situation in the United States is currently very dynamic, in
that we are rapidly developing alternate sources of fuel to supplement
conventional petroleum sources. These alternate sources include lower
grade petroleum crudes, as well as alternative and synthetic fuels
derived from coal and oil shale. Some of the new fuels will be alcohols
including methanol. These newer fuels may have a dramatic effect on
emissions and, as such, ECTD has performed some characterization on
these emissions as well as remained abreast of the field in general.
Also, some testing has been done on emissions from Diesel vehicles, as
these emissions may be impacted by fuel parameters. The ECTD fuels
characterization program will continue in an effort to more fully
characterize the future fuels. This work is of critical importance in
that it helps assure that alternate fuels are environmentally
acceptable. One can probably tailor fuel composition and processes to
obtain maximum environmental benefit from these fuels if one does this
characterization before these 'fuels are widely produced.
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4. Characterization of pollutants from engines/vehicles that are involved
in a transition environment.
There are many engines/vehicles that are involved in a transition
environment created by various regulatory initiatives, .fuel economy
incentives, etc. ECTD is very interested in characterizing the
emissions from these vehicles/engines to be able to evaluate the impact
that this transition may have. For example, the heavy-duty Diesel
engine manufacturers are now currently changing many of their engines
from the traditional, naturally aspirated type over to the turbocharged
type. In an effort to evaluate this change and how it affects
pollutants, some testing has been done on equivalent engines. Also,
there is currently a trend towards Dieselization of both the light-duty
fleet as well as the mid-range heavy-duty fleet. Comparative
application engines for both of these fleets have been tested so that an
estimate can be made of how such a change will impact the environmental
loading of pollutants. Also, a variety of other technologies have been
evaluated so that their influence can also be estimated. These include
the influence of indirect injection in a heavy-duty Diesel engine, the
influence of high pressure injection in a Diesel engine, and others.
With these objectives in mind, a variety of programs and projects have
been performed. The more recent and more important of these projects
are summarized in the following section.
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II. Summary and Conclusions
EPA-OMSAPC is conducting a thorough characterization of unregulated
emissions on a variety of current and prototype engines. Extensive work is
also underway to see how various fuel parameters affect regulated and
unregulated emissions. This latter work includes projects on alternate
fuels such as methanol as well as fuels derived from coal or oil shale.
Based on the recent work the following conclusions can be made.
1. The effects of a number of engine parameters on regulated and
unregulated emissions were examined for several heavy duty Diesel
engines. It was found for two Daimler-Benz engines that turbocharging
generally decreased all emissions with the major exception being NOx,
for which a slight increase was noted.
It was found on a Caterpillar 3406 engine that advanced injection timing
increased HC, CO, NOx, sulfates, and aldehydes while reducing
particulates and extractable organics. It was found on a Caterpillar
3406 engine that changing from a direct to an indirect injection system
increased HC, brake specific fuel consumption, and sulfates but
decreased CO, NOx, particulates, organic extract, and odor. With a Mack
ETAY(B) 673A engine, water injection (30% volume) was found to reduce
. NOx slightly, increase HC and CO slightly, but increase particulates and
extractable organics greatly.
Different fuel pumps and the effect of EGR on regulated and unregulated
emissions were also examined. The use of a high pressure pump reduced
particulates greatly but increased NOx. Use of EGR decreased NOx but
increased particulates.
2. The soluble organic emissions from four different heavy duty Diesel
engines were compared with those from a heavy duty gasoline engine
burning leaded fuel. The Diesel engines showed a higher percent of
organic extractables from the particulate than the gasoline engine. The
percent extractables decreased greatly as load increased for the Diesel
engines.
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Also, the gasoline engine was compared to a Diesel used in similar
applications. The Diesel engine had much lower HC and CO with slightly
higher NOx emissions. The Diesel emitted a much higher quantity of
particulates and percent extractables but had somewhat: lower BaP
emissions. Sulfate emissions were greater but aldehydes were less for
the Diesel engine.
3. Limited testing has been done on Diesel bus engines under malfunction
conditions which would simulate emissions under in-use conditions where
engines are frequently not tuned up to manufacturers' specifications.
The one engine tested so far shows an increase in HC, CO, brake specific
fuel consumption, and a large increase in both particulates and
extractable organics. A second engine is being tested.
4. Work has been done comparing emissions from an Oldsmobile and VW Diesel
with their gasoline counterparts. These tests showed generally higher
HC, much higher particulates, higher BaP, higher sulfates but lower CO
from the Diesel versions. There was no clear trend with aldehydes
although the aldehydes were usually higher with the Oldsmobile Diesel
versus gasoline engine.
5. EPA has conducted extensive tests on four oxidation and four three-way
catalyst equipped gasoline vehicles under malfunction conditions. The
malfunction conditions tested include rich-best-idle, 12% misfire,
disabled EGR, higher oil consumption, and faulty air injection. Both
the oxidation and three-way catalyst-equipped vehicles generally showed
higher regulated and unregulated emissions.
These results were compared with data from a non-catalyst equipped
vehicle.
It appeared as though sulfate, ammonia, and nitrous oxides were higher
from catalyst equipped cars than from the one non-catalyst car.
Hydrocarbons and aldehydes were highest from the non-catalyst car.
Ammonia and cyanides were highest from the three-way catalyst cars. It
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appeared that the unregulated exhaust emissions composition from
catalyst equipped cars operating under malfunctioning conditions was, in
general, distinguishably different from that of the non-catalyst cars.
6. EPA has also conducted a program to examine how Diesel fuel parameters
affected emissions from typical light duty Diesels (a VW and Mercedes
Benz 240D). Five different Diesel fuels were tested. It was found that
the minimum quality fuel frequently adversely affected emissions. A
follow-on project was conducted in which very specific fuel parameters
were varied to determine their effect on emissions. This work showed
that phenol emissions were strongly affected by the shale oil blend.
Particulate rates were reduced with the fuel containing the light-end
blend and the olefin blend, by 14 percent and 6 percent, respectively.
The two blends containing aromatics were associated with increases in
particulate emissions of about 27 percent. The cetane-improved aromatic
fuel blend increased particulate emissions about 68 percent over those
observed with base fuel. Heavy ends fuel apparently did not cause an
increase in particulate emissions. Also, blends containing aromatics
resulted in slightly less organic solubles extracted from the
particulate matter. Olefins, light ends, and heavy ends of fuels were
associated with increases in the amount of organic solubles.
7. EPA has just started a program to investigate how alternate fuels
(including fuels derived from coal and oil shale) affect emissions.
Four fuels (a #2 Diesel fuel, #2 Diesel fuel marine from oil shale, a
Paraho JP-5 from oil shale, and a Coal Case 5A fuel (a fuel containing
solvent refined coal (SRC II) and petroleum materials blended by the
U.S. Army)) are being tested with a VW Diesel. There was virtually no
change in HC, CO and NOx emissions with the shale marine fuel. This was
also true of the particulate emission rate. The aldehydes, however,
decreased slightly. The phenols stayed much the same, as well as the
odor. There was a slight increase in the fuel economy. In looking at
the Paraho JP-5, a slight increase was seen in HC, CO, NOx as well as a
slight decrease in fuel economy. The particulate was unchanged, as well
as aldehydes and odor while phenols decreased somewhat with use of the
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JP-5. The coal case resulted in a rather dramatic increase in HC, CO,
NOx and particulate, on the order of approximately 50 percent. Fuel
economy also increased, and phenols and odor went up slightly.
A solvent refined coal (SRC-2) fuel is currently being tested. While
EPA has tested only Diesel fuels to date, EPA plans to test a Mobil MGT
process gasoline (derived from methanol made from coal) and other
gasolines as they are available. EPA will also test more Diesel fuels
as they become available.
8. EPA has tested a heavy duty Volvo Diesel bus engine designed to run on
methanol and Diesel fuel, each injected through its own injection
system. The emission results from this engine were compared with those
from a conventional Volvo Diesel engine using regular Diesel fuel. The
use of the dual-fuel resulted in a 50% reduction in total particulate
emissions compared to the single fueled engine. The particulate emitted
from the engine using methanol had 70% organic extractables from the
particulate, indicating far less elemental carbon type substances being
formed compared to the conventional Diesel fueled engine, where about
30% organics were found. Less sulfate was also produced due to lower
fuel sulfur levels. It was also found that the use of methanol
decreased NOx by 56% for the 13 mode test and 35% for the transient
cycle.
The use of methanol resulted in a hydrocarbon emissions increase, as
measured by the heated FID, of about 40% for the 13 mode and 70% for the
transient cycle compared to the Diesel fueled engine. Large quantities
of unburned alcohol (which is only partially measured by the heated FID)
were emitted. In one case, the amount of unburned methanol was four
times the amount of hydrocarbons. Aldehyde emissions were also
increased with the use of alcohol. The use of methanol resulted in a CO
increase of about 60%. It was found that the use of an oxidation
catayst reduced both hydrocarbons and CO but some increase in NOx was
found. The catalyst did not reduce particulate levels.
EPA is currently testing a Ford Escort with Anafuel (gasoline with a
methanol based additive) and plans to test a VW designed . to burn 100%
methanol fuel.
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9. EPA has also conducted work measuring nitrosamines (a potent carcinogen)
in both Diesel crankcase emissions and vehicle interiors. Nitrosamines
were found in Diesel crankcase emissions, possibly resulting from oil
additives. Nitrosamines have also been found in vehicle interiors.
Finally, nitrosamines may be present in Diesel exhaust, although this
possibility is still unconfirmed. Preliminary data show that
3
nitrosamine levels may be high (1 jig/m ) along roadways arid apparently
these nitrosamines are mobile source related. It is not known if the
Diesel crankcase and vehicle nitrosamines are entirely responsible for
the roadside nitrosamine levels reported.
10. Various research projects, including some at EPA, have identified some
of the compounds responsible for the Ames test activity of Diesel
particulates. Apparently, polynuclear aromatic hydrocarbons themselves
are responsible for only a small portion of the activity. However,
various oxygenated polynuclear aromatic hydrocarbons (including hydroxy,
ketone, carboxaldehyde, quinone, acid anhydride, and nitro compounds)
have been identified in the "transition" fraction that accounts for
significant Ames test activity.
11. EPA is currently developing a method to collect the gas phase HC in the
exhaust for bioassay tests. A promising method being developed by ORD
appears to be a cleaned-up XAD-2 resin. The hydrocarbons collected by
this method may not have much Ames test activity compared with that of
the particulate. However, OMSAPC has run some tests with a back-up
filter containing treated Diesel particulates which shows that the HC
collected does have Ames test activity that could be significant.
12. A number of Ames bioassay tests have been run on various samples
collected by OMSAPC recently. Ames test work on the Diesel fuels
project (discussed in Conclusion 6) showed that an increase in Ames test
activity is associated with fuel aromatics. An increase in Ames test
response was also seen when the cetane improver was used. Ames test
work on samples collected from the dual fueled Volvo Diesel engine
(discussed in Conclusion 8) indicated that the particulate from the dual
fueled engine had lower Ames test activity than did the baseline engine
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(i.e. pure Diesel fuel) over the transient cycle but higher activity
over the 13 mode cycle. This apparent discrepancy may be explained by
the fact that the dual-fueled engine showed much higher Ames test
response for heavily versus lightly loaded modes. The 13 mode cycle is
considered to be more heavily loaded than the transient cycle. There
are also some data showing that the presence of a catalyst resulted in
increased Ames test activity.
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III. Recommendations for Future Work
The ECTD recommendations for future work are the following:
1. Synfuels. With the dramatic change in petroleum and fuel sources about
to occur, it is extremely important that EPA remain abreast of the
developments in this area. This is especially important wi'th respect to
the influence that these fuels may have on exhaust emissions products.
There is currently a large level of effort on-going in the area of
alternate fuel plant source emissions. However, very little work is
currently planned on ultimate use or in-use emissions from the
combustion of these fuels in vehicles. The fuels that should be tested
in vehicles include coal liquids such as refined SRC-2, refined EDS and
H coal liquids (made from direct coal liquefaction). The shale oil
liquids should include those that may be available through the Union Oil
process. Also it will be important to analyze different types of shale
products, such as those made by in-situ retorts and other such methods.
Other fuels that will be important to characterize include coal derived
methanol, as well as actual methanol fuels (blends) from non-petroleum
sources. Such alcohols should be looked at as well as
alternative-source fuels. Also, gasolines should be tested, such as
those from the Mobil MGT process as well as Naptha fractions, and others
that are currently envisioned to be produced. By analyzing the
emissions from these fuels, EPA will then be able to estimate the
influence that they will have on ambient air quality.
2. New Technologies. As new technologies are developed it will be very
important to remain abreast of .the pollutants that may be emitted by
them. Many technologies that have been introduced in the past have
resulted in lower quantities of some pollutants. However, some of them
have also resulted in increasing some pollutants that have been a
concern. It is important to remain abreast of these new techologies so
that if any pollutants are emitted that are hazardous to human health,
an appropriate assessment of their impact can be made. New technologies
might include the Ethyl lean burn system, various Diesel systems, such
as the turbocompound and ceramic adiabatic engine or possibly various
Diesel particulate trap technologies. New systems will be developed in
the continued desire for improved fuel economy.
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3. Bioassay. It will be very important to continue to analyze emissions
from a variety of vehicles with bioassay techniques. For example,
emissions from locomotives, possibly aircraft, motorcycles and other
such sources that have never been analyzed should be given at least a
preliminary bioassay characterization. Also, there is evidence showing
that certain fuel additives appear to increase biological activity and
this should be further investigated.
To date, ECTD has relied heavily on the Ames test to more or less
routinely test Diesel particulates and other samples. While the Ames
test has been a useful tool in comparing and investigating the
bioactivity of various systems, the Ames test does have some limitations
(e.g. it may not respond accurately to some nitrogen containing
compounds). Future efforts should involve helping develop and use a
simplified tier bioassay test system so that more accurate bioassay test
data are obtained.
4. Malfunction conditions. Additional work should be done especially with
•V \
Diesel engines under conditions outside of thos,e normally ^recommended by
the manufacturer. By analyzing emissions frjpm vehicles under these
conditions, a more realistic view of the pollutant burden emitted by
such vehicles can be obtained.
This is especially important for heavy duty Diesel buses which operate
in urban environments where the Diesel emissions can come in contact
with large numbers of people. This is also important for light duty
Diesels since very little work investigating their emissions under
malfunction conditions has been done.
5. Gas phase analyses. EPA-ORD is currently completing the development of
a gas phase sampling technique. ECTD should perform some testing with
this technique to more adequately and fully characterize the gaseous
emissions from a variety of different mobile sources. In this manner,
EPA will be able to obtain a thorough estimate of the potential
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impact of emissions from these mobile sources. This sampling should be
performed on both light and heavy duty engines, including both gasoline
and Diesel engines.
