A-600/3-75-010e
pt ember 1975
Ecological Research Series
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, '
U.S. Environmental Protection Agency, have been grouped into
five series. These five broad categories were established to
facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL RESEARCH series.
This series describes research on the effects of pollution on
humans, plant and animal species, and materials. Problems are
assessed for their long- and short-term influences. Investigations
include formation, transport, and pathway studies to determine the
fate of pollutants and their effects. This work provides the
technical basis for setting standards to minimize undesirable
changes in living organisms in the aquatic, terrestrial and
atmospheric environments.
This document is available to the public through the National
Technical Information Service, Springfield, Virginia 22161.
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EPA-600/3-75-010e
September 1975
ANNUAL CATALYST RESEARCH PROGRAM REPORT APPENDICES
Volume IV
by
Criteria and Special Studies Office
Health Effects Research Laboratory
Research Triangle Park, North Carolina 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
HEALTH EFFECTS RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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CONTENTS
Page
CATALYST RESEARCH PROGRAM ANNUAL REPORT
EXECUTIVE SUMMARY 1
INTRODUCTION 5
PROGRAM SUMMARY 7
TECHNICAL CONCLUSIONS 17
DISCUSSION 22
REFERENCES 45
APPENDICES TO CATALYST RESEARCH PROGRAM ANNUAL REPORT
VOLUME 1
A. OFFICE OF AIR AND WASTE MANAGEMENT
A1 . AUTOMOTIVE SULFATE EMISSIONS 1
A2. GASOLINE DE-SULFURIZATION - SUMMARY 53
A2.1 Control of Automotive Sulfate Emissions
through Fuel Modifications 55
A2.2 Production of Low-sulfur Gasoline 90
VOLUME 2
B. OFFICE OF RESEARCH AND DEVELOPMENT
B1. FUEL SURVEILLANCE
B1.1 Fuel Surveillance and Analysis 1
B1.2 The EPA National Fuels Surveillance
Network. I. Trace Constituents in Gasoline
and Commercial Gasoline Fuel Additives ... 19
B2. EMISSIONS CHARACTERIZATION
B2.1 Emissions Characterization Summary .... 44
B2.2 Sulfate Emissions from Catalyst- and Non-
catalyst-equipped Automobiles 45
B2.3 Status Report: Characterize Particulate
Emissions - Prototype Catalyst Cars 68
B2.4 Status Report: Characterize Particulate
Emissions from Production Catalyst Cars. . . 132
B2.5 Status Report: Survey Gaseous and Particu-
late Emissions - California 1975 Model Year
Vehicles 133
B2.6 Status Report: Characterization and Meas-
urement of Regulated, Sulfate, and Particu-
late Emissions from In-use Catalyst Vehicles -
1975 National Standard 134
B2.7 Gaseous Emissions Associated with Gasoline
Additives - Reciprocating Engines. Progress
Reports and Draft Final Report - "Effect of
Gasoline Additives on Gaseous Emissions" . . 135
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Page
B2.8 Characterization of Gaseous Emissions from
Rotary Engines using Additive Fuel -
Progress Reports 220
B2.9 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Oxygen- and Sulfur-
containing Additives , 232
B2.10 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Various Nitrogen-
containing Additives 233
B2.11 Status Report: Characterize Diesel Caseous
and Particulate Emissions with Paper "Light-
duty Diesel Exhaust Emissions" 234
B2.12 Status Report: Characterize Rotary Emissions
as a Function of Lubricant Composition and
Fuel/Lubricant Interaction 242
B2.13 Status Report: Characterize Particulate
Emissions - Alternate Power Systems (Rotary) 243
VOLUME 3
B.3 Emissions Measurement Methodology
B3.1 Emissions Measurement Methodology Summary 1
B3.2 Status Report: Develop Methods for Total
Sulfur, Sulfate, and other Sulfur Compounds
in Particulate Emissions from Mobile Sources 2
B3.3 Status Report: Adapt Methods for SO2 and SO3
to Mobile Source Emissions Measurements 3
B3.4 Evaluation of the Adaption to Mobile Source
SO2 and Sulfate Emission Measurements of
Stationary Source Manual Methods 4
B3.5 Sulfate Method Comparison Study. CRC APRAC
Project CAPI-8-74 17
B3.6 Determination of Soluble Sulfates in CVS
Diluted Exhausts: An Automated Method 19
B3.7 Engine Room Dilution Tube Flow Characteristics .... 41
B3.8 An EPA Automobile Emissions Laboratory 52
B3.9 Status Report: Protocol to Characterize Gaseous
Emissions as a Function of Fuel and Additive
Composition - Prototype Vehicles 89
B3.10 Status Report: Protocol to Characterize Particu-
late Emissions as a Function of Fuel and Additive
Composition 90
B3.11 Interim Report and Subsequent Progress Reports:
Development of a Methodology for Determination
of the Effects of Diesel Fuel and Fuel Additives
on Particulate Emissions 192
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Page
B3.12 Monthly Progress Report #7: Protocol to
Characterize Gaseous Emissions as a Function
of Fuel and Additive Composition 200
B3.13 Status Report: Validate Engine Dynomometer Test
Protocol for Control System Performance 218
B3.14 Fuel Additive Protocol Development 221
B3.15 Proposed EPA Protocol: Control System
Performance 231
VOLUME 4
B3.16 The Effect of Fuels and Fuel Additives on Mobile
Source Exhaust Particulate Emissions 1
VOLUME 5
B3.17 Development of Methodology to Determine the
Effect of Fuels and Fuel Additives on the Perform-
ance of Emission Control Devices 1
B3.18 Status of Mobile Source and Quality Assurance
Programs 260
VOLUME 6
B4. Toxicology
B4.1 Toxicology: Overview and Summary 1
B4.2 Sulfuric Acid Effect on Deposition of Radioactive
Aerosol in the Respiratory Tract of Guinea Pigs,
October 197A 38
B4.3 Sulfuric Acid Aerosol Effects on Clearance of
Streptococci from the Respiratory Tract of Mice.
July 1974 63
B4.4 Ammonium and Sulfate Ion Release of Histamine
from Lung Fragments 89
B4.5 Toxicity of Palladium, Platinum and their
Compounds 105
B4.6 Method Development and Subsequent Survey
Analysis of Experimental Rat Tissue for PT, Mn,
and Pb Content, March 1974 128
B4.7 Assessment of Fuel Additives Emissions Toxicity
via Selected Assays of Nucleic Acid and Protein
Synthesis 157
B4.8 Determination of No-effect Levels of Pt-group
Base Metal Compounds Using Mouse Infectivity
Model, August 1974 and November 1974 (2
quarterly reports) 220
B4.9 Status Report: "Exposure of Tissue Culture
Systems to Air Pollutants under Conditions
Simulating Physiologic States of Lung and
Conjunctiva" 239
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Page
B4.10 A Comparative Study of the Effect of Inhalation of
Platinum, Lead, and Other Base Metal Compounds
Utilizing the Pulmonary Macrophage as an Indicator
of Toxicity 256
B4.11 Status Report: "Compare Pulmonary Carcinogenesis
of Platinum Group Metal Compounds and Lead Com-
pounds in Association with Polynuclear Aromatics
Using ir^ vivo Hamster System 258
B4.12 Status Report: Methylation Chemistry of Platinum,
Palladium, Lead, and Manganese 263
VOLUME 7
B.5 Inhalation Toxicology
B5.1 Studies on Catalytic Components and Exhaust
Emissions 1
B.6 Meteorological Modelling
86.1 Meteorological Modelling - Summary 149
B6.2 HIWAY: A Highway Air Pollution Model 151
B6.3 Line Source Modelling 209
B.7 Atmospheric Chemistry
B7.1 Status Report: A Development of Methodology to
Determine the Effects of Fuel and Additives on
Atmospheric Visibility 233
Monthly Progress Report: October 1974 255
B7.2 Status Report: Develop Laboratory Method for Collec-
tion and Analysis of Sulfuric Acid and Sulfates • • • 259
B7.3 Status Report: Develop Portable Device for Collection
of Sulfate and Sulfuric Acid 260
B7.4 Status Report: Personal Exposure Meters for
Suspended Sulfates 261
B7.5 Status Report: Smog Chamber Study of SO2
Photo-oxidation to SO under Roadway
Condition • 262
B7.6 Status Report: Study of Scavenging of SO_ and
Sulfates by Surfaces near Roadways 263
B7.7 Status Report: Characterization of Roadside
Aerosols: St. Louis Roadway Sulfate Study .... 264
B7.8 Status Report: Characterization of Roadside
Aerosols: Los Angeles Roadway Sulfate Study • • • 269
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Page
VOLUME 8
B.8 Monitoring
B8.1 Los Angeles Catalyst Study. Background Pre-
liminary Report
B8.2 Los Angeles Catalyst Study; Summary of Back-
ground Period (June, July, August 1974)
B8.3 Los Angeles Catalyst Study Operations Manual
(June 1974, amended August 1974).
B8.4 Collection and Analysis of Airborne Suspended
Paniculate Matter Respirable to Humans for
Sulfates and Polycyclic Organics (October 8, 1974).
1
13
33
VOLUME 9
B.9 Human Studies
1974.
.194
1
B9.1 Update of Health Effects of Sulfates, August 28,
B9.2 Development of Analytic Techniques to Measure
Human Exposure to Fuel Additives, March 1974 .... 7
B9.3 Design of Procedures for Monitoring Platinum
and Palladium, April 1974 166
B9.4 Trace Metals in Occupational and Non-occupation-
ally Exposed Individuals, April 1974 178
B9.5 Evaluation of Analytic Methods for Platinum and
Palladium 199
B9.6 Literature Search on the Use of Platinum and
Palladium 209
B9.7 Work Plan for Obtaining Baseline Levels of Pt
and Pd in Human Tissue 254
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Appendix B3.16
The Effect of Fuels and Additives on Mobile
SourceJIxhaust Particulate Emissions
ABSTRACT
This report describes work carried out to develop a method-
ology for the determination of the effect of fuel additives
on exhaust particle size, concentration, and composition,
from light-duty vehicles.
In order to determine the best methodology, particulate emis-
sions were examined using a 350 CID Chevrolet engine, and
several 350 CID Chevrolet vehicles. The engines and vehicles
were operated under steady-state cruise conditions, and under
the federal 23-minute cycle. Particulate mass measurement
techniques have included tailpipe measurement methods and
air dilution sampling methods using impaction separators,
and filters.
Two different fuel additives as well as a baseline fuel were
used to determine the validity of the methods employed. The
engine dynamometer runs were correlated with vehicles using
the same fuel and additives. Engine runs were made using
both manufacturer's suggested and higher than suggested addi-
tive concentrations.
i
The data collected suggests that the methods employed do
allow the determination of any adverse effects on particulate
emissions due to the inclusion of an additive in the fuel.