6. Specific pollutants. In the past, there has been some testing done on
specific pollutants that are potentially very hazardous. Some
additional work should be performed, for example, in the area of
nitrosamines. Nitrosamines should be analyzed in Diesel exhaust where
there is a tentative indication that they may be found. Also, there
should be some additional nitrosamine monitoring along roadways to
confirm the preliminary evidence of their existence there. Also in the
past there have been specific compounds, such as dioxins, that had to be
analyzed in a variety of exhaust sources. As these "pollutants of the
month" arise, EPA should be in a position to respond in a rapid fashion
and be able to analyze them.
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IV. Characterization Results
A. Heavy Duty Diesels
1. Normal Operation
The more recent work with heavy duty Diesels has been done under EPA
contract Number 68-03-2417, wherein a number of different engine variables
were analayzed for their effect on engine pollutant emissions. The
variables which were investigated included effects of 1) turbpcharging, 2)
exhaust gas recirculation (EGR), 3) changes in timing, 4) combustion system
(direct or indirect injection), 5) fuel injection pressures, and 6) water
injection. The data from this study of these six variables are presented in
Table 1* and are discussed in the following paragraphs (1, 2 and 3).**
The engine which was used to determine the effects of turbocharging was a
Daimler-Benz OM-352 and the turbocharged version, the Daimler-Benz OM-352A.
Turbocharging, it is noted, decreased almost all of the pollutants for which
analyses were made. The major exception to this was NOx, which showed a
slight increase. Aldehydes were almost unchanged, and the brake specific
fuel consumption decreased.
The effects of timing were determined by testing a Caterpillar 3406 direct
injection engine. By advancing the timing, increases were observed in HC,
CO, NOx, brake specific fuel consumption, sulfate and a very dramatic
increase in aldehydes. The amount of particulate was reduced as well as the
percent of extrac table organics. By retarding the timing., a slight
reduction in HC was observed, as well as a very slight increase in CO, a
rather dramatic decrease in NOx, and a slight increase in brake specific
fuel consumption. The particulate rate increased rather markedly (i.e., by
a factor of almost three), the percent of extractable organics also
increased, as did the BaP emission rate and the sulfate emission rate. The
odor level decreased; however, aldehydes.increased by almost a factor of two.
* The data in this and other tables are usually based on single emission tests.
**Numbers in parentheses designate references given at the end of the paper.
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Table 1
IIC, g/kW-hr
CO. g/kW-hr
NOx, g/kW-hr
BSFC. kg/kW-hr
Participate, g/kW-hr
Organlcs, X
BaP, ug/ku-hr
Sulfate, og/kU-hr
Odor, TIA
Aldehydes, mg/kW-hr
Effect of Varying Engine Parameters on Pollutant Emissions
Daimler-Benz Caterpillar 3406 DI Caterpillar 3406
OM-352
Naturally
Aspirated
3.20
7.00
9.98
0.294
1.33
34.2
1.43
19.0
2.2
375.0
OH-352A
Turbo-
chargcd
3.02
4.08
11.95
0.284
0.75
29.2
1.17
18.7
2.32
372.0
Standard
Timing
\
0.47
3.13
13.09
0.253
0.47
17.9
0.20
28.5
2.0
97.9
5X
Advanced
Timing
0.53
5.63
18.53
0.262
0.36
12.9
1.26
34.4
2.0
326.3
10Z
Retarded
Timing
0.43
3.16
7.02
0.273
1.36
19.2
0.69
37.2
1.8
165.1
Dl - Std.
Without
EGR
0.47 ••
3.13
13.09'
0.253
0.47
17.9
0.20
28.5
2.0
97.7
Timing
With
EGR
0.23
6.43
7.35
0.268
1.24
19.5
0.11
28.7
1.7
107.0
- 13 Mode Cycle U
Caterpillar
3406 DI
Direct
Injection
0.47
3.13
13'. 09 '•-.'.
0.253
0.47
17.9
0.20
28.5
2.0
97.9
3406 ID1
Indirect
Injection
, 0.16
1.68
: 6.88
0.272
0.37
11.1
0.14
41.0
1.4
106.9
MACK ETAY(B) 6/3A
Standard
R. Bosch
Pump(APE)*
APS R.
Bosch Pump
111 Pressure
0.64
2.13
8.87
0.243
0.821
16.3
0.23
A4.9
1.8
87.0
0.69
1.08
12.06
0.234
0.40
16.9
0.08
42.8
1.7
105.0
HACK ETAY(B) 673A
Standard Standard
Bosch APE Pump
Pump(APE)* + 30^ H20
0.60
1.64
8.52
0.240
0.71
40.0
0.18
42.2
49.0
0.62
1.
6.
.75
.49
0.239
0.30
49.6
0.22
39.3
53.0
These were 2 separate experimental runs using different APE pumps.
Thus, the data are not necessarily the same.
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The effect of EGR was tested with the Caterpillar 3406 direct injection
engine with standard timing. By applying EGR, a slight increase in HC, a
doubling of CO, a 50% reduction in NOx, a slight increase in brake specific
fuel consumption and a 2.5 fold increase in particulate with associated
increase in the percent of extractable organics were observed. The BaP went
down almost by factor of two, the sulfates remained the same, there was a
slight increase in odor and aldehydes were virtually unchangedi
The effect of direct and indirect injection were studied with the
Caterpillar 3406 engine, which was tested in the direct injection mode and
then changed to the indirect injection mode. With this change to indirect
injection, a dramatic decrease was observed in HC, a decrease in CO, and
again a decrease in NOx. Brake specific fuel consumption increased
somewhat; however, the particulate rate decreased as well as the percent of
extractable organics. The BaP rate also decreased but the sulfate rate
increased somewhat. There was a rather marked decrease in odor; however,
aldehydes were virtually unchanged.
The effect of the pump system was investigated with a Mack ETAY(B) 673A
engine, wherein the engine was tested with a standard Robert Bosch fuel pump
and then with a very high pressure pump. The results showed a slight in-
crease in HC, a decrease in CO, a slight increase in NOx, and a slight de-
crease in brake specific fuel consumption. The most dramatic influence was
the approximately 50% reduction in the particulate emission rate with almost
no change in the percent of extractable organics. The BaP rate with the
high pressure injection was 1/3 that obtained with the normal pump. Almost
no change in sulfate, a slight decrease in odor, and a slight increase in
aldehydes were seen.
The same Mack engine was used to analyze the effect of water injection on a
variety of emissions. This testing involved the injection of approximately
30% water along with the fuel (DF-2) and here a slight increase was seen in
HC and CO, a slight reduction in NOx, and brake specific fuel consumption
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was almost unchanged. However, there was a very dramatic decrease in the
particulate emission rate with an accompanying increase in the percent of
extractable organics. The BaP rate also increased; however, it was noted
that most of this increase was at idle conditions where presumably such an
increase could be reduced by modulating water injection to eliminate water
injection at idle speeds. The aldehyde emission rate was virtually un-
changed.
Table 2 presents the percent organic extractables for particulate from four
Diesel engines and one gasoline fueled engine burning leaded fuel. This
showed a number of things including the trend towards much higher percent of
organic extractables from the Diesel relative to the gasoline engine. It
also showed that there was generally a dramatic decrease in the percent
extractables as the load on the engine increased for the Diesel engines.
The medium duty fleet of trucks is currently undergoing a rather marked
conversion from gasoline to Diesel engines. In order to assess how such a
conversion may influence regulated and unregulated emissions, a number of
comparsions can be made between two engines of comparable applications in
heavy duty trucks. These data are presented in Table 3 for two engines; one
a Caterpillar 3208 which employed EGR and which was designed for California
NOx standards, and a Chevrolet 366 CID gasoline-fueled engine designed for
the same 1977 California standards. Here, much lower hC and CO emissions
were generally seen with the Diesel engine along with slightly higher NOx
emissions. Much lower brake specific fuel consumption was seen with the
Diesel engine. However, the Diesel engine emitted over 12 times more
particulate than the corresponding gasoline engine as well as a much Higher
percent of organics extractables. The BaP emissions, however, were somewhat
lower from the Diesel engine than from the gasoline engine. Sulfate was
much higher, due, of course, to the much higher level of sulfur in the
Diesel fuel. The aldehydes from the Diesel engine were lower by a factor of
approximately 10 compared to the gasoline engine.
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Condition
Speed/Load.(%)
Inter /02
Inter /50
Inter/100
Idle
Inter/CT*
High/100
High/50
High/02
High/CT*
-19-
Table 2
Percent Organic Extractables
From Particulate For
Four Diesel And One Gasoline
Fueled Engines
MACK
ETAY(B)
'673A
34.8
9.3
3.5
15.5
NT@
1.0
6.3
38.5
NT
Cater-
pillar
3208 EGR
17.0
6.7
2.7
8.2
23.3
2.7
2.2
9.4
23.7
Cater-
pillar
3406IDI
12.9
4.5
5.1
9.9
NT
0.8
11.7
35.9
NT
Daimler
Benz OM-
352 N.A.
37.3
57.2
7.1
17.1
NT
7.4
51.6
59.1
NT
Chev-
rolet
366
2.4
4.0
2.0
6.1
5.6
3.9
2.6
1.7
2.9
@ NT = Not tested
* close throttled
-------
-20-
Table 3
Emissions From
Two Engines Used in Comparative
Application Vehicles - 23 Mode
Steady State Test
HC, g/kW-hr
CO, g/kW-hr
NOx, g/kW-hr
BSFC, kg/kW-hr
Particulate, g/kW-hr
Organics, %
BaP, ug/kW-hr
•\ \
1 \Sulfate, mg/kW-hr
Odor, TIA
Aldehydes, mg/kW-hr
Caterpillar 3208
with EGR - Diesel
Chevrolet 366 CID
California (1977) Stds,
Gasoline
1.78
8.51
5.07
0.290
3.48
10.97
2.31
24.36
2.4
109.0
3.34
73.76
4.56
0.463
0.28
3.92
3.02
1.38
1-NA
1017.0
-------
-21-
2. Malfunction Conditions
Almost all of the emissions data that are available from heavy duty engines
have been gathered from engines that were tuned up to manufacturers'
specifications. However, many of the engines that are operating on the
roads today are not operating under a similar set of conditions, due to
factors such as normal wear patterns, maintenance procedures, etc.
Consequently our perception of their emissions could be dramatically
different than may be the actual case.
In order to test this hypothesis, two engines were to be tested under EPA
Contract No. 68-03-2706 with Southwest Research Institute (4). The first
engine tested was a Cummins VTB-903 engine which is an engine normally used
in bus applications. The engine was tested in its baseline condition (manu-
facturers' recommended specifications) and then altered to a malfunction
condition. This malfunction condition was an increase in the fuel injector
lash and a bleed-off of a certain portion of the turbocharger boost. Such a
condition was one in which there would be virtually no noticeable decrease
in power and therefore the operator would probably not bring in the vehicle
for maintenance but would probably continue to operate it on the road. The
data from this condition are presented in Table 4. When tested under this
malfunction condition, increases in HC, CO, and a very slight decrease in
NOx were seen along with an increase in the brake specific fuel con-
sumption. The brake specific particulate also increased by a factor of
approximately two, along with the organics, which went up by a factor of
three on a g/km basis. Sulfates decreased somewhat, odor changed slightly,
depending on whether the data were taken on the thirteen mode test or the
transient cycle. Aldehydes increased by a factor of approximately five
under the 13 mode test and stayed the same under the transient test.
Phenols generally increased quite a bit under the 13 mode test condition but
stayed almost the same or decreased somewhat under the transient test.
EPA is currently testing a Detroit Diesel 6V-71 N engine under a set of mal-
function conditions that are similar to those of the Cummins in that they
are severe enough to alter the emissions yet not severe enough that the
operator would return the vehicle to the shop for maintenance. These data
-------
-22-
Table 4
Emissions Results from
A 4-Strbke Cycle Heavy Duty
Engine (Cummins VTB-903)
Operated Under Baseline And
Malfunction Conditions
13 Mode Transient
Baseline/Malfunction
HC, g/kW-hr
CO, g/kW-hr
NOx, g/kW-hr
BSFC, kg/kW-hr
Particulate, g/kw-hr
Organics , %
Organics, g/kw-hr
Sulfate, mg/kW-hr
Odor, TIA
Aldehydes, mg/kW-hr
Phenols, mg/kw-hr
0.96
2.20
9.29
0.254
0.32
38.4
0.123
39.5
1.58
33.4
5.7
3.94
3.55
9.25
0.269
0.57
55.4
0.316
33.3
1.74
108.12
66.0
Baseline/Malfunction
1.79
1.87
7.83
0.269
0.50
51.2
6.256
38.4
1.17
101.0
15.4
6.98
3.12
7.63
0.288
1.08
76.9
0.829
33.4
1.32
99.0
10.2
-------
-23-
will be available within the next several months. Malfunction data of this
type are very important as they give a realistic view of how these engines
operate under actual conditions. Additional work should be done on heavy
duty engines but an more extensive effort should be performed with light
duty Diesel engines for which no data of this type are available.
B. Light Duty Diesels
Table 5 presents data from the work performed under EPA contract 68-03-2414
wherein the emissions from what were, at the time of testing, prototype
Diesels were compared against their gasoline counterparts (5 arid 6). This
work showed that the hydrocarbon emissions were generally higher from the
Diesel than the gasoline fueled vehicles. However, CO was lower as well as
oxides of nitrogen. The fuel economy for the Diesel engine was, of course,
much better from the Diesel than the gasoline fueled engine. The Diesel
engine also had a much higher particulate rate as well as an organic
emissions rate. The BaP and sulfate emission rates from the Diesel engine
were much higher than those from the gasoline engine. Aldehydes from the
Oldsmobile vehicles were much higher with the Diesel than the gasoline
engine; however, aldehydes were almost equal from the Volkswagen Diesel and
gasoline vehicles.
Continued work should be done on a spot monitoring basis to evaluate the
emissions from light duty Diesel engines.
C. Light Duty Gasoline Vehicles
Much of the testing of light duty gasoline vehicles has been performed when
the vehicles have been tuned to manufacturers' specifications. However,
many vehicles operate in a condition that is outside those specified by the
manufacturer. In order to estimate the levels of pollutants that are
emitted by vehicles under such operating conditions, EPA conducted a
thorough program (7, 8, 9, 10, 11, 12 13) to test a number of vehicles
operated under several malfunction conditions. These conditions included
rich-best-idle, 12% misfire, disabled exhaust gas recirculation, higher oil
consumption (obtained by oil injection), and rich-best-idle with no air
injection.