In addition, a study was made of probable trends in fuel
additive chemistry.
An additional task of this study was the collection and anal-
yses of exhaust gas condensate, to be used in animal health
studies.
1
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I. INTRODUCTION
The use of fuel additives has been shown to have an
effect on the size, quantity, and composition of parti-
culate matter emitted from light duty gasoline engines.
Work involving particulate measurements primarily on
leaded and unleaded fuel has been reported in EPA-R2-72-
066. The purpose of the study covered in this report
was to determine methodology for assessing the effect on
particulate emissions of other types of fuel additives.
This study, performed from December 1971 to July 1973, .is
part of a fuel additive study program which was developed
by EPA to determine the total range of fuel additive
effects on emissions, and to develop methodology, where
appropriate, to assist in the generation of data which is
required by EPA for fuel additive registration. Other
contracts in the fuel additive program include studies
on the effect of fuel additives on the composition of
the hydrocarbon exhaust portion (Bureau of mines), the
effect of fuel additives on catalyst performance (The Dow
Chemical Co.), the effect of fuel additives ,on exhaust
visibility (Cornell aeronautics lab) and development of
a model for fuel additive emissions determinations
As a result of this study, and prior work done on the
collection and analyses of particulate emissions, reproduci-
ble generation, collection and analysis techniques have been
developed. The additives used in this study were a poly-
buteneamine and methylcyclopentadienyl manganese tricarbonyl.
Both additives were used at the levels recommended at the
time by the manufacturer, and also at 3 times the manufacturer's
recommendation. The polybuteneamine, designated additive A,
was used at 1.87 grams/gal, and at 5.61 grams/gal. The
manganese additive, designated additive B, was used at
.25 grams/gal, measured as manganese, and at .75 grams/gal.
2
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The manufacturer,s recommendation for this additive has
since been reduced.
The engines used on the dynomometer were broken in accord-
ing to a specified break in procedure and were conditioned
for 75 hours using repeated 23 minute federal cycles.
Particulate sample was collected from the diluted exhaust
(approximately 12 to 1 air/exhaust dilution at a flow rate
of 550 cfm diluted). Four filter systems were used to
collect particulate from the dilution tube: or Andersen
-.
impactor with a 142 millipore back-up filter at 1 cfm, a
47 mm glass fiber filter at 1 cfm, and two 142 mm glass
fiber filters at 1 cfm.
Collections for analyses were made from the dilution tube
under steady state (60 mph) conditions, and also using
the 23 minute Federal cycle. Collected particulate was
analyzed for the following:
Total particulate mass emissions
Mass/size distribution
C, H, N content
Benze-a-Pyrene
Trace elements
In addition, aldehydes, measured as HCNO, and NH_ were
measured from condensed exhaust gas. Specific studies on
particulate size and composition were made on selected
particulate samples using a scanning electron microscope.
Standard gaseous analyses for CO, No and unburned hydro-
1^.
carbons were made on the raw exhaust, primarily as an
engine performance monitor.
In addition to the engine dynamometer tests, three vehicles
were operated for approximately 17,000 miles on the base-
line and the two additive fuels. These vehicles were
driven by employees in their normal fashion, and were
rotated periodically to eliminate operational variables.
3
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Before active testing was begun on either engine stand or
vehicles, an attempt was made at surveying the current
fuel additive technology, with hopes of identifying what,
if any, future trends were developing. On balance, this
attempt was basically unsuccessful. Most research in this
area was treated as proprietary, and questions on future
additive trends were unvariably answered with "We don't
know". A summation of the information which was gathered
is in Section VI.
•.
Midway through the contract, an addition was granted for
the collection of exhaust gas condensate samples for use
in animal health studies. These samples were sent to
Dr. Schubik of the Eppley Institute for Research in Cancer,
University of Nebraska Medical Center, and were used for
research on the effects of exhaust gas on the lung tissue
of animals. The condensate samples collected were analyzed,
and the data is reported in Section VII.
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II. GENERAL CONCLUSIONS
1. Under the conditions used for vehicle and engine stand
tests, described in section V, additive concentrations of
three times the manufacturer's recommended dosage, when run
for 75 hours of repetitive 23-minute Federal cycles, showed
the same trend toward increased particulate in the case
of additive B as seen in the vehicles using the additive at
the recommended level for approximately 17,000 miles. Addi-
tive A showed essentially the same trend in the engine
runs and in the vehicles, which was no noticeable increase
compared to the baseline.
2. The use of repetitive 23-minute Federal cycles on the
engine stand with additive fuels did not show significant
differences compared to the baseline fuel, with respect to
grams/mile particulate, when the additive was used at the
recommended dosage. The 75-hour conditioning period is
equivalent to approximately 1,500 miles. When total grams/mile
particulate was less than .1, any variation beneath that
point is considered insignificant since the collection and
weighing precision is poor below that point.
3. Chemical analyses of collected particulate from both
the engine stand and vehicles showed variations in C, H,
and N levels, to the extent that no meaningful conclusions
as to the organic content of the particulate can be drawn.
In many cases the sample size was so small that any differences
could be due solely to the inherent imprecision.
4. In general, the manganese-containing additive, methyl-
cyclopentadienyl manganesetricarbonyl, (Additive B) gave
higher grams/mile of emitted particulate than did the
polybuteneamine (Additive A) and baseline fuel, in both
engine stand and vehicle tests. The increase was from 50%
to 100% above the baseline. Additive A was not significantly
different from the baseline.
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5. Additive Af in general, gave larger particles than the
baseline, while Additive B in general gave particulate
smaller than the baseline, for either additive. The
use of 3 times the recommended concentration did not
significantly change the mass medium equivalent diameter,
when compared to the recommended concentration.
6. As a result of this study, and prior studies on
particulate emissions, a methodology has been developed
which can be used to reproducibly generate, collect and
n
analyze particulate emissions. It must be recognized however,
that any particulate collection system will entail equipment
and technique not currently used for other emissions studies,
In addition, any quantitative or qualitative analyses of
particulate will require instrumentation and technique
which may not be readily available.
It also must he recognized that any particulate collection
system different from the one described in this study may
be quite satisfactory for the intended purpose, but cannot
be used to compare with particulate mass emissions or
particulate size data generated under this study, since
the collection system geometry and conditions themselves
define the particulate. Comparisons of data generated in
a given system with a baseline measured in the same system.
7. The use of the Federal Cycle, 23 minutes or 41 minutes,
with unleaded fuel under the conditions described, in
general gives such small amounts of collected particulate
that qualitative analyses are often meaningless, if not
impossible. Steady state conditions (60 mph, collected
for 2 hours) will give larger amounts of collected parti-
culate which can be analyzed more thoroughly. The effect
of other collection parameters such as temperature, filter
face, velocity and collection time is discussed in detail
in EPA report APTD-1567, titled "Characterization of
particulates and other non-regulated emissions from mobile
sources and the effects of exhaust emissions control devices
on these emissions". fi
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III. PROPOSED METHODOLOGY
The basic purpose of this study was to build on existing
particulate collection and analyses technology, and from
this and the additional studies run under this contract,
develop a methodology which could be used to generate
data for use in fuel additive registration. Under current
regulations, the EPA can request data from suppliers of
fuel additives relative to the effect of a given fuel
additive on emissions. However, in order to allow EPA to
make meaningful decisions as to the future registration
of these additives, a test protocol must be issued so that
data can be generated in a consistent and repeatable
fashion. An attempt was made in this contract to build a
logical, relatively inexpensive, but thorough method of
generating and collecting exhaust particulate emissions,
which would allow an effect on particulate emissions due
to an additive to be identified.
The details of the particulate collection system which
has been set up are covered in section IV, experimental
procedures( as well as in previous reports on particulate
i
studies. (APTD-1567: "Characterization of Particulates
and Other Non-regulated Emissions from Mobile Sources and
the Effects of Exhaust Emission Control Devices on these
Emissions". EPA-R2-72-066: "Effect of Fuel Additives on
the Chemical and Physical Characteristics of Particulate
Emissions in Automotive Exhaust". EHS 70-101: "Development
of Particulate Emission Control Techniques for SparkI
Ignited Engines.)
The engine stand testing in this study consisted of
repetitive 23 minute federal cycles. The particulate
collection was made during one 23 minute segment, both
cold start and hot start. Since the gross amount of
particulate collected during one 23 minute cycle is low,
the precision of both the mass emission figures and the
7
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analytical data is low. In addition, the same engine was
used for all the testing and only one 75 hour series of
tests was run for each additive concentration. Because
of the scatter in data points experienced under normal
conditions, the statistical significance of the data is
low as far as being representative of an absolute
grams/mile figure. However, based on previous work it
is felt that the method used for particulate collection
is reproducible enough so that any trends which developed
as a result of a fuel additive effect are legitimate,
even though a statement on the magnitude of the trends
would lack statistical significance. An example of a
trend which is felt to be meaningful is the increase in
particulate mass emissions noted with Additive B after
17,000 miles on the vehicles, and also the increase noted
with Additive B when used at 3X the recommended level in
the engine stand tests.
Some key conclusions concerning the proposed methodology
are as follows:
1. The cos.t involved in setting up a particulate study
such as the one described in this report will be somewhat
less than the cost of setting up to do CVS gaseous emissions
analyses. Assuming that a suitable structure exists
housing either an engine or chassis dynamometer, the cost
for setting up the collection system will range from
$10,000-$20,000. The most critical cost factor will
involve the analyses of the particulate for the various
chemical species which might be of interest.
2. A correlation does appear to exist between the engine
stand runs of 75 hours continuous 23 minute cycles at 3 x
recommended additive concentration, and the 17,000 vehicle
tests. Statistically speaking however, this correlation
8
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is of little impact. More statiscally significant is the
trend noted in the 17,000 mile vehicle tests.
3. Ambient conditions have a definite effect on particulate
emissions collection. Since the operating and collection
conditions can be controlled easier for engine tests than
they can for vehicle tests, engine stand tests would tend
to give data with less scatter. However, a statistically
significant fleet test can be set up utilizing 8-10 total
vehicles and the scheduling of tests can be made in such
a way that only one collection system would be necessary.
The effect of different ambient conditions would then be
somewhat lessened in a comparison of test vehicles against
a baseline.
Following is a discussion of ways in which the tests can
be run and equipment necessary to gather the appropriate
data. More detail on procedures and techniques is in
section IV.
A. EQUIPMENT
The equipment which was used in the experimental work by
Dow is described in Section IV. The key parts of the equip-
ment package needed for this methodology are the dilution
tube and sampling devices. In general, the geometry of the
dilution tube is not critical, although the total flow through
the tube should be about 550 cfm. The diameter of the
tube should be from 16-18 inches. With a smaller diameter
the residence time in the dilution tube will be low,
velocity high, and the temperature will be so high that
particulate measurements of any meaning will be difficult.