-------
-24-
Table 5
Emissions Results From
Comparative Diesel and Gasoline
Fueled Vehicles - FTP Cycle
Oldsmobile Cutlass
Volkswagen Rabbit
Displacement in 3
HC, g/km
CO, g/km
NOx, g/km
Fuel
Economy, mpg
Particulate, g/km
Organics , %
BaP, ug/km
Sulfate, rag/km
Odor, TIA
Aldehydes, mg/km
Diesel
350**
0.47
1.24
0.70
21.7
0.57
13.3
4.54
9.96
1.2
80.7
Gasoline
260**
0.24
1.34
0.85
15.6
0.006
10. 7@
0.17@*
1.37
N.T.@@
14.0
Diesel
89.7
0.23
0.49
0.54
42.7
0.18
21.4
2.67
3.66
1.1
39.6
Gasoline
97.1
0.14
2.30
0.63
24.6
0.004
42.3*
0.17@*
0.04
N.T.
35.1
@ = FET cycle
* = Hot FTP cycle
@* = BaP values are considered conservative and should be used
with caution due to inadequacies of sampling method.
@@ = NT=not tested
** = These engines were selected to have equal performance (e.g.
equivalent vehicle acceleration) rather than equal displacement,
-------
-25-
The data from four oxidation catalyst equipped vehicles and one baseline
non-catalyst equipped vehicle are presented in Table 6 which gives the
number of vehicles that experienced emissions increases during malfunction
relative to the baseline state. Most of the malfunctions resulted in an
increase in hydrocarbon emissions as well as carbon monoxide. The misfire
and disabled EGR conditions resulted in increases in oxides of nitrogen,
whereas the remainder of the malfunctions did not have any influence • on
NOx. Most of the malfunctions resulted in increases in most of the other
emission (e.g. unregulated) with a few minor exceptions.
In trying to estimate the importance of these data, the maximum emission
rate (MER) that was experienced by any of the vehicles tested under any of
the conditions tested was related to the threshold limit value (TLV) as
given in Table 7. The threshold limit values are those established by OSHA
for exposure in an eight-hour work shift. For the compounds listed it would
appear that the higher the MER to TLV ratio the more likely the maximum
emission rate would be a source of concern. However, it should be empha-
sized that definite conclusions are currently inappropriate for any of the
compounds studied with a possible exception of those for which automotive
emissions standards have been established. EPA is currently looking at
various unregulated emissions and plans to define an acceptable level from
many of these unregulated emissions to the extent possible. It should also
be observed that some of the compounds which are considered by OSHA and
other agencies as being non-toxic can have a potential indirect harmful
effect. An example of this would be nitrous oxide, due to its potential
negative effect on the upper atmospheric ozone layer. In reviewing Tables 6
and 7 it is observed that the maximum FTP composite emission rates for HC
and NOx greatly exceeded the standards for 1983. The maximum value for
total particulates, however, was less than one-half of the proposed 0.2 gpm
particulate standard for 1983 Diesel vehicles which would be expected since
gasoline vehicles using unleaded fuel typically have very low particulate
emissions. The maximum undiluted exhaust emission rates for carbon monoxide
and oxides of nitrogen exceed the TLV by over 100. Other compounds in the
undiluted exhaust which exceed an established TLV include benzene and
-------
-26-
Table 6
Number of Cars with Emissions Increase During Malfunction*
-Baseline (non-catalyst) and Oxidation Catalyst Equipped Vehicles-
Number of Cars for Which Emissions Increased/
The Total Cars Evaluated in that Configuration
Rich Best 12% Disabled High Oil R.B.I, and
Idle Misfire EGR Consump. No Air Inj.
Regulated Emissions
Hydrocarbons 4/5 5/5 a
Carbon Monoxide 5/5 5/5 a.
Oxides of Nitrogen 0/5 5/5 5/5
Particulates
Total Particulates 2/4 4/5 3/5
Sulfate 1/5 2/5 0/5
Compound Group Totals
Aldehydes & Ketones 4/5 5/5 5/5
Individuals Hydrocarbons** 4/4 2/2 1/2
Organic Sulfides 2/3 2/4 0/3
Organic Aminesb 5/5 1/4 2/5
Other Compounds
Ammonia 3/5 3/5 ^ 2/5
Cyanide & Cyanogen 4/5 3/5 " 5/5
DMNAC
Hydrogen Sulfide 4/5 1/5 1/5
Nickel Carbonyld
Nitrous Oxide 2/5 2/3 3/3
Other Elements0
3/3
3/3
0/3
3/3
3/3
1/3
1/3
1/3
1/3
0/1
2/2
2/2
0/2
2/2
1/2
1/2
1/2
1/2
1/1
1/1
2/2
1/2
Changes were relatively minor and inconsistent
Changes in organic amines were relatively minor
c Discussed separately
d No nickel carbonyl was ever detected
* Vehicles were:
Emission Controls
Year Make and Model
1977 AMC Pacer
1978 Chev. Malibu
1978 Chev. Malibu (Cal.)
1978 Ford Granda
1978 Ford Mustang II
Engine
CID/CYL
258/6
305/8
305/8
302/8
302/8
Oxidation
Catalyst
None
Pelleted
Pelleted
Monolith
Monolith
Air
**Individual HC consist of lower molecular weight hydrocarbons (methane,
ethane, ethylene, acetylene, propane, propylene, benzene, and toluene)
measured by gas chromatography.
-------
-27-
Table 7
Relative Importance of Malfunction Emission Rates
Baseline (non-catalyst) and Oxidation Catalyst Equipped Vehicles
Regulated Emissions
Hydrocarbons
Carbon Monoxide
Oxides of Nitrogen
Maximum
Emission
Rate (MER)
in mgAma
10800b
52900
4200
Equivalent
Emission MER in
Standard Undiluted
for 1983 Exhaust in
in mg/km mg/m3 (MEC)
255
2113
622C
7000
34400
2700
Threshold
Limit Value Ratio
(TLV)in mg/m3 of MEC
OSHA Re to TLV
55
9
625
300
Particulates
Total Particulates
, Sulfates
48*
17
124d
31
15
1
1
31e(12)f
15e
Compound Group Totals
Aldehdyes & Ketones 228b
Organic Sulfides 2
Organic Amines <1
228
2
10
Other Compounds
Ammonia
Cyanide & Cyanogen
Hydrogen Sulfide
Nickel Carbonyl
Nitrous Oxide
57
7b
4
0.00
70
37
7
4
0
60
00
35
0.007
5
10
Formaldehyde
Benzene
1511
230t
151
182
4
33
38(2)
* FTP rate recorded for the regulated emissions
Value for non-catalyst car - Highest HC value for catalyst car was 2300
c 255 mg/km in California
d Proposed for diesel cars
e Based on values for some similar or Related compounds as set by OSHA(9)
or Recommended by the 1968 American Conference of Governmental Industrial
Hygientists(lO)
f Value for catalyst cars given within the parentheses if the value for
non-catalyst and catalyst equipped vehicles differs substantially
-------
-28-
formaldehyde. Even though benzene and formaldehyde are both suspected
carcinogens, they also are toxic and the TLVs are based on their toxicity.
(The maximum value for ammonia was approximately equal to the TLV). As a
matter of possible interest, the value for carbon dioxide was over 20 times
the established TLV. For the remaining compounds and compound groups, it
was necessary to estimate an equivalent TLV based on best available data.
Based on these estimated values, the maximum levels for total particulates
and sulfate were above the estimated values for an equivalent TLV.
Emissions from a total of four 3-way and 3-way plus oxidation catalyst
vehicles have also been analyzed and the resultant data are presented in
Tables 8 and 9. The same general trend is apparent with these vehicles as
with the oxidation catalyst vehicles, wherein the emissions of a variety of
compounds tend to increase with the malfunction conditions. The same type
of analysis was made with regards to the maximum emission rate compared to
the OSHA eight-hour TLV. It is observed that the maximum undiluted exhaust
emission concentrations for carbon monoxide and oxides of nitrogen exceeded
the TLV by more than the factor of 100. Other compounds for which the
maximum emission rate exceeded an established TLV included benzene and
ammonia. (The maximum values for organic sulfides, hydrogen sulfide, and
formaldehyde were almost equal to the TLV). As a matter of possible,
interest, the value for carbon dioxide was again over 20 times the
established TLV. For the remainder of the compounds it was necessary to
estimate an equivalent TLV based on best available data. Based on these
estimated values, the maximum levels for total particulate, sulfates, and
cyanide and cynanogen were above the estimated values for an equivalent TLV.
It appears as though the following general comparisons may be made for this
malfunction work. Sulfate, ammonia, and nitrous oxides were higher from
catalyst equipped cars than from the one non-catalyst car. Hydrocarbons and
aldehydes were highest from the non-catalyst car. Ammonia and cyanides were
highest from the three-way catalyst cars. It appears that the unregulated
exhaust emissions composition from catalyst equipped cars operating under
malfunctioning conditions is in general distinguishably different: from that
of non-catalyst cars.
-------
Table 8 - Selected FTP Regulated and Unregulated EmI salons
From 3-Way Catalyst Equipped Gasoline Fueled Vehicles
Car 41, Pinto (3-Uay +
Hydrocarbons
Carbon Monoxide
Oxides of Nitrogen
Fuel Consumption
Total Partlculates
Sulfates
Ammonia
Cyanide & Cyanogen
Car 42, Sunblrd (3-way
Hydrocarbons
Carbon Monoxide
Oxides of Nitrogen
Fuel Consumption***
Total Partlculates
Sulfates
Ammonia
Cyanide & Cyanogen
Car 42, Saab 99 (3-way
Hydrocarbons
Carbon Monoxide
Oxides of Nitrogen
Fuel Consumption
Total Partlculstes
Sulfates
Ammonia
Cyanide & Cvannnen
Car 51, Marquis (3 way
Hydrocarbons
Carbon Monoxide
Oxides of Nitrogen
Fuel Ccr.suBpilon
Total Partlculates
Sulfatea
Ammonia
Cyanldu & Cyanogen
Unmodified
Oxld/Alr
0.1
1.3
0.5
11.1
15.3
3.13
6.0
0.1
only)
0.2
2.6
0.5
10.9
5.6
0.21
11.1
1.01
only)
0.1
2.1
0.1
10.8
4.9
0.19
ou.o
1.1
••• 0*ld./A«r>
0.1
1.6
0.8
15.8
2.0
0.85
5.1
0.31
Disabled
Oxygen
Sensor
0.1
1.9
0.3
12.0
2.9
1.03
10.2
- .
1.5*
57.5*
0.1
12.7**
11.1
0.32
68.1
4.13
0.7*
20.0*
0.2
11.6
8.9
0.40
4uJ.5
66.9
0.1
1.0
2.5*
15.5
5.8
1.30
3.4
0.13
12Z
Misfires
0.4
2.4
0.3
11.2
6.5
0.80
6.53
0.1
1.1*
4.7
0.4
10.9
7.5
0.16
36.7
4.09
2.2*
11.1*
0.1
13.0**
17.1
0.31
142.5
7.5
1.7*
8.9*
0.6
16.4
10.0
0.13
30.9
1.57
Disabled
ECRb
0.1
1.8
0.7
11.8
19.7
12.25
13.2
0.0
1.4*
47.6*
0.2
12.2**
28.7
0.12
93.9
6.97
_ _
—
—
—
—
—
—
1.5*
36.5*
0.6
17.1
5.8
0.17
172.4
69.96
High
Oil
Cons.
—
—
—
—
—
—
—
0.2
3.0
0.6
11.3
6.0
0.20
5.31
5.40
0.1
2.3
0.1
11.8
6.4
u.ll
63.3
5.5
__
—
—
—
__
—
—
—
Other
MalfC
1.2*
38.7*
0.1
11.6
7.5
0.05
63.3
10.1
—
—
—
—
—
—
—
0.8*
29.9*
0.1
11.4
12.3
0.18
318.1
36.7
1.8*
52.4*
0=4
18.5**
11.3
0.21
253.0
112.29
I
l-o
8Wlth air to bypaaa for Car 51.
^Oxygen sensor disabled with Cars 41 and 42 and air to bypass with Car 51.
cDlsabled oxygen sensor and air pump with Car 41, disabled oxygen senosr and rich-
bcst-ldle with Car 43, and disabled cold temperature sensor with Car 51.
•Values exceeding 1978 California standards (0.25, 5.6, 0.9 for HC, CO, NOx).
'•Greater than ten percent Increase in fuel consumption relative to unmodified.
•••Liters / 100km
-------
-30-
Table 9
Relative Importance of Maximum Emission Rates
From 3-way Catalyst Equipped Vehicles
Maximum
Emission
Rate (HER)
in mg/km
Emission
Standard.
for 1983
in mg/km
Equivalent
HER in
Undiluted
Exhaust in
mg/m3 (MEG)
Threshold
Limit Value
(TLV) in mg/m3
OSHA(8) Rc
Ratio of
MEQ to TLV
Regulated Emissions
Hydrocarbons
Carbon Monoxide
Oxides of Nitrogen
1,800
52,400^
2,500=
255
2,113
6221
1,100
31,400
1,500
55
9
571
167
Particulates
Total Particulates
Sulfate
Compound Group Totals
Aldehydes & Ketones
Organic Sulfides
Organic Amines
27
3
1
124
24
2
1
1
1
10
7
24
Other Compounds
Ammonia
Cyanide & Cyanogen
Hydrogen Sulfide
Nickel Carbonyl
Nitrous Oxide
253
112
3
0
88
152
67
3
0
53
35
0.007
5
10
4
13
Formaldehyde
Benzene
2
125
2
75
4
33
a FTP rate recorded for the regulated emissions and total particulates
255 mg/km in California
C Based on values for some similar or Related compounds as set by OSHA(8)
or Recommended by the 1968 American Conference of Governmental Industrial
Hygienists (9)
Proposed for Diesel cars
Values were 44 for the HFET
-------
-31-
D. Fuels
1. Fuels Variables
Under EPA contract 68-03-2440 with Southwest Research Institute, the emis-
sions from two different light duty Diesel vehicles (Mercedes Benz 240D and
Volkswagen Rabbit) were tested as a function of five different fuels that
were blended for use in this program (5 and 14). These fuels were 1) the
Emissions Test Fuel that has been used by EPA for Diesel testing since the
late 1960's, 2) a fuel that has the properties of the "national average"
Diesel Fuel, 3) Diesel Fuel number 1, 4) a minimum quality fuel more
typical of the direction towards which today's Diesel fuels are headed, and
5) a premium quality fuel. The data from this testing are presented in
Tables 10 and 11. When the vehicles were tested with those fuels, little
change was seen in hydrocarbon emissions with the exception of the minimum
quality fuel, which increased the HC emission rate. The same was true of
carbon monoxide emissions. The Volkswagen was generally insensitive to
fuels variables with regards to NOx emissions; however, the NOx emissions
went up in the Mercedes with the use of the minimum quality and the premium
quality fuel. Fuel economy generally decreased with the minimum quality and
the premium quality fuels. The most marked change came with particulate
with the minimum quality fuel resulting in a much higher particulate rate in
both vehicles. The percent extractables also was higher. These results,
when combined together, showed a much higher organics emissions rate for the
minimum quality fuel in the Volkswagen; however, in the Mercedes Benz virtu-
ally no change in the organics emissions rates in terms of g/km was seen as
a function of the five fuels. BaP was generally unaffected by four of the
fuels; however, the minimum quality fuel showed a marked increase in the BaP
emission rate. With aldehydes, a marked increase occurred with the minimum
quality fuel.
This work was followed by EPA contract 68-03-2707 wherein the very specific
fuel properties were varied with a base fuel to note their effect on emis-
-------
HC, g/km
CO, g/km
NOx, g/km
Fuel Economy,
mi/gal
Particulate, g/km
Organics, %
Organics, g/km
;\
BaP, ug/km \\
I1
Aldehydes, mg/'km
-32-
Table 10
Emissions Results
From a Volkswagen Rabbit Diesel
Operated on Five Different Fuels
- FTP Cycle -
2D
Emissions-
Test
Fuel
0.18
0.49
0.59
41.2
0.225
10.8
0.024
1.13
28.7
2D
National
Average
0.20
0.51
0.65
42.0
0.218
13.2
0.029
1.33
12.6
ID
"Jet A"
0.17
0.55
0.57
41.2
0.177
15.0
0.027
1.18
18.0
2D
Minimum
Quality
0.71
0.81
0.58
38.1
0.375
15.6
0.059
3.64
52.5
2D
Premium
Quality
0.20
0.52
0.63
39.9
0.194
13.6
0.026
1.05
13.4
-------
-33-
Table 11
Emissions Results
From a Mercedes Benz 240D Diesel
Operated on Five Different Fuels
- FTP Cycle -
HC, g/km
CO, g/km
NOx, g/km
Fuel economy,
mi /gal
Particulate, g/km
Organics, %
Organics, g/km
BaP, ug/km \
Aldehydes, mg/km
2D
Emissions
Test
Fuel
0.12
0.57
0.78
27.7
0.329
11.2
0.037
0.39
16.9
2D
National
Average
0.19
0.64
0.79
27.3
0.314
9.8
0.031
0.46
15.9
ID
"Jet A"
0.09
0.57
0.73
27.6
0.235
12.0
0.028
0.32
16
2D
Minimum
Quality
0.20
0.71
0.88
25.1
. 0.380
7.6
0.029
0.62
23.9
2D
Premium
Quality
0.12
0.68
0.85
25.1
0.292
8.9
0.026
0.23
16.9
-------
-34-
sions (15). The test vehicle was a Mercedes Benz 240D. The data are
presented in Table 12. The principal results that were observed from this
work are the following.
1. Regulated gaseous emissions were not strongly affected by the fuel
variables studied. Hydrocarbon and CO emissions increased slightly
with the high aromatic and cetane-improved aromatic blends. The
cetane-improved aromatic blend also resulted in a small NOx in-
crease. The cetane improver (DII-3) is an alkyl nitrate compound
made by by Ethyl Corporation.
2. Aldehyde emissions were largely unaffected by fuel changes, with
the exception of a fuel designated EM-405-F (base fuel +
isoquinoline at 0.1% N). The increase in aldehydes was sub-
stantial, but not completely understood. The light-end and heavy-
end blends also resulted in slight aldehyde increases, but not of
the magnitude observed with EM-405-F.
3. Phenol emissions (which are co-carcinogenic) were strongly affected
by the shale oil blend. They increased to over 60 times the level
observed with base fuel. The only other pronounced increase in
phenols occurred while testing EM-405-F, base + isoquinoline (0.1%
N).
4. Particulate rates were reduced with the light-end blend and the
olefin blend, by 14 percent and 6 percent, respectively. The two
blends containing aromatics were associated with increases in par-
ticulate emissions of about 27 percent. The cetane-improved aro-
matic fuel blend increased particulate emissions about 68 percent
over those observed with base fuel. Heavy ends fuel apparently did
not cause an increase in particulate emissions, as might have been
expected.
5. Blends containing aromatics resulted in slightly less organic
solubles extracted from particulate matter. Olefins, light ends,
and heavy ends were associated with increases in the amount of
organic solubles.
-------
Table 12
Emissions Results From
A Mercedes 240D Diesel Vehicle Operated
on a Variety of Fuels - FTP Cycle
Base Fuel
C, g/km
3, g/km
Ox, g/km
uel Economy, ml/gal
Articulate, mg/km
rganlcs, Z
rganlcs, mg/km
aP, ug/kra
dor, T1A
Idehydea, mg/km
lenols, mg/km
(H 320)
0.09
0.52
0.75
24.9
165
18.4
30.4
0.53
0
0.61
1.34
Base +
Isoquinollne
0.05 Z N
0.08
0.47
0.76
24.8
162
• 16.0
25.9
0.26
0
t
0.31
4.33
Base +
Isoquinollne
0.1Z N
0.08
0.46
0.89
24.5
162
16.0
25.9
0.35
0.98
15.22
29.40
Base +
Shale Oil Cut
0.05Z N
0.09
0.52
0.87
24.1
180
12.7
22.9
0.96
0
0.00
127.96
Base +
31Z Exxon
"HAN" heavy
aromatlcs
0.12
0.59
0.88
24.7
212
11.8
25.0
0.37
1.31
2.79
0.66
Base +
6% Chevron
alpha
olef Ins
0.09
0.48
0.85
23.9
155
13.9
21.5
0.21
1.45
0.00
0.14
Base +
light
ends
0.11
0.48
0.82
24.7
142
19.9
28.3
0.51
1.35
8.18
0.21
Base +
30% Pure
aroma tics
0.13
0.60
0.92
24.6
219
11.7
25.6
0.73
0.89
0.00
1.30
Base +
heavy
ends
0.08
0.47
0.86
24.4
159
17.5
27.8
0.43
1.09
8.83
0.55
Base +
31Z "HAN"
+ 0.7Z
DII-3
0.13
0.66
1.04
24.4
287
10.8
31.0
0.43
1.05
0.00
0.18
1
OJ
Ln
1
-------
-36-
6. BaP emissions were generally low for the fuel blends tested,
ranging from 0.25 to 0.96 ug/km. A slight reduction was associated
with the olefin blend. A significant increase in BaP, 3 times, was
exhibited by the shale oil blend EM-430-F when compared to the base
fuel.
2. Alternate Fuels
a. Middle Distillates Derived from Alternate Sources
Under the current task order contract (EPA Contract No. 68-03-2884) with
Southwest Research Institute, some alternate fuels evaluations are being
conducted with a Volkswagen Rabbit Diesel (15). So far, four fuels have
been tested which include a base Diesel fuel #2, a Diesel fuel marine #2
obtained from shale oil, a Paraho JP-5 as well as a Coal Case 5A. These
fuels are described in Table 13. The emissions from these fuels are
presented in Table 14. Here it was seen that there was virtually no change
in HC, CO and NOx emissions with the shale marine fuel. This was also true
of the particulate emission rate. The aldehydes, however,, decreased
slightly. The phenols stayed much the same, as well as the odor. There was
a slight decrease in the fuel economy. In looking at the Paraho JP-5, a
slight increase was seen in HC, CO, and NOx as well as a slight decrease in
fuel economy. The particulate was unchanged, as well as aldehydes and odor
while phenols decreased somewhat with use of the JP-5. The coal case
resulted in a rather dramatic increase in HC, CO, NOx and particulate (on
the order of approximately 50 percent), fuel economy also increased, and
phenols and odor went up slightly.
A combination blend of 35% Solvent Refined Coal 2 (SRC2) has been tested,
which resulted in smoke levels that were very very high during the first 105
seconds of the LA4. The smoke and particulate levels were so high that the
sampling system failed and thus testing was unable to be continued. The
SRC2 will be blended at a lower level (approximately 25%) in an attempt to
have the engine operate without exceeding the limits of the sampling
system. Other fuels such as an Exxon EDS fuel and a naptha cut will be
tested in the near future. Other such fuels will also be tested as they
become available (16).
-------
TABLE 13 FUEL PROPERTIES AND COMPOSITION
Substance
Fuel Code (EM-
Cetane No. (D613)
Cetane Index (D976)
Gravity, °API @ 60°F
Density, g/ml @ 60°F
Carbon, wt. %
Hydrogen, wt. %
Nitrogen, ppm (oxid. pyrolysis)
Sulfur (lamp) , %
Calculated H/C, numeric
Carbon No. range (G.C.)
Aromatics, vol. %
Olefins, vol. % (D1319)
Paraffins, vol. %
Viscosity, cs @100 °F (D445)
Gum, mg/100 ml (D481)
Total solids, mg/ic.
Metals in fuel, x-ray
Boiling Range, °C (IBP-EP, D86)
10% point
20% point
30% point
40% point
50% point
60% point
70% point
80% point
90% point
95% point
Residue, wt. % (D86)
Base
DF-r2
329-F
50
52
37.5
0.837
85.8
13.0
48
0.24
1.81
B-r24
21.3
1.7
77.0
2.36
14.3
7.4
oa
191-340
219
231
242
251
260
269
278
290
307
323
1.3
Shale Diesel
Marine
453-F
49
56
37.9
0.835
86.3
13.4
5
<0.005
1.85
9-20
28.5
2.1
69.4
2.61
0.3
0.3
oa
207-317
236
246
252
259
266
272
278
286
295
302
1.0
Paraho
JP-5
473-F
45
46
43.6
0.808
85.9
13.7
<1
<0.005
1.90
22.
2.
76.
1.38
0.0
179-248
189
192
196
198
202
206
211
218
228
237
1.5
Coal Case
5A
474-F
42
41
31.1
0.870
86.5
12.4
0.10
1.71
34.9
1.4
63.7
3.08
42.4
192-366
234
244
253
259
267
276
277
292
330
353
1.5
SRC-II
Med. cetane
475-F
Broadcut
Mid-Continent
476-F
35
57
44.1
0.806
86.1
13.2
0.17
1.83
16.2
0.0 i
83.8 ^
I
1.53
21-354
93
137
159
197
230
250
262
282
327
_
1.0
-------
TABLE 13 (Cont'd). FUEL PROPERTIES AND COMPOSITION
Substance
Fuel Code (EM-
Boiling Range, °C (IBP-EP, D2887)
10% point
20% point
30% point
40% point
50% point
60% point
70% point
80% point
90% point
95% point
Residue, wt. % (D2887)
Composition, Volume %
Kerosene
Petroleum
JP-5
JP-8
Diesel
Petroleum
Shale DFM
Coal SRC- I I
Light Cycle Oil
LSR Naptha
HSR Petroleum
Shale
Coal (Simulated)
N-Butane
Base
DF-2
329-F
104-387
197
220
239
256
268
280
292
307
330
347
0.0
0.0
0.0
0.0
100.0
0.0
0.0
0=0
0.0
0.0
0.0
0.0
0.0
Shale Diesel
Marine
453-F
118-341
216
237
254
265
274
285
297
307
319
325
0.0
0.0
0.0
0.0
0.0
100.0
0.0
0.0
0.0
0.0
0.0
- __^-^6-°
0.0
Paraho
JP-5
473-F
0.0
100.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Coal Case
5A
474-F
17.3
0.0
0.0
66.7
0.0
16.0
0.0
0.0
0.0
0.0
0.0
0.0
SRC-II
Med. Cetane
475-F
0.0
0.0
0.0
65.0
0.0
35.0
0.0
0.0
0.0
0.0
0.0
0.0
Broadcut
Mid-Continent
476-F
.
22.0
0.0
0.0
23.0
0.0
6.2
5.2
7.4
4.8
20.9
0.0
10.5
of Cr, Fe, Ni, Cu, Zn, and Mq; <70 ppm Pb; <100 ppm Al and Si
<10 ppm
-------
-39-
Table 14
Emissions
From Volkswagen Rabbit
Diesel Operated on a Baseline
DF2 Diesel Fuel and Three "Synthetic" Fuels
Fuel •— :
Emissions
HC, g/km
CO, g/km
NOx, g/km
Fuel Economy, mi/ gal
Particulate, g/km
Aldehydes, mg/km
Phenols, mg/km
> Base
DF-2
0.31
0.96
0.66
36.9
0.25
14.0
12.0
Shale
Diesel
Marine
#2
0.31
1.06
0.67
35.5
0.27
9.0
11.0
Paraho
JP-5
0.38
1.20
0.70
35.5
0.25
13.0
0.5
Coal
Case
5A
0.39
1.21
0.83
37.8
0.32
N.Y.A.*
14.0
Odor, TIA
2.3
2.2
2.4
2.8
* N.Y.A. = not yet available
-------
-40-
b. Gasolines Derived from Alternate Sources
In the near future, EPA will be testing a gasoline made from methanol via
the Mobil MGT process and also a gasoline that was blended to
specifications. This latter fuel was blended by the Army Fuels and
Lubricants Laboratory at Southwest Research Institute and will have
properties similar to a synthetic gasoline from oil shale. Also future
possibilities include the SASOL/Kentucky coal run that is currently
underway, which should produce some gasoline that may become available for
EPA tests. Also, Union Oil Company is currently under contract to DOE to
produce some gasoline from oil shale which may be tested by EPA. These last
two sources of alternate gasolines are very tentative and would only be seen
in the somewhat distant future. Efforts continue to obtain these samples
for ECTD testing (16).
To date, ECTD has performed no characterization on alternate source
gasolines due to their lack of availability. In spite of the fact that EPA
had a contract since 1976 with Southwest Research Institute to do gasoline
synthetic fuel work, EPA has been unable to obtain synthetic gasoline
samples (17). Efforts were made to obtain some from the SASOL plant in
South Africa, but they were unwilling in the end to provide fuel samples to
EPA.
c. Alcohol Fuels
Some testing and characterization has been performed by ECTD/CTAB on vehi-
cles fueled with alcohols with more such testing planned for the near
future. One major project that has just been completed involved the testing
of an alcohol-fuel/Diesel-pilot compression-ignition engine from Volvo, as
well as its heavy duty Diesel counterpart (18, 19). The dual-fueled engine
uses Diesel fuel for pilot injection, which initiates combustion and then
uses a variable amount of alcohol, injected subsequent to the pilot
injection for the principal combustion. This engine was tested .with both
methanol and ethanol plus water, as well as a limited number of tests with
an oxidation catalyst added to the dual fueled engine. The counterpart
engine, fueled exclusively with Diesel fuel, was also tested.