For consistent and reliable particulate sampling, the fol-
lowing steps must be observed:
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1. Four sampling probes, each sized to allow a 1 cfm sam-
pling rate of dilute exhaust from the dilution tube, should
be installed.
2. The sample probes must be water jacketed to allow the
temperature of the dilute exhaust to be maintained at 100°F
at the filter.
3. The filters to be used are described in detail in Sec-
tion III-B, along wi >:h a description of the Andersen samplers
4. The filter media used, both Gelman glass fiber and Milli-
pore, should be from the same batch for any series of runs.
The millipore filter is used for mass emission measurements,
as well as true metal analyses. The glass fiber media is
for organic measurements.
5. A baseline for the measured particulate must be estab-
lished using the same engine, base stock fuel, and filter
paper batch each time an additive is to be tested.
The engine-used for this testing was a 1972 Chevrolet
350 CID V-8. Although a variety of engines could undoubtedly
be used, assuming a consistent baseline is established, it
is recommended that the 350 Chevrolet be specified. This
will allow for easier correlation of data between testing
facilities.
The engine should be broken in using the procedure outlined
in Table I, Section IV. Low lead gas was used to insure
that during the break-in procedure the engine was given enough
octane and valve lubricity.
After break-in, the engine should be partially dismantled,
any combustion chamber deposits removed, and the condition
of the valves and cylinders noted. The engine was then
reassembled according to manufacturer's specifications.
10
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Before any testing is to be done, the engine must be sub-
jected to a blowby test as described in Table 3 Section IV.
If the CFM blowby, after conversion to standard conditions,
is higher than an established baseline, a standard leak-down
test should be conducted, and the engine should be corrected
to meet manufacturer's specifications before proceeding with
the testing.
An original equipment exhaust system is to be attached to
one side of the engine. The exhaust heat passage through
the intake manifold is to be plugged off, so that the ex-
haust from each side of the V-8 is entirely separate. Only
one bank of cylinders is used for particulate testing. The
other is exhausted through a straight pipe to the atmosphere.
For testing purposes, the engine must be equipped with the
turbo-hydromatic 350 automatic transmission, which is the
unit used in vehicles containing the 350 CID Chevrolet engine,
Any dynamometer with the capability of handling the loads
necessary in the 23 or 41-minute Federal cycle can be used.
The important aspect of the dynamometer is its ability to
run continuous 23-minute cycles. During the Dow work, a
mode monitor system manufactured by Northern Ampower Corp-
oration, was used to control the dynamometer. The Federal
cycle was transcribed from the Federal register onto Mylar
computer tape. The program was written such that after one
23-minute cycle the engine would idle until the computer
had reset itself to run another cycle.
B. PROCEDURE
In attempting to develop a screening technique for fuel add-
itives which could be run on an engine stand, in a relatively
short period of time, and would correlate to a mileage accu-
mulation of about 15,000 on a vehicle, the idea of running
11
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continuous high speeds on the engine stand for one week or
more was ruled out since this type of operation would be
non-typical of normal driving. In addition, seven days of
around the clock operation at 60 mph would only be 10,000
miles. The approach finally settled on was to take the Federal
23-minute cycle, which contains all commonly encountered
modes of operation and continuously cycle the engine. From
prior work it had been determined that about 75 hours was
sufficient to reach a stabilized situation with respect to
particulate emission, for a given additive. As a result
of the experimental work reported in Section V, the pro-
cedures outlined below are suggested as a screening technique
for fuel additive effect on particulate emissions.
1. The continuous 23-minute cycles are to be run for 19
hours each day. This was done by starting the engine at
10:00 a.m. on a given day, and shutting it down at 5:00 a.m.
the following morning. A cold start test is to be run when
the engine is restarted at 10:00 a.m. After four 19-hour
cycling periods, the engine is to be allowed to stand for
12 hours before running the final cold start. After the
final cold start, two or more hot starts are to be run.
If the amount of particulate collected during the hot or
cold start is too low for detailed chemical analyses, a
2-hour 60 mph steady-state run should be made following the
last hot start.
2. The test sequence should involve a baseline run of 75
hours for each additive tested, unless several additives
are to be done within a short time period. If this is the
case, baseline runs should be interspersed between the addi-
tive runs as follows:
Additive at recommended concentration
Additive at 3 times recommended concentration
12
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Engine tear-down, clean-off deposits, then baseline
run
Additive at recommended concentration
Additive at 3 times recommended concentration
If three or more additives are to be tested, each additive
series should be separated by a baseline run.
3. The runs involving additive concentrations three times
the recommended level are necessary to amplify the effect
of the additive on particulate emissions. While it was recog-
nized that using a given additive at greater than recommended
levels could cause other exhaust abnormalties, the experi-
mental work on the two additives in question showed that
the vehicles correlated well with the increased additive
concentration.
C. PARTICULATE ANALYSES
The analytical procedures described in Section IV should
be used to determine the basic chemical make-up of th par-
ticulate. In addition, the grams/mile emission rate should
be calculated as described in Section IV.
It is recognized that additives of varying chemical compo-
sition can be expected to give particulate emissions contain-
ing those chemicals, of modifications. This is especially
true for additives with inorganic components. Specific
analytical techniques for the determination of the quantity
and form of these elements are necessary. No attempt was
made in this contract to develop techniques for compositions
other than those outlined in Section IV and discussed in
Section V.