-------
-41-
The results from this work are presented in Table 15. It was found that the
use of methanol. resulted in a 50% reduction in total particulate emissions
compared to the single fueled engine. The particulate emitted from the
engine using methanol had 70% organic extractables from the particulate,
indicating far less elemental carbon type substances being formed as was the
case with the conventional Diesel fueled engine, where about 30% organics
were found. Less sulfate is also produced due to lower fuel sulfur levels.
It was also found that the use of methanol decreased NOx by 56% for the 13
mode test and 35% for the transient cycle.
The use of methanol resulted in a hydrocarbon emissions increase as measured
by the heated FID, of about 40% for the 13 mode and 70% for .the transient
cycle compared to the Diesel fueled engine. Large quantities of unburned
alcohol (which is only partially measured by the heated Fill'), were emitted.
In one case, the amount of unburned methanol was four times the amount of
hydrocarbons. Aldehyde emissions were also increased with the use of
alcohol. The use of methanol resulted in a CO increase of about 60%. It
was found that the use of an oxidation catalyst reduced both hydrocarbons
and CO but some increase in NOx was found. The catalyst did not reduce par-
ticulate levels. Ames test data were accumulated on these fuels and will be
presented in the Ames test data section.
Testing has also been performed on a Ford Escort fueled by gasoline as well
as a blend of Anafuel, which is an alcohol-based additive blended with gaso-
line (15). The preliminary results from this work, based on limited
testing, showed a slight decrease in exhaust HC, approximately a 70%
decrease in CO, a 25% increase in NOx, no change in fuel economy, and a
decrease in particulate when the Anafuel case was compared to the gasoline
case. No ethanol or methanol was emitted from the engine when either fuel
was used. With the base fuel, there were negligible quantities of aldehydes
emitted and when the Anafuel was used, there was a very slight increase in
this level of aldehyde. The vehicle appeared to run well on both fuels.
Again, the results with the Anafuel are preliminary and may not be confirmed
with further testing. Some additional EPA in-house testing showed similar
results and also a large increase in evaporative HC emissions.
-------
AND Tllli VG1A/O TIJ-iUUA
PXL.UX/ /n.
Composite emission Kates
Fcdeial Tost Procedure (fTP)
liyd coca i bun, lie*1
g/kw-hr, (g/hp-hr)
Carbon Monoxide, CO
g/kw-hr, (g/hp-hr)
Oxides of Nitrogen, NOXC
q/kw-hr, (g/hp-hr)
lirake Specific Fuel Consump.d
kg fuel/kw-hr, (Ib fuel/hp-hr)
Test Cycle
Total Individual IIC
uig/kw-lir
Total llnbuined Alcohols
mc|/kw-hr
Total Aldehydes6
iwj/kw-lir
Total rhenols
nuj/kw-hc
Total {'articulate
g/kw-hr, 1'i/lip-hr)
Snl fate, SO.=
mg/kw-lir, (t of Part.)
Soluble Organic Fraction (SOF)
mg/kw-hr, (1 of Hart.)
Dal> in SOF
llg/kw-hr
Amos Response (TA9U)
revertant/mg SOF
— — Engine-Teat Configuration -
Uiescl
Volvo TO-100C
13-niode
1.05
(0.78)
3.1U
(2.37)
ll.Bflf
(8.86)
0.262
(0.431)
7 -mode
100
Does Not
Apply
19
Not
Kun
0.69
(0.52)
45
(6.5%)
2OO
(20't)
Transient
1.15
(0.85)
4.04
. (3-01)
11.19
(8.34)
0.288
(0.473)
Transient
130
Does Not
Apply
14
35
0.70
(0.52)
38
(5.4%)
220
(321)
Methanol
Volvo TD-100A
13-niode
1.45
(l.OQ)
9.55
(7.12)
5.26
(3.92)
0.486
(0.799)
7-mode
67
2200
88
17
0.30
(0.23)
14
(4.6%)
200
(66%)
Transient
1.95
(1.45)
10.29
(7.67)
7.31
(5.45)
0.531
(0.873)
Transient
180
4900
250
24
0.39
(0.30)
16
(4.1%)
280
(73%)
Hethanol-Catalyst
Volvo TO- 100 A
13-modeh
0.16
(0.12)
O.B3
(0.62)
6.79
(S.06)
0.482
(0.792)
7-mode
32
950
140
14
0.51
(0.38)
220
(43%)
70
(14%)
Transient^
0.22
(0.1C)
3.74
(2.79)
7.89
(5.89)
0.547
(0.900)
Transient
66
890
260
48
0.37
(0.27)
98
(27%)
60
(16%)
Ethanol
Volvo TD-100A
13 mode
1.65
(1.23)
10.53
(7.85)
6.88
(5.13)
0.396
(0.651)
7-mode
Not
Run
Transient
2.27
(1.69)
12.89
(9.61)
7.38
(5.50)
0.435
(0.715)
Transient
600
2300
240
44
0.35
(0.26)
14
(4.0%)
190
(53%)
Ethanol -Catalyst3
Volvo TD-IOOA
13 mode
0.60
(0.45)
3.10
(2.31)
7.98
(5.95)
0.400
(0.657)
7-mode
Not
Run
Transient
0.63
(0.47)
4.24
(3.16)
8.62
(6.43)
0.448
(0.737)
Transient
220
480
250
33
0.38
(0.28)
89
(23%)
40
(11%)
Ethanoli 301 Water
Volvo TD-IOOA
13-moclo
1.U9
(1.41)
9.99
(7.45)
4.46
(3.32)
0.495
(0.814)
7-mode
220
860
91
Not
Run
0.33
(0.243)
17
(5.2%)
190
<5B'l)
Transient
Not
Run
Transient
Not
Run
(>Hun with backpressure device engaged during idle and motoring.
IIC vulue reported here in based on measurements by IIL'ID. FID response is
( very low (or unbiirned alcohols- and other species of unregulated emissions
13-mode HOX correction factor for intake humidity was computed but not
applied
Computed on the basin of measured diesel consumption and alcohol consumption
combined
•e
^Uenzaldehyde was not included In the total composite value
HOX value is reduced to 10.89 g/kw-hr (8.12 g/hp-hr) when the intake
d
humidity correction for NOX is applied.
I'henols were determined from only selec
nly selected modes
"Without backpressure device at idli
Average of data with ami without backpressure device
-------
TAHLIi .1.5. SUMMAUY OL1 COMPOSITE EMliJblUN KAius r KVJI-I mii vwi-,v
AND THE VOLVO TD-100A DIESEL PILOT/ALCOHOL ENGINE
Composite Emission Rates
Federal Tost Procedure (FTP)
hydrocarbon, MC^
g/kw-hr, (g/hp-hr)
Carbon Monoxide, CO
g/kw-hr, (g/hp-hr)
Oxides of Nitrogen, NOXC
g/kw-hr, (g/hp-hr)
Brake Specific Fuel Consump.d
kg fuel/kw-hr, (Ib fuel/hp-hr)
Test Cycle
Total Individual IIC
mg/kw-hr
Total Unburned Alcohols
mq/kw-hr
Total Aldehydes6
mg/kw-hr
Total Phenols
mg/kw-hr
Total Particulate
g/kw-hr, (<|/hp-hr)
SulCate, S04=
mg/kw-hr, (* of Part.)
Soluble Organic Fraction (SOF)
mq/kw-hr, (I of Part.)
DaP in SOF-
pg/kw-hr
Ames Response (TA98)
revertant/mg SOF
Engine Teat Configuration
Diesel
Volvo TD-100C
13-mode
1.05
(0.78)
3.18
(2.37)
11. 88^
(8.86)
0.262
(0.431)
7-mode
100
Does Not
Apply
19
Not
Run
0.69
(0.52)
45
(6.5t)
200
(2fH)
Transient
1.15
(0.85)
4.04
. (3.01)
11.19
(8.34)
0.288
(0.473)
Transient
130
Does Not
Apply
14
35
0.70
(0.52)
38
(5.4%)
220
(32%)
Methanol
Volvo TD-100A
13-mode
1.45
(1.08)
9.55
(7.12)
5.26
(3.92)
0.486
(0.799)
7-mode
67
2200
88
17
0.30
(0.23)
14
(4.6%)
200
(66%)
Transient
1.95
(1.45)
10.29
(7.67)
7.31
(5.45)
0.531
(0.873)
Transient
180
4900
250
24
0.39
(0.30)
16
(4.1%)
280
(73%)
Methanol-Catalyst
Volvo TD-100A
13-modeh
0.16
(0.12)
0.83
(0.62)
6.79
(5.06)
0.4B2
(0.792)
7-mode
32
950
140
14
0.51
(0.38)
220
(43%)
70
(14%)
Transient^
0.22
(0.16)
3.74
(2.79)
7.89
(5.89)
0.547
(0.900)
Transient
66
890
260
48
0.37
(0.27)
98
(27%)
60
(16%)
Ethanol
Volvo TD-100A
13 mode
1.65
(1.23)
10.53
(7.85)
6.88
(5.13)
0.396
(0.651)
7-mode
Not
Run
Transient
2.27
(1.69)
12.89
(9.61)
7.38
(5.50)
0.435
(0.715)
Transient
600
2300
240
44
0.35
(0.26)
14
(4.0%)
190
(53%)
Ethanol-Catalysta
Volvo TD-100A
13 mode
0.60
(0.45)
3.10
(2.31)
7.98
(5.95)
0.400
(0.657)
7-mode
Not
Run
Transient
0.63
(0.47)
4.24
(3.16)
8.62
(6.43)
0.448
(0.737)
Transient
220
480
250
33
0.38
(0.28)
89
(23%)
40
(11%)
ethanoli-301 Water
Volvo TD-100A
13-mode
1.89
(1.41)
9.99
(7.45)
4.46
(3.32)
0.495
(0.814)
7-mode
220
SCO
91
Not
Run
0.33
(0.243)
17
(5.2%)
190
(581)
Transient
Not
Run
Transient
Not
Run
^Kun with backpressure device engaged during idle and motoring.
IIC value reported here in based on measurements by IIF1D. FID response is
(.very low for unhurried alcohols and other species of unregulated emissions
13-mode NOX correction factor for intake humidity was computed but not
applied
Computed on tho basin of measured dier.el consumption and alcohol consumption
combined
e
^Bcnzaldchyde was not included in the total composite value
NOX value is reduced to 10.89 g/kw-hr (8.12 g/hp-hr) when the intake
humidity correction for NOX is applied.
Phenols were determined from only selected modes
.Without backpressure device at idle
Average of data with and without backpressure device
-------
-43-
Future work in the alcohol area will include the testing of a Volkswagen
that is fueled exclusively by methanol and compared to the results from a
Volkswagen fueled exclusively by gasoline. It is also hoped that an Escort
designed for use with 100% methanol can be obtained such that its emissions
data can be compared to the data discussed above. The Volkswagen will be
tested and its emissions analyzed by mass spectroscopy so that a broad
characterization, in a qualitative sense, can be made between the emissions
from these gasoline-fueled and methanol-fueled engines.
E. Nitrosamines
Nitrosamines are a group of compounds that take the general form of
R?N=NO. Nitrosamines have been described as among the most broadly acting
and the most potent carcinogens. More than 100 nitrosamines have been
tested for carcinogenic activity and most of them have induced tumors in
rats. A smaller number have been tested in hamsters, mice, or guinea pigs,
and again most of those tested have been carcinogenic. As a result nitro-
samines are considered to be very hazardous to humans because of their
assumed carcinogenicity in humans.
Very little monitoring of roadside nitrosamines has been performed. How-
ever, what limited work has been done to date has shown instances of nitro-
samines up to approximately one microgram per cubic meter. It appears as
though these roadside levels are mobile source related. However, only two
sources of nitrosamines have been confirmed, as well as one possible
source. The confirmed sources included are 1) crankcase emissions from
heavy-duty Diesels, and 2) automobile interior emissions (20, 21, 22, 23,
24). The possible source of nitrosamines is indicated by one datum point
that showed nitrosamines may be present in heavy-duty Diesel exhaust. This
latter datum point is, as of yet, unconfirmed.
The work on nitrosamines from heavy-duty Diesel crankcases indicated that
the most likely source for these nitrosamines was the oil additives that are
used for purposes of improving the performance characteristics of the oil.
There is a clear association between the nitrosamine emissions from an
engine using new oil and the level of nitrosatable amines that is measured
-------
-44-
by a bench procedure. There was also an influence due to engines (probably
those factors influencing NOx emission rates) as well as a probable associ-
ation -with the amount of time that the oil is used. However, this latter
association has not been totally confirmed. There would also be nitro-
samines from light-duty Diesel blowby. A number of different sources have
indicated that neither nitrosamines nor nitrosamine precursors are emitted
in the exhaust of gasoline vehicles. -It is very likely that gasoline
engines would also have nitrosamines in their blowby. However, the blowby
from gasoline vehicles is currently recirculated through the engine.
The significance of the roadside concentrations is not easy to estimate very
accurately, due to the lack of models specifically tailored for that purpose
and the lack of adequate nitrosamine roadside monitoring data. However,
some very rough approximations have shown that the number of cancer
incidences per year may not be insignificant for the exposure levels
detected.
Also, some recent EPA work has shown nitrosamines to be present: in vehicle
A
interiors (23). In the Vehicle interior work, 56 vehicles were sampled for
nitrosamines. Of these \56 vehicles, detectable levels of nitrosamines were
found in 47. Concentrations of detectable nitrosamines in these vehicles'
interiors ranged from 0.01 to 0.16 micrograms per cubic meter. The test
results indicated an N-dimethyl nitrosamine (NDMA) dependence on mileage and
time with NDMA levels decreasing slightly with time and mileage. Also, an
NDMA dependence on -temperature was observed, with higher temperatures giving
higher levels of NDMA. The levels of NDMA in vehicles during operation was
observed to decrease somewhat, but they rebounded quite rapidly after
operation. Also similar levels of NDMA in vehicles were observed after
either an overnight soak or for vehicles closed for only a short time.
Nitrosamines were found in passenger cars, stationwagons, passenger and
cargo vans, pick-up trucks, as well as in new and used heavy-duty trucks.
Nitrosamines were not detected in motor homes. A very rough analysis was
made and it was observed that on the average, the daily intake of nitro-
samines from vehicle interiors would be less than the amount contained in a
can of beer (before nitrosamines in beer were regulated to lower levels) and
more than the level found in a strip of bacon (bacon is currently regulated
for nitrosamine content).
-------
-45-
F. Identification of Types of Compounds Responsible for Ames Test Activity
in Diesel Particulates
Many investigators including those in EPA, the automotive industry, and
private investigators such as those at the University of California at
Berkeley, are conducting studies to identify the compounds responsible for
the Ames test activity of Diesel particulate extract. These researchers
have spent effort in separating the methylene chloride extract of Diesel
particulates by high pressure liquid chromatography (HPLC). Three major
fractions have been obtained by HPLC: non-polar, moderately polar (tran-
sition), and highly polar.
The non-polar fraction consists of aliphatic and polynuclear aromatic hydro-
carbons (many of them alkyl substituted) which were responsible for only a
portion of the Ames test activity.
The transition and polar fractions accounted for most of the Ames test
activity. About 50% by weight of the material in the transition fraction
consisted of various oxygenated polynuclear aromatic hydrocarbons (including
hydroxy, ketone, carboxaldehyde, quinone, acid anhydride, and nitro com-
pounds). The polar fraction consisted of carboxylic acid polynuclear aro-
matic hydrocarbons which also have significant Ames test activity (25).
Appendix 1 (26) lists the compounds which have been identified so far in the
joint project on Diesel particulate fractions being conducted by Ford Motor
Company and EPA.
Appendix 2 lists the compounds which have been identified by Sklarew et al.
of Battelle Northwest.
G. Development of Method to Collect/Characterize Gas-phase Hydrocarbons
OMSAPC has been concerned about the potential hazard of automooile exnaust
hydrocarbons for several years- As such. OMSAPC has been very interested in
the development of a method to collect artifact-free samples ot gas phase
-------
-46-
hydrocarbons in motor vehicle exhaust for bioassay testing. EPA/ESRL has
evaluated both a filter cartridge and a condensate method and ECTD has done
some limited gas phase sampling and analysis.
Preliminary tests performed by ESRL have been done with a method involving
filtering the exhaust particulates and then condensing components in the gas
stream. The condensate appeared to have low Ames test activity. If the
filter upstream of the condenser were removed, the condensate contained some
Diesel particuate and had somewhat higher Ames test activity.
The filter cartridge method involved passing a gas stream sample after a
conventional particulate filter through a cartridge or bed of treated XAD-2
resin. After the gas stream was passed through the XAD-2, the hydrocarbons
adsorbed onto the XAD-2 were removed from the resin by methylene chloride
extraction. The lower molecular weight hydrocarbons (e.g. below C-10) were
sufficiently volatile that they were probably lost during the extraction.
However, hydrocarbons above C-10 were retained and could then be subject to
the Ames test. Since the conventional particulate filter generally retained
hydrocarbon compounds above C-15, the XAD-2 traps could provide a good
method to collect hydrocarbons in the C-10 to C-15 range (25).
A very preliminary result of Ames testing on the gas phase hydrocarbon col-
lected by this method for a VW Diesel Rabbit showed that the activity may be
low compared to that of the particulate.
ECTD/TAEB has done some work wherein a light-duty Diesel vehicle was used to
load a large filter with particulate. The volatile organic material was
then driven off by heating the filter to 1000°F which is slightly below the
ignition point of carbon. These "organic free" filters were then put
downstream of a particulate filter in a stream of Diesel exhaust. Thus,
presumably the "organic free" filters would be subjected only to the gas
phase hydrocarbons of the exhaust stream. The carbon on the downstream
filter provided a media for collection of the hydrocarbons. The preliminary
results of this work indicated 1) collection of some hydrocarbon material
on the filter, and 2) some apparently significant Ames test activity
associated with the hydrocarbons thus collected (27).
-------
-47-
H. Ames Testing
ECTD has conducted a number of experiments wherein the emissions were
sampled and subjected to the Ames bioassay test. One such study was with
the Diesel fuels project (discussed in section IV D 1.) and these data are
summarized in Tables 16 and 17. These data seemed to show little effect
from fuel nitrogen levels when the nitrogen was introduced in the form of
isoquinoline. There also appeared to be a trend towards a decrease in
activity when olefins were introduced to the base fuel. The heavy ends
indicated a possible trend towards increasing Ames test activity and also
the same could possibly be said for the cetane improver as it appeared to
increase .the Ames test activity. The other trend appeared to be towards an
increase in Ames test activity with the use of aromatics. This included the
heavy aromatic naptha (HAN) as well as the individual aromatics (15).
These findings tend to be corroborated with the preliminary results reported
by Sklarew from Battelle Northwest. Sklarew et al. rather extensively char-
acterized Diesel particulate extract from filters provided by ECTD from the
Southwest .Research Institute fuels project discussed above. These samples
were taken when the vehicle was operated on 1) base fuel, 2) base fuel +
isoquinoline (0.05% N), 3) base fuel + isoquinoline (0.10% N), and 4) base
fuel + HAN + cetane improver. They concluded that there was a slight but
positive correlation between higher aromatic content in- the parent fuel and
mutagenicity of the chemical fractions from combustion particulates of that
fuel. No correlation was found by them between increased mutagenicity and
the nitrogen content (from isoquinoline) of the parent Diesel fuel.
However, they also observed that the fuel with isoquinoline added prior to
combustion appeared to have lower mutagenic activity than the same fuel
without isoquinoline. Their preliminary data suggested that the high
aromatic Diesel fuels gave rise to higher concentrations of indirect acting
mutagens in the aromatic hydrocarbons, moderately polar or neutrals and
highly polar neutrals than do the low aromatic Diesel fuels (28).
The other set of Ames test data that has been recently analyzed was that
from the Volvo testing wherein the dual fueled Volvo (which employed Diesel
-------
-48-
TABLE 16... SUMMARY OF AMES BIOASSAY ANALYSIS OF ORGANIC SOLUBLES FROM
PARTICULATE MATTER COLLECTED DURING FTP
' Fuel Code
EM-395-F
EM-404-F
EM-405-F
1 EM-430-F
; EM-434-F
EM-438-F
EM-448-F
i
EM-401-F
EM-460-F
EM-461-F
'EM-463-F
Description
base
base + isoquinoline
(0.05% N)
base + isoquinoline
(0.10% N)
base + shale
oil cut
base + "HAN"
base + olefins
base + light ends
JP-7
base + individual
aromatics
base + heavy ends
EM-434-F *
cetane improver
RLI-16
Activation
No
Yes
No
Yes
No
Yes
No
Yes
NO
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
,, Yes
Model Predicted
Mean Slope, revertants/ug extract
TA-1535
0.0
0.0
0.0
0.1
0.0
0.2
0.3
0.0
0.0
0.1
0.0
0.0
0.0
0.1
0.0
. 0.1
• 0.0
0.1
0.0
0.1
0.0
0.1
TA-1537
0.2
0.3
0.7
0.5
0.1
1.1
0.2
0.2
0.7
0.5
0.1
0.2
0.4
1.3-
0.2
0.3
0.7
0.4
0.3
0.5
0.7
0.6
TA-1538
0.7
0.4
1.7
1.0
0.5
0.9
0.6
0.7
1.7
1.1
0.3
0.5
0.9
0.7
1.4
0.9
1.7
0.9
1.2
1.0
1.7
0.9
TA-98
3.2
0.9
3.3
3.0
1.9
0.8
1.3
1.0
3.7
1.1
0.8
1.3
4.1
0.9
3.0
3.3
3.5
2.9
3.6
2.7
5.7
2^5
TA-100
3.9
1.9
5.1
1.9
5.5
1.3
4.9
1.9
6.9
2.2
3.0
1.2
3.3
1.4
1.4
8.7
2.6
6.6
2.3
14.0
2.4
-------
-49-
TABLE 17. AMES BIOASSAY ANALYSIS RESULTS IN REVERTANTS PER
DISTANCE DURING FTP
Fuel Code
: EM-395-F
EM-404-F
' EM-405-F
EM-430-F
EM-434-F
i EM-438-F
EM-448-F
EM-401-F
EM-460-F
EM-461-F
1 EM-463-F
Description
base
base + isoquinoline
(0.05% N)
base + isoquinoline
(0.10% N)
base + shale
oil cut
base + "HAN"
base + olefins
base + light
ends
JP-7
base + individual
aromatics
base + heavy
ends
EM-434-F +
cetane improver
RLI-16
Activation
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
Model Predicted
Mean Slope, 103 revertants/kiria
TA-1535
0.0 .
0.0
0.0
2.
0.0
5.
7.
0.0
0.0
3.
0.0
0.0
0.0
3.
0.0
3.
0.0
3.
0.0
3.
0.0
3.
TA-1537
7.
11.
16.
12.
3.
29.
5.
5.
18.
13.
2.
4.
11.
37.
5. .
8.
18.
10.
8.
14.
22.
19.
TA-1538
25..
14..
40.
23.
13.
24.
14.
16.
43.
28.
6.
11.
25.
20.
. 36.
23.
44.
' 23.
33.
28.
53.
28.
TA-98
112.
32.
77.
70.
50.
21.
30.
23.
93.
28.
17.
28.
116.
25.
77.
85.
90.
74.
100.
75.
176.
77.
TA-100
137.
67.
119.
44.
145.
34.
112.
43.
173.
55.
65.
26;
93.
40.
^ ,_
36.
223.
67.
184.
64.
433.
74.
^calculation incorporates particulate mass rates based on 47 mm Pallflex filters,
percent organic solubles extracted from Pallflex "20x20" filters, and data in Table 23.
-------
-50-
fuel pilot injection and alcohol main injection) was tested and compared
against a baseline pure Diesel Volvo engine.
Table 18 shows that the change between the methanol and methanol plus
catalyst case resulted in a 20% decrease in particulate and an 82% decrease
in organics with use of the catalyst. However, the use of the catalyst also
resulted in a very dramatic increase in the revertants per plate as seen in
the first column of data. This increase was between about 300 and 5,400%.
However, when the accompanying reduction in organics was incorporated into
the data, the increase in revertants per kilowatt hour column was not nearly
as dramatic. However, there was still generally an increase per kilowatt
hour associated with the methanol with catalyst configuration. Basically
the same trend was exhibited by the ethanol and ethanol catalyst comparison.
Table 19 shows the data from the pure Diesel fueled baseline engine compared
against the dual-fueled engine using methanol. Both transient and the
steady state data are presented. Some preliminary conclusions can be made
from these new data. For example, the Ames test activity results from the
dual fueled engine using methanol tested over the transient cycle were
generally lower than the baseline/pure Diesel fueled engine. However, the
dual fueled engine using methanol and Diesel fuel seemed to show higher
activity than the baseline engine over the 13 mode cycle. This apparent
discrepancy may be explained by looking at the modal data which showed that
the heavier loaded modes tend to result in higher Ames test activity than
lightly loaded modes (an interesting observation in-and-of itself). This
trend was much more pronounced for the dual fueled engine using methanol
than for the pure Diesel fuel engine. This, combined with the fact that the
transient cycle is more lightly loaded than the 13 mode test, could account
for the above mentioned apparent conflict. The steady state runs (13 mode)
with the dual fueled engine using methanol and Diesel fuel with the catalyst
tended to have slightly higher specific activity in revertants per micro-
grams of extract but lower revertants per kilowatt hour responses than the
same engine but without the catalyst. This is in some conflict with the
earlier data as presented in Table 18 wherein the transient cycle comparison
showed both the specific activity and the revertants per kilowatt hour to be
-------
Table 18
Average Percent Change Between Two Variables
Dual Fueled Volvo TD100A - Transient Composite Test Cycle
Variable A
Variable B
Particulate g/kW-hr
METHANOL
METHANOL W/CAT
-20%
Organics g/kW-hr
Ames Data
TA 98
TA 98
TA 100
TA100
TA1535
TA1535
TA1537
TA1537
TA1538
TA1538
-82%
Rev/Plate-ug Rev/kW
No Act.
Act.
No Act.
Act.
No Act.
Act.
No Act.
Act
No Act.
Act.
A
1001%
457
285
745
None*
1050
4463
1473
5402
296
ce Percent B
Change
Where: A
Bi
A2
B2
99%
0
-30
53
None*
125
694
194
331
-29
B - A
/inns A J
*• ' A
Al
= Results from
= Results from
= Results from
= Results from
ETHANOL
ETHANOL W/CAT
+8%
-79
hr Rev/Plate-ug
899%
534
165
1041
100
25
7608
18699
708
2809
B_ - A,
1+2 2
A2
2
Variable A tested on
Variable B tested on
Variable A tested on
Variable B tested on
Rev/kW hr
115%
36
-43
144
100
-67
1573
3883
73
523
2/11/80
2/11/80
1/27/81
1/17/81
METHANOL
ETHANOL
-13%
-36%
Rev/Plate-ug
126%
125
169
163
None*
200
208
214
242
58
'
METHANOL
W/CAT
ETHANOL W/CAT
+17%
-25%
Rev/kW hr
43%
42
72
68
None*
88
85
105
114
0**
Rev/Plate-ug
110%
146
40
186
225
-61
470
1797
-50
861
Rev/kW hr
58%
86
4
116
100
-63
325
1312
61
621
I
1/1
* "None" indicates no change in the two variables.
** "0" indicates no or negligible Ames test repsonse.
-------
Table 19
Average Percent Change Between Two Variables
Dual Fueled Volvo TD100A
Variable A -^
Diesel-transient Diesel 13-Mode
Variable B —> Methanol-transient Methanol 13-Mode
'articulate g/kW hr -44% -57%
jrganics g/kW hr
\raes Data
TA 98
TA 98
TA 100
TA 100
TA1535
TA1535
TA1537
TA1537
TA1538
TA1538
No Act.
ACT.
No Act.
Act.
No Act.
Act.
No Act.
Act.
No Act.
Act.
+27%
Rev/Plate/ug
-81%
-76%
-81%
-65%
0%
0%
-94%
-90%
-89%
-83%
Rev/kW-hr
-76%
-69%
-75%
-54%
0%
0%
-91%
-86%
-85%
-79%
-0%
Rev/Plate/ug
+156%
+367%
—
3%
0%
0%
0%
0%
0%
0%
Methanol 13-Mode
Diesel 13-Mode
Methanol + Catalyst 13-Mode Ethanol + H20 - 13-Mode
+70% -52%
-65%
Rev/kW-hr
+156%
+367%
—
+ 3%
0%
0%
+ 50%
- 17%
0%
0%
Rev/Plate/ug
- 43%
- 21%
+ 13%
+ 44%
0%
0%
0%
0%
- 33%
+188%
Rev/kW-hr
-80%
-73%
-60%
-50%
0%
0%
-33%
-60%
-75%
0%
- 5%
Rev/Plate/ug
- 56%
0%
__
+ 60%
0%
- 67%
-100%
- 83%
- 83%
- 38%
Rev/kW-hr
- 56%
- 08%
—
+ 61% ,
0% £
- 67% '
-100%
- 83%
- 83%
- 38%
-------
-53-
higher with the catalyst than without the catalyst. Therefore, one would
conclude that the test cycle is very important when analyzing the Ames test
data from those engines (18).