13,
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IV. EXPERIMENTAL PROCEDURES
A. PARTICLE GENERATION
1. Engine Dynamometer Studies
The test engine was completely disassembled, cleaned and
reassembled according to manufacturer's specifications.
•It was then mounted on the dynamometer bed plate and attached
to a fully instrumented General Electric dynamometer. Appro-
priate control and sensing devices were attached to the
engine. A 1972 350 CID Chevrolet engine was used for all
engine tests. It was equipped with standard emission control
devices for that model and year. The following procedure
(Table 1) was then employed to run-in the new engine, using
Indolene .5 cc TEL/gal. fuel.
TABLE I
NEW ENGINE BREAK-IN PROCEDURE
(28 hours)
1) Warm up engine to 180°F coolant outlet temperature at
1000 rpm, no load, set spark advance, timing, and idle
according to manufacturer's specifications.
2) Run one hour at 1500 rpm, no load, automatic spark
advance and fuel flow. Shut down, retorque cylinder
heads, drain and change lubricating oil.
3) Run Cycle 1
RPM Man. Vac. (In. Hg) Time (Iir.)
1500 15.0 1.0
2000 14.0 1.0
2400 14.0 1.0
2600 14.0 1.0
2000 11.0 1.0
5.0
' 14
-------
4)
Run Cycle 2
RPM
1500
2000
2500
3000
2000
Man. Vac. (In. Hg)
7.0
7.0
7.0
7.0
7.0
Time (hr.)
0.2
0.6
,0
,0
1,
1.
0.2
3.0
5) Repeat Cycle 2.
6)
Run Cycle 3
RPM
2000
2500
3000
3500
2800
Man. Vac. (In. Hg
WOT*
WOT
WOT
WOT
WOT
Time (hr.)
*WOT - wide open throttle
1,
1,
1,
0.5
0.5
4.0x4 cycles
16 hours
7) While engine is hot, run motoring compression and conduct
leak-down check.
The engine was removed from the dynamometer, drained, par-
tially dismantled, cleaned, reassembled, and placed back
on the dynamometer stand. A typical vehicle exhaust system
for the specific test engine was attached to one bank of
cylinders. The other bank of cylinders was attached to the
dynamometer cell exhaust system. Suitable engine monitors
were attached to the engine in order to provide continuous
monitoring of oil pressure and temperature, coolant temper-
ature, carburetor air flow rate (using a Meriam Laminar Flow
Element 50MC-2-45F) and temperature, etc.
After the break-in procedure, the engine was run, with trans-
mission, using repetitive 23-minute Federal cycles. The
15
-------
engine was operated for approximately 75 hours, with one
5-hour shut-down in each 24-hour period. The engine was
monitored during this period by performing gaseous analyses,
sampled from the Dow dilution tube, during the course of
one 23-minute cycle.
At the termination of the test run, the engine was removed
from the dynamometer stand, dismantled, and samples for anal-
ysis were removed. ^he engine was completely cleaned, reas-
sembled, and reinstalled on the dynamometer stand.
Subsequent tests did not require the break-in procedure noted
in Table 1 unless a new engine was used. If the same engine
was used again, the next test series began with the running
of the repetitive 23-minute cycles discussed above.
2. Chassis Dynamometer Procedures
A Clayton CT-200-0 chassis dynamometer with a variable iner-
tia flywheel assembly was used in all tests conducted under
this program. A Chelsa direct-drive Model PLDUP-200A fan
was located in front of the test vehicle, and operated at
1750 rpm providing 18,750 scfm air flow. In these tests,
the vehicle was operated under approximately 60 mph road-
load cruise conditions (2250 rpm - 17" Hg manifold vacuum)
and under cyclic conditions of the Federal Test Procedure
(1970) and LA-4 (1975) procedure driven by a vehicle opera-
tor following the cycle on a strip-chart recorder driver
aid.
Table 2 indicates specific procedures employed to prepare
each vehicle for test run.
16
-------
TABLE 2
VEHICLE TEST PROCEDURE - CHASSIS DYNAMOMETER
1) General Vehicle Inspection
Exhaust System;
a) Inspect for holes or cracks, dents, and collapse
b) Inspect for leaking joints
Engine check
a) All fluid levels
b) All coolant hoses
c) Air pump fan, power steering, and belts
d) Check heat riser (if applicable) for fullness
of operation
e) Check automatic choke operation and adjustment
2) Engine Analysis and Tune-up
Leak-Down Test
a) Remove all spark plugs
b) Determine percent leak-down of each cylinder
c) Install recommended, new, and gapped spark
plugs, points, and condenser
Scope Check
a) Start engine and allow to warm up for at least
15 minutes
b) With engine running at fast idle, check
.Spark plugs
.Spark plug wires
.Distributor cap and rotor
.Coil output
.Points
c) With engine running at idle, check
.Dwell
.Timing
d) With engine running at 1500 and 2400 rpm, check
.Timing advance
e) Carburetor Adjustment
.Tighten intake manifold and carburetor
.Install new air cleaner element
.With engine running at specified idle speed,
adjust air to fuel ratio to specifications
.Make final adjustment on idle speed
f) Recheck all scope patterns for normal appearance
17
-------
3) Instrumentation and Equipment Installation
Thermocouples - install thermocouples in
a) Engine oil - dipstick
b) Coolant - upper radiator hose engine out
c) Carb air - air filter element
Vacuum and rpm monitors
a) Attach tachometer to ignition coil
b) Connect "U" tube monometer to intake manifold
c) Install throttle cable (if running under cruise
mode)
Wheels
a) Remove rear wheels
b) Install test tires and wheel assemblies to
insure safe operation
4) Procedure for Cold, Hot Starts, and Engine Temperature
Stabilization
Cold Start
a) Place vehicle on the dynamometer rolls, set inertia
weights for specific vehicle, and go through the
preparation for test as well as the tune-up procedure.
b) Allow at least a 12-hour soak period.
c) Connect vehicle tailpipe to dilution tube.
d) Start the vehicle and proceed with the individual
test.