-------
-54-
V. References
1. Springer, Karl J., "Characterization of Sulfates, Odor, Smoke, POM, and
Particualates From Light and Heavy Duty Engines - Part IX", EPA-OMSAPC
Contract 68-03-2417 with Southwest Research, Report No.
EPA-46013-79-007, June 1979.
2. Ullman, T.L., Springer, K.J., and Baines, T.M., "Effects of Six
Variables on Diesel Exhust Particulate", ASME Paper 80-DEP-42, February
1980.
3. Baines, Thomas M., Somers, Joseph H., and Harvey, Craig A., "Heavy Duty
Diesel Particulate Emission Factors", Journal of the Air Pollution
Control Association, 29, 616, 1979.
4. EPA-OMSAPC Contract No. 68-03-2706 with Southwest Research, "Unregulated
Emissions Characterization of Heavy-Duty Diesel and Gasoline Engines and
Vehicles", contract in progress.
5. Hare, Charles T., "Characterization of Gaseous and Particulate Emissions
from Light Duty Diesels Operated on Various Fuels", EPA-OMSAPC Contract
No. 68-03-2440 with Southwest Research Institute, Report No.
EPA-460/3-79-008, July 1979.
6. Springer, Karl J. and Baines, Thomas M., "Emissions from Diesel Versions
of Production Passenger Cars", SAE Paper 770818, September 1977.
7. Dietzmann, Harry E., Smith, Lawrence R., Parness, Mary Ann, and Fanick,
E. Robert, "Analytical Procedures for Characterizing Unregulated
Pollutant Emissions from Motor Vehicles", EPA-ORD Contract No.
68-02-2497 with Southwest Research Institute, Report No.
EPA-600/2-79-017, February 1979.
-------
-55-
8. Smith, Lawrence, Parness, Mary Ann, Fanick, E. Robert, and Dietzmann,
Harry E., "Analytical Procedures for Characterizing Unregulated Emissions
from Vehicles Using Middle Distillate Fuels", EPA-ORD Contract 68-02-2497
with Southwest Research Institute, Report No. EPA-60012-80-068, April 1980.
9. Urban, Charles, "Regulated and Unregulated Exhaust Emissions from
Malfunctioning Non-Catalyst and Oxidation Catalyst Gasoline Automobiles",
EPA-OMSAPC Contract No. 68-03-2499 with Southwest Research Institute,
Report No. EPA-460/3-80-003, January 1980.
10. Urban, Charles, "Regulated and Unregulated Exhaust Emissions from
Malfunctioning Three-Way Catalyst Gasoline Automobiles", EPA-OMSAPC
Contract No. 68-03-2588 with Southwest Research Institute, Report No.
EPA-460/3-80-004, January 1980.
11. Urban, Charles, "Regulated and Unregulated Exhaust Emissions from a
Malfunctioning Three-Way Catalyst Gasoline Automobile", EPA-OMSAPC
Contract No. 68-03-2694 with Southwest Research Institute, Report No.
EPA-460/3-80-005, January 1980.
12. Urban, Charles M. and Garbe, Robert J., "Regulated and Unregulated Exhaust
Emissions from Malfunctioning Automobiles", SAE Paper 790696, June 1979.
13. Urban, Charles M. and Garbe, Robert J., "Exhaust Emissions From
Malfunctioning Three-Way Catalyst Equipped Automobiles", SAE Paper 800511,
February 1980.
14. Hare, Charles T. and Baines, Thomas M., "Characterization of Particulate
and Gaseous Emissions from Two Diesel Automobiles as Functions of Fuel and
Driving Cycle", SAE Paper 790424, March 1979.
15. EPA-OMSAPC Task Order Contract No. 68-03-2884 with Southwest Research
"Basic Characterization Support for the Emission Control Technology
Division", contract in progress.
-------
-56-
16. EPA-OMSAPC Task Order Contract No. 68-03-3073 with Southwest Research
Institute, "Pollutant Assessment Support for the Emission Control
Technology Division", contract in progress.
17. Newman, Frank M., Russell, John A., Bowden, John N., and Johnston, Alan
A., "Impact of Coal and Oil Shale Products on Gasoline Composition
1976-2000, Task 1 Final Report", EPA-OMSAPC Contract 68-03-2377 with
Southwest Research Institute, December 1976.
18. Ullmann, Terry L., and Hare, Charles T., "Emission Characterization of an
Alcohol Fueled/Diesel Pilot Compression-Ignition Engine and its Heavy-Duty
Diesel Counterpart", EPA-OMSAPC Contract No. 68-03-2884, Task 6, with
Southwest Reearch, Final. Report in Press.
19. Holmer, E., Berg, P.S., and B-I Bertilsson, "The Utilization of
Alternative Fuels in a Diesel Engine Using Different Methods", SAE Paper
800544, February 1981.
20. Hare, Charles T. and Montalvo, Daniel A., "Diesel Crankcase Emissions
Characterization", EPA-OMSAPC Contract No. 68-03-2196, Task 4, with
Southwest Research, May 1977.
21. Fine, David H. and Goff, Ulku, "Nitrosamine Analysis of Diesel Crankcase
Emissions", EPA-OMSAPC Contract 68-03-2719 with New England Institute of
Life Sciences, Report No. EPA-460/3-81-008, March 1980.
22. Baines, Thomas M. , "Nitrosamines and Other Hazardous Emissions From Engine
Crankcases", EPA-OMSAPC Report No. EPA/AA/CTAB/PA/81-15, June 1981.
23. Smith, Lawrence R., "Nitrosamines in Vehicle Interiors", EPA-OMSAPC
Contract No. 68-03-2588 with Southwest Research, Final Report in Press.
24. Goff, E. Ulku, Coombs, James R. , Fine, David H. , and Baines, Thomas M.,
"Nitrosamine Emissions from Diesel Engine Crankcases", SAE Paper 801374,
October 1980.
-------
-57-
25. Somers, Joseph H., "Brief Synopsis of EPA Office of Research and
Development and Health Effects Institute Mobile Source Work", EPA-OMSAPC
Report No. EPA/AA/CTAB/PA/81-10, May 1981.
26. Schuetzle, Dennis, Lee, Frank S.C., and Prater, Thomas J., "The
Identification of Polynuclear Aromatic Hydrocarbon Derivatives in
Mutagenic Fractions of Diesel Particulate Extracts", International Journal
of Environmental Analytical Chemistry, 9_, 93, 1981. _
27. Penninga, Thomas J., "Evaluation of Mutagenic Characteristics of Diesel
Gaseous Hydrocarbons", EPA-OMSAPC Report No. EPA/AA/TEB/81-22, July 1981.
28. EPA-ORD Mobile Sources/Health Effects Project Status Report, 1981 - Work
in progress.
-------
-58-
VI. Appendixes
Appendix 1
Compounds Identified in Diesel Particulate Emissions
This Appendix is reprinted directly from the following publication:
Dennis Schuetzle, Frank S.C. Lee, and Thomas J. Prater, Ford Motor Co., and
Silvester B. Tejada, EPA, "The Identification of Polynuclear Aromatic Hydro-
carbon Derivatives in Mutagenic Fractions of Diesel Particulate Extracts",
presented at the 10th Annual Symposium on the Analytical Chemistry of Pol-
lutants, Dortmund, Germany, May 28-30, 1980 which was published in the
"International Journal of Environmental Analytical Chemistry", 9, 93 (1981).
-------
-59-
TABLE IV
RELATIVE A1TJMDANCZS OF PAH SPECIES IDENTIFIED 3Y
GC/MS (25m DEXSIL 300 CAPILLARY COLUMN7) AND H2MS FOR THE PAH!
HPLC FRACTIONS OF A DIESEL PARTIOJLATE EXTRACT (OL-1)
Compounds
Phenanthrene and Anthracene
Methyl (Phenanthrenes and Anthracenes)
Flvioranthene
Pyfene
Dihydro (Fluoranthenes and Pyrenes)
Diaethyl (Phenanthrenes and Anthracenes)
Benzofluorenes
Methylpyrenes
Behzylnaphthalenes
Trimechyl (Phenanthrenes or Anthracenes)
Cyclopentapyrene
Berizo(a) Anthracene(BaA); Chrysene»and Triphenylene
Diphenylbenzene
Methyl (BaA, Chrysene and Triphenylene)
Benzofluoranthenes
Benzo(e) Pyrene(BeP), Benso(a) Pyrene(BaP) and Perylene
Methyl Benzofluoranthenes
Methyl (BeP, BaP, Perylene)
Benzo(g,h,i) Perylene and Anthanthrene
Coronene
Dibenzopyrenes
Formula
C14H10
C15H12
C16H10
CI&HIO
C16H12
Cl6H14
C17H12
C17H12
C17H14
C17H16
CisH^o
C18H12
C18H14
C19H"4
^20^12
C20Hi2
^21^14
^21^14
C22H12
C2/Kj.2
C24H14
1
Mass
178.078
192.094
202.078
202.078
204.094
206.110
216.094
216.094
218.110
220.126
226.078
228.094 .
23o.no
242,110
252.094
252.094
266.nO
266.110
276.094
300.094
302.no.
Relative2
Abundance
0.27
0.54
0.41
• 0.41
0.09
1.00
0.67
0.55
0.18
0.37
0.47
0.16
0.11
0.42
0.33
0.48
0.13
0.16
0'.25
0.06
0.02
"Measured to within + 10 ppm at 12K resolution.
2 , .
Abundance relative to dimethyl (phenanthrenes and anthracenes)
-------
TABLE V
CHEMICAL COMPOSITION OF THE fl - IJPLC FRACTIONS OF A DIESEL PARTICULATE EXTRACT (NI-1)
COMPOUND
Anthaulhroiie or Isomera (C22"l2)
Methyl Am hanthrene or Isomers (C23"l4)
Coronene (C2/,l'l2)
I)il>ai»/o|>yrune (C2/lUi/,) - 2 leoiners
Methyl Coronenu
llydroxy Coronene
Cyclopentacoronene or
MASS
Found
276.097
290.108
300.092
302 . 106
314.109
316.091
326.111
Theory 24 25
276.094 0.181 0.009
290.109 0.362 Q.,269
300.094 0.121 ' 0.159
302.109 0.481 0.097
314.109
316.089 0.034 0.042
326.110
RELATIVE ABUNDANCE
26 27
'
-.-!••
1.000 0.480
0.068 0.128
0.010
0.049 0.051
0.053
(FRACTION (1)
28 29
-
-
0.293 0.073
0.202 0.174
.0.028
0.032
i
0.162 0.109
30
-
-
-
-
'-
~ i
cr>
0.043 °
-------
COMPOUND
2-Naphthalene Carboxaldehyde
.1-Naphthalene Carboxaldehyde
Methyl Naphthalene Carboxaldehyde
i Naphthalene Acetaldehyde
Naphthalene Acetaldehyde
Dimethyl Naphtliaiene-Aarhoxaldehyde
i
9-Fluorenone
'Naphthalene DiearboxarWehyde
Phenanthrene or Anthracene
Naphthalene Dicar^oxaidehyde
i
.Phenanthrone or-iAnchroTte
Naphthalene Dicar-boxald«hyde
j9-Anthrone
Trimethyl Naphthalene Carboxaldehyde
Phenanthrone or Attthrooe
Trlmethylnaphthalene Carboxaldehyde
Fluorene Carfaoxaldehyde
Methyl (Anthracene or Phenanthrene)
Methyl (Anthracene or Phenanthrene)
Fluorene Carboxaldehyde
9-Xanthone
Triaethyl Naphthalene Carboxaldehyde
Fluorene Carboxaldehyde
Methyl (Anthracene or Phenanthrene)
-51-
TASLE VI
>r£CIES IDENTIFIED BY GC/MS (S? 2250 COLUMN) IK THE
. 0? A DIESEL PARTICULATE EXTRACT-OL-I
FORMULA
C11H8°
C1IH8°
C12H10°
C12H10°
C12H10°
C12H8°2
C13H8°
C12H8°2
C14H10
C12H8°2
C14H10°
C12H8°2
C14H10°"
C14H14°
C14H10°
C14*14°
C14H10°
C15H12
C15H12
C14H10°
C13H8°2
C14H14°
C14H10°
C15H12
MASS
156.061
156.061
170.073
170.073
170.073
184.052
180.058
184.052
178.078
184.052
194.073
184.052
194.073
198.104
194.073
198.104
194.073
192.094
192.094
. 194.073
196.052
198.104
194.073
192.094
SCANtf
660
673
779
789
795
868
881
894
895
925
941
943
947
950
961
965
989
991
998
1000
•1004
1010
1021
1022
RELATIVE
ABUNDANCE
0.035
0.059
0.062
0.073
0.015
0.098
1.000
0.1^0
0.260
0.047
0.110
0.028
0.040
0.061
0.197
0.062
0.176
0.128
0.168
0.176
0.039
0.031
0.134
0.136
-------
-62-
COMPOUXD
Trimechyi Naphthalene Carboxaldehyde
2-Methyl S-Anthror.e
Methyl (Anthrone or Phenanthrone)
Dimethyl (Anthracene or Phenanthrene)
9,10 Phenanthreae Quinone
(Pheaanthrene or Anthracene) Quinone
Dimethyl (Anthracene or Phenanchreae)
9,10 Anthracene Quinoae
(Phenanthrene or Anthracene) Quisone
•
Pyrene
Methyl 9,10 Phenanthrene Quinone
Unknown
trimethyl (Anthracene or Phenanthrene)
Methyl 9,10 (Anthracene or Phenanthrene) Quinone
Trimethyl (Anthracene or Phenanthrene)
Fluoranthene
Thioxanthone
Trimethyl (Anthracene or Phenanthrene)
Methyl 9,10 Anthracene Quiaoae
Pyrone
Thioxaathone
(Phenanthrene or Anthracene) Carboxaldehyde
9-Thioxanthone
(Phenanthrene or Anthracene) Carfaoxaldehyde
Fluoranthone or Pyrone
i
Fluoranthone or Pyrone
Methyl (Phenanthrene or Anthracene) Carboxaldehyde
FORMULA
C14E14°
C15K12°
C15H12°
C16H14
C14H10°2
C14E10°2
C16E14
C14H10°2
C14H10°2
C16H10
C15E19°2
C15H8°
C17E16
C15H10°2
C17H16
C16H10 '
C13H8°S
C17E16
C15H10°2
C16E10°
C13H8OS
C15H10°
C13E8°S
C15E10°
C16E10°
C16H10°
C16H12°
MASS
198.104
208.089
208.089
206.109
208.052
208.052
206.109
208.052
208.052
202.078
222.068
204.057
220.125
222.068
220.125
202.078
212.030
220.125
222.068
218.073
212.030
206.073
212.030
206.073
218.073
218.073
220.089
SCAN:?
1040
1057
1077
1090
1094
1105
1111
1122 .
1142
1157
1171
1172
1175
1193
1199
1205
1208
1217
1231
1235
1237
1249
1251
1260
1270
1284
1316
RELATTvl
ASU^DAI-CE
0.030
0 . 241
0.144
0.121
0.063
0.070
0.057
0.231
0.044
0.237
0.180
1.041
0.020
0.092
0.095
0.190
0.057
0.046
0.095
0.087
0.061
0.354
0.269
0.254
0.041
0.043
0.085
-------
-63-
COM?OU!vD
Unknown
'Methyl (Phenanthrene or Anthracene) Carboxaldehyde
Methyl Pyrene
•
Pyrene Quinone
• iMethyl (Phenanthrene or Anthracene) Carfaoxaldehyde
Methyl Fluoranthene
Fluoranthene Quinone
Methyl (Phenanthrene or Anthracene) Carboxaldehyde
Dimethyl (Phenanthrene or Anthracene)
Carboxaldehyde
Pyrene or Fluoranthene Carboxaldehyde
Dimethyl (Phenanthrene or Anthracene)
Carboxaldehyde.
Benzo(d,h) Anthrone
Dimethyl (Phenanthrene or Anthracene)
Carboxaldehyde
(Benzo(a)anthracene, Chrysene or Triphenylene)
Carboxaldehyde
(Benzo(a)anthracene, Chrysene or Triphenylene)
Carboxaldehyde
(Benzo(a) anthracene, Chrysene or Triphenylene)
Carboxaldehyde
(Benzo(a)anthracene, Chrysene or Triphenylene)
Carboxaldehyde •
1-Nitro Pyrene
ihe relative abundance of 9-Fluorenone is arbitrarily given a value of 1.000.
•>
"Mass accuracy is poor due to low ion abundance, therefore, exact empirical formula is
'difficult to establish.
FORMULA
C16H12°
C17H12
C16H8°2
C16H12°
C17H12
C16H8°2
C16H12°
C17H14°
C17H1Q0
1/14
1/10
C17H14°
C19H12° •
C19H12°
C19H12°
C19H12°
C16H9N°2-
MASS
2262
220.089
216.094
232.052
220.089
216.094
232.052
220.089
234.104
230.073
234.104
230.073
234.104
256.089
256.089
256.089
256.089
247.063
SCAN)?
1318
1338
1338
1338
1355
1357
1357
1369
1413
1415
1440
1450
1462
1499
1518
1523
1536
1624
RELATIV:
ABUNDA:-;
0.02^
0.188
0.024
0.024
0.126
0.221
0.023
0.094
0.057
0.409
0.051
0.073
0.027
0.032
0.028
0.028
0.032
0.027
-------
-64-
TASLE VII
A COMPARISON OF THE RELATIVE ABUNDANCES 0? PAH DERIVATIVES
IDENTIFIED BY DIRECT PROSE ERMS AND GC/MS FOR THE
TRANSITION (f HPLC FRACTION OF A DIESEL PARTICULATE EXTRACT (OL-i)
RELATIVE ABUNDANCE
POSSIBLE COMPOUNDS FORMULA MASS KRKS GC/TlS71 HRMS -GC/MS
9-Fluorenone C. ,H00 180.058 1.00 1.00 0.00
J.J 0
Hydroxy Fluorene* C13H10° 182'073 °'15 °-°° 0.15*
Naphthalene Dicarboxaldehyde . C12H8°2 18*'052 °'29 °'32 -0.03
Methyl (Anthracene or Phenanthrene) C15K12 192. 09 A 0.45 0.43 0.02
(Anthrone or Phenanthrone C14H10° I94-073 °-96 °-83 0.13*
Fluorene Carboocaldehyde
Methyl Fluorenone
Hydroxy (Anthracene or Phenanthrene)*
Fluorene Quinone
9-Xanthone C13H8°2 196'052 °'66 Q-^ 0.62*
Hydroxy Fluorenone*
Hydroxy Xanthene* C13H10Q2 198'068 • °'30 °'00 °-30*
Dihydroxy Fluorene*
Trimethyl Naphthalene Carboxaldehyde CiAHiA° 198-10A °-29 0.19 • 0.10
Pyrene or Fluoranthene C.,H,n 202.078 0.37 0.43 -0.05
ia 1U
Unknown C. CH00 204.057 0.80 1.04 -0.24
-L.J o
Anthracene or Phenanthrene (Carboxaldehyde)C.-H..O 206.073 0.76 0.65 0.11
(Phenanthrene or Anthracene) Quinone ' C..H-0. 208.052 0.39 0.4.1 -0.02
-v C..H..O 208.089 0.35" 0.39 -0.04
'Methyl(Anthrone or PhenanthroneJ 15 12
Thioxanthone' C.-H-OS 212.030 0.47 0.39 0.08
J.J o
Methyl Naphthalene Dicarboxylic AcidL c -11-0, 212.047 0.39 0.00 0.39*
Anhydride: 13 5 3
Hydro-xy Xanthone
-------
~65~ RELATIVE ABUNDANCE
POSSIBLE COMPOUNDS FORMULA MASS HRMS GC/MS KRMS-CC/MS
Fluoranthone or Pyrone C .H 0 21S.073 <0.15 0.17 -0.02
iO J. J
'Methyl (Anthrone or Phenanthrene) C.,E..O 220.089 0.60 0.59 0.01
lo lx
(Dihydropyrone or Dihydrofluoranthene)
Aceanthrone or -Aoephenanthrone
Methyl (Anthracene or Phenanthrene) Quinone c1eH1o°2 222t068 °*39 °'37 °'01
Unknown
Dimethyl (Phenanthrone or Anthrone) C^H^O 222.104 0.76 - 0.76*
Dimethyl Hydroxy (Phenanthrene or Anthracene)*
Trimethyl Fluorenone
Dihydroxy Methyl (Anthracene or C15H12°2 224-084 °'4* ~ 0.44*
Phenanthrene)*
Hydroxy Nitro Fluorene* . C13H9N03 227.058 0.18 - 0.18*
(Pyrene or Fluoranthene) Carboxaldehyde C^-H 0 230.073 0.48 0.52 -0.04
Benzo(d,H) Anthrone
\
Dimethyl (Anthracene or Phenanthrene) ci7Hi/° 234.104 0.49 0.14 0.35*
Carboxaldehyde; iy 1
i
Unknown*
Dihydrodihydroxy (Pyrene or Fluoranthene)* C-,H.-0. 236.084 0.30 - 0.30*
XO 1-jL L
Hydroxy Trimethyl (Anthracene or C17H16° 236-120 °'18 " 0.18*
Phenanthrene)*
Nitro Methyl (Anthracene or Phenanthrene)* CL5H11N02237.079 0.14 - 0.14*
1 Those "species that were not eluted in the GC/MS procedure but may be present based upon
HRMS relative abundance values are designated bv a star*
2 Error in relative abundance values are jr7%.
GC/MS identifications for this fraction are presented in Table VI.
-------
-66-
TAELE VIII
RELATIVE ABUNDANCE Or CHEMICAL SPECIES IDENTIFIED BY GC/MS (DEXSIL 300) IN THE
ANALYSIS OF A TRANSITION (Y2) K?LC FRACTION OF A DIESEL PARTICULARS EXTRACT (OL-1)
Compound
9-Fluorenone
Metnyj. Fluorenone
Methyl Fluorenone
Methyl Fluorenone
I Naphto (c,d) Pyrone
Dimethyl Naphthalene Carboxaldehyde
An'throne or Phenanthrone
Lvsphto, 2-3-B-Furan-4,9-dione
Naphthalene Dicarboxaldehyde
Fluorene Quinone
Fluorene Quinone
9-Xanthone
Unknown
Flucrene Quinone
Unknown
Naphthalene Dicarboxylic Acid Anhydride
(Phenanthrene or Anthracene)'Quinone
iferhyl (Anthrone or Phenanthrone)
(Anthracene or Phenanthrene). Carboxaldehyde
rluorene Quinone
CPhenanthrene or Anthracene) Quinone
Methyl Naphthalene Dicarboxylic Acid Anhydride
-iethyl Fluorene Quinone
Methyl Fluorene Quinone
Methyl Fluorene Quinone
•iethyl Naphthalene Dicarboxylic Acid Anhydride
Diaechyl Fluorene Quinone
•isthyl Naphthalene Dicarboxylic Acid Anhydride
}imethyl Fluorene Quinone
)imethyl Naphthalene Dicarboxylic Acid Anhydride
)iaethyl Fluorene Quinone
Jiaethyl Naphthalene Dicarboxylic Acid Anhydride
«
.-iaethyl Naphthalene Dicarboxylic Acid Anhydride
Flucranthene or Pyrene) Quinone
.ethyl (Pyrene or Fluoranthene) Quincne
Benzo(a)Anthracene, Chrysene or Triphenylene) Quinone
Benzo(a)Anthracene, Chrysene or Triphenylene) Quinone
Foraula
C13HgO
ci4BioO
C14H1QO
C14H10°
C12H802
C13H120
Ci4H100
Cj^2Hft03
C12H802
C13HS02
C13H802
C13H802
^12^10^3
C13H802
Cl2Ki003
C12H603
C15E120
C13H802
^14^10^2
Ci3H803
^14^10^2
C14Hio02
C14H10°2
C13H803
C15Hi202
C13EB03
C15H1202
C]_4Hi n03
C15H1202
Cl4Hl(j03.
Ci4H1003
Cj_gE802
C17H10°2
^18^10^2
C1SK10°2
Mass
180.058
194.073
194.073
194.073
184.052
184.089
194.073
198.032
184.052
196.052
196.052
196.052
202.064
196.052
202.064
198.032
208.052
208.089
206.073
196.052
208.052
212.047
•210.063
210.068
210.068
212.047
224.084
212.047
224.084
226.064
224.084
226.064
226.064
232.052
246.063
258.068
253.068
Scar. T?
719
758
787
801
808
846
853
862
863
876
888
900
901
904
912
913
913
923
928
935
948
970
973
979
995
980
1010
1015
1030
1030
1055
1059
1093
1148
1210
1225
1235
• Relative
Abundance
0.157
0.069
0.041
0.046
0.105
0.040
0.175
0.099
0.054 .
0.033
0.040
0.073
0.037
0.133:
0.030
1.000
0.123 :
0.162
0.020
0.053.
0.064
0.123 •
0.102
0.091
0.005
0.111
0.043
0.108
0.035
0.036
0.021
0.120
(2 Isomers)
0.012
0.026
0.005
0.006
0.012
-------
-67-
TABLZ IX
A COMPARISON OF THE RELATIVE ABUNDANCES OF PAH DERIVATIVES IDENTIFIED BY DIRECT PROBE
AND CC/MS FOR TEE TRANSITION (^2) H?LC FRACTION OF A DIESEL PARTICULARS EXTRACT (OL-1)
Relative Abundance.___
r.
Possible Compounds
-Fluorenone
ydroxy Fluorene*
aphthalene Dicarboxaldehyde
iaethyl Naphthalene Carboxaldehyde
athrbne or Phenanthrone
Methyl Fluorenone
9-Xanthone; Fluorene Quinone
ethyl Hydroxy Fluorene*
aphthalene Dicarboxylic Acid Anhydride
/droxy Xanthene*
Dihydroxy Fluorene*
iknown
3henanthrene or Anthracene) Carboxaldehyde
Phenanthrene or Anthracene) Quinone
ithyl (Anthrone or Phenanthrone)
Diaethyl Fluorenone
Methyl Hydroxy (Anthracene or Phenanthrene)*
Jthyl Fluorene Quinone: Dihydroxy Anthracene*
Laethyl Hydroxy Fluorene*
ithyl Naphthalene Dicarboxylic Acid Anhydride
Lhydroxy Methyl Fluorene*
^droxy Naphthalene Dicarboxylic Acid Anhydride*
rihydroxy Fluorene*
;thyl (Anthracene or Phenanthrene) Quinone
^thracene or Phenanthrene) Dicarboxylic
Acid Anhydride
Lnethyl Fluorene Quinone
jnethyl Naphthalene Dicarboxylic Acid Anhydride
Lnydroxy Methyl Fluorene*
iknown*
:knowh*
'luoranthene or Pyrene) Quinone
.hydroxy Dinethyl Anthracene*
.known*
Those species that were not eluced in the GC/MS
Formula
C]jH80
C13Hi00
C12H802
C].3Hi20
Gi4Hi00
C]^H802
Cl4H120
C12H603
Cl3H8°2
C12H1003
C15H100
C1AK802
C15H120
Cl4H]_o02
^15^140
C13H803
^14^12^2
C12H604
C13H1003
C15H1002
C1AH803
C15H1202
Cj_4H]_Q03
Ci5H]_402
C^3H804
^14^12^3
C16H8°2
Cl6Hl4°2
procedure
Mass
180.058
182.072
184.052
184.089
194.073
196.053
196.089
198.031
198.067
202.064
206.073
208.052
208.089
210.068
210.104
212.047
212.084
214.026
214.063
222.068
224.047
224.084
226.064
226.099
228.042
228.078
232.052
238.100
242.094
but nay be
KRMS
0.23
0.30
0.11
0.11
0.30
0.29
0.13
1.00
0.38
0.05
0.03
0.20
0.23
0.27
0.07
0.36
0.20
0.32
0.06
0.26
0.21
0.17
0.16
0.08
0.06
0.03
0.04
O.OS
0.03
present
GC/MS
0.16
-
0.12
0.03
0.33
0.33
-
1.00
-
0.07
0.02
0.19
0.15
0.20
-
0.34
-
-
-
(?) .,
_ (.'
0.10
0.17
-
-
-
0.03
-
••
based
' KRMS-GC/:
0.07
0.30*
-0.01
0.08
-0.03
-0.03
0.13*
-
0.38*
-0.02
0.01
0.01
0.07*
0.07*
0.07*
0.02
0.20*
0.32*
0.06*
i\ ""
0.07
-0.01
0.08*
0.06*
0.06*
0.01
0.08*
0.03*
upon HRMS
relative 'abundance values arc designated by a star*
GC/MS identifications for this fraction are presented in Table VIII.
Presence of compound not confirmed by GC/MS
-------
-68-
Appendix 2
Compounds in Diesel Particulates Found by
Battelle Northwest (Reference 28)
Compound
Polycyclic Aromatic Hydrocarbons
Alkylated fluorenones
Alkylated phenols
Aliphatic acids
Methyl esters
Alkanones
Phenanthrenequinone
Benzoic Acid
Xanthen-9-one
Isobenzofuranone
N-aminopiperidine
------- |