Hot Start
The hot start procedure is the same as for the cold start
except" that the vehicle was warmed up and allowed to sit
for 10 minutes before starting.
Engine Temperature Stabilization
Upon completion of the tune-up procedure the vehicle
is started cold and driven a total of 32 highway miles
at 60 mph to allow the engine temperature to stabilize.
The vehicle was then driven on-to the dynamometer rolls
and prepared for the test during which time the engine
idles for approximately five minutes. When preparation
has been completed, the vehicle was placed in gear and
the speed was increased to 2250 rpm and the intake mani-
fold vacuum was set at 17.0" Hg by controlling the amount
of load imposed on the drive wheels. At the time, when
18
-------
the load and the speed become stabilized, the tailpipe
is connected to the dilution tube inlet pipe and sampling
is started.
Table 3 is a description of the blowby test procedure used
to ascertain that proper piston ring and valve guide seating
is occurring.
TABLE 3
BLOWBY TEST PROCEDURE
Clayton CT-200 Chassis Dynamometer Used
1) Thermocouples installed as follows to record accurate
temperatures:
a) Top radiator hose
b) Carburetor venturi
c) Oil pan
d) Ambient air
e) Blowby gas flow tube
2) Close oil dip stick tube
3) Close rocker cover vent to carburetor (right side on
350 CID Chevrolet)
4) Install tube from PCV (left side) to sharp orifice
meter intake (1/4" port)
5) Install Vernier band throttle
6) Place wind fan in front of car
7) Connect accurate tachometer
8) Connect blowby apparatus as follows (see diagram for
details):
a) Use cooling water to maintain 75-85°F blowby
b) Connect condensate trap to tube from PCV
c) Connect outlet from condensate trap to sharp
orifice meter (use 1/4" orifice)
d) Connect incline water monometer across orifice
meter
e) Connect mercury monometer to engine vacuum
19
-------
9) All test run at 2000 rpm
10) Collect the following data at each load condition:
a) MPH
b) RPM (maintain at 2000)
c) Load
d) Intake manifold pressure
e) Ambient air
-f) Carburetor air
g) Coolant temperature
h) Oil temperature
i) Barometer reading
j) Wet and dry bulb temperatures
k) Blowby temperature before orifice meter
1) Pressure drop observed across water monometer
m) Observed cfm blowby - read from sharp orifice
meter chart relating pressure drop to cfm
11) CFM at standard conditions is calculated using a dfm
correction factor to compensate for barometric pressure
and a standard conversion factor to bring the final result
to cfm at standard conditions.
12) The initial reading is taken at the lowest horsepower
load measurable. Subsequent readings at multiples of
10 hp.
13) See attached data collection sheet for an example of
one blowby run.
B. PARTICLE COLLECTION
Exhaust particles were collected after air dilution of the
exhaust in the large dilution tube described below. During
the engine stand studies, one-half of the engine exhaust
was fed into the tube while the other half was exhausted
through the dynamometer cell exhaust system. With vehicles,
the entire exhaust stream was diluted.
1. Dilution Tube
Air dilution and cooling of the exhaust was accomplished
by a dilution tube 16 inches in diameter and 27 feet in
20
-------
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22
-------
length constructed of extruded polyvinyl chloride (PVC),
except for a 6' stainless steel inlet Section, in several
sections with butt joints which were taped during assembly
prior to each run (Figure 1). The diluent air coming into
the tube is filtered by means of a Dri-Pak Series 1100
Class II PIN 114-110 020 untreated cotton filter assembly.
This filter assembly is 24" x 24" and has 36 filter socks
which extend to 36 inches in length. This filter will
pass particles 0.3y in size and smaller. Pressure drop
at 600 cfm flow rate was minimal.
Exhaust was delivered to the tube via a tailpipe extension
which was brought into the bottom of the tube downstream
of the dilution air filter assembly. The extension was
bent 90 degrees inside the tube, thus allowing the introduction
of the exhaust stream parallel to the tube axis. Within
the dilution tube, along the perpendicular plane of the
end of the exhaust extension was a mixing baffle which has
an 8-inch center hole and was attached to the inside
diameter of the tube. The baffle presented a restriction
to the incoming dilution air in the same plane as the end
of the exhaust extension and performed three essential
i
functions.
a. Provided a turbulent mixing zone of exhaust gas and
dilution air.
b. Eliminated engine exhaust pulsations in the tube.
c. Caused the tube to perform as a constant volume device
over a wide range of engine exhaust output volumes.
2. Sampling Devices
The particulate sampling zone for particles smaller than
15vi was located at the exhaust end of the dilution tube.
Four isokinetic sample probe elbows are located in the ex-
23
-------
haust-air stream. One probe is connected to an Andersen
Impact Sampler Model 0203, a filter assembly, and a vacuum
pump, in that sequence. The probes are 0.754 inch ID stain-
less steel tubes which are located as shown in Figure 1.
A mercury manometer was connected between the dilution tube
probe and the exhaust side of the filter assembly, to mea-
sure the pressure drop across the filter. A flow meter was
used to monitor and regulate the flow through the Andersen
Sampler during the course of each run. Two other sample
probes, each were connected to 1 cfm Millipore filter
*.
holders (142 mm) fitted with Gelman Type A glass fiber
filter pads and vacuum pumps. The fourth filter was a 47
mm, 1 cfm glass fiber.
Prior to use, all the filters were stored in the instrument
room which was temperature- and humidity-controlled. The
filters were placed on the tray of the Mettler Analytical
Balance, allowed to reach equilibrium, and then weighed out
to 0.1 milligram (mg).
After the test, the filters were removed from the holders
and again allowed to reach equilibrium, noted by no further
change in weight, and then weighed to 0.1 mg. This was done
in the same room in which the papers were stored. The Milli-
pore filter pads used were 142 Type AAWP 0. 8y. The glass
fiber filter pads used were Gelman 0.3y Type A. It is
extremely important that all filters used in a given sequence
of tests be from the same batch. Variations in batch lots
have been found to lead to gross differences in collected
particulate.
Andersen Sampler Model 0203 with a back-up 142 mm Millipore
filter was used as the basic particle collection device for
determining mass size distribution. Sample probes sized
to deliver an isokinetic sample from the dilution tube were
connected to the Andersen Sampler through which a proportional
sample was drawn at 1 cfm. The D cut-off values for the
24
-------
-------
are j.istea in Taoie 4. The D _ value is
the size at which 50% of those particles are collected, while
the remaining 50% pass on through to be collected on the
next stage.
TABLE 4
D50 VALUE - ANDERSEN MODEL 0203
Stage 1 DS() 9y
Stage 2 DSQ 5.45y
Stage 3 DSQ 2.95y
Stage 4 D™ 1.55y
Stage 5 D^ 0.95vi
Stage 6 D5Q 0.54y
Preweighed glass collection plates were used in this study.
Back-up filters were either Millipore Type AAWP 0. 8y or
Gelman 0.3y Type A 142 mm diameter. Gelman glass fiber
filters were routinely used while the Millipore filters
were used for special analytical applications. Particulate
larger than 15y was collected as gravimetric fallout in the
dilution tube.
c. CQNDENS'ATE COLLECTION
Exhaust gas condensate was collected for aldehyde and NH_
analyses. A tap was placed into the raw exhaust gas stream,
as close to the tailpipe of a vehicle as practical (about
12 inches in most cases) and 8 feet from the muffler in an
engine run. Raw exhaust was drawn through a three-stage
cold trap at the rate of 1 cfm. The cold trap consisted
of three flasks connected in series containing 40 grams
each of DI water, immersed in an ice water bath. The ex-
haust gas flow bubbles through the water in the flasks.
Condensate was collected for 41 minutes during a modified
Federal cycle cold start, and for 23 minutes during a Federal
cycle hot start. Sampling was terminated at 25 minutes during
a steady-state run.
26
-------
The condensate from the exhaust gas was analyzed for ppm
of HCHO and NH~. It was felt desirable to express this anal-
ysis in volume percent to compare to the other components
analyzed in the exhaust gas. The procedure for this calcu-
lation is as follows:
The "Ideal Gas Law" was used
PV = n RT
V = n RT
The total liters of exhaust that was put through the conden-
ser is known, the liters of the aldehyde can be calculated
from the formula above, so the volume percent can be calcu-
lated. This volume percent is reported as volume parts per
million in the exhaust.
D. ANALYTICAL METHODS
Collected exhaust particles have been analyzed for both phy-
sical and chemical character. Many analytical techniques
have been employed in the past, some of which provide very
similar data in the interest of correlating trends observed.
This section reviews the basic analytical concepts applied
to each of the many test components from fuels to exhaust
particles. Detailed descriptions of the specific analytical
procedures employed are then presented. Table 5 is a summary
of the techniques used on the exhaust emissions.
27
-------
TABLE 5
ANALYTICAL TECHNIQUES FOR EXHAUST SPECIES
O2, N2/ CO, CO2 Fisher Gas Partitioner
Total Hydrocarbons Beckman Model 10 9A Flame
lonization Detector
Oxides of Nitrogen Beckman UV and IR Analyzer
C, H Pyrolysis
Benzo-a-pyrene Chroma tograph, Fluorescence
Trace Metals Emission Spectroscopy,
Atomic Absorption
Aldehydes Polarography
NH_ Steam Distillation, Titration
1. Fuels .
Each test fuel was analyzed to verify concentrations of addi-
tives under study. Additionally, complete physical analyses
were determined on the base stock test fuel. These analyses
include distillation, octane numbers, fluorescence indicating
analysis (FIA) composition, Reid vapor pressure (RVP), and
trace metals. The test fuel was Indolene 0, and was
from the same batch for all engine and vehicle runs.
The additive blending was done in a large batch, and the
fuel was then drummed off for future use.
28
-------
2. Oils
Engine oils were examined for trace metals both before and
after test runs. Compliance of physical properties with
specifications was verified. The oils were only checked
on the engine stand runs, not on vehicles.
3. Diluent Air
Mass and composition of the filtered diluent air particulate
was determined with the engine or vehicle operating in the
air pick-up zone as during a test run. This data was neces-
sary to provide a correction factor applicable to the mass
emission rates determined during a test run.
4. Exhaust Gases
Engine exhaust gases were analyzed routinely several times
during the conditioning sequence and during sampling runs.
Schematically, exhaust gas sample points are as shown earlier
in Figure 1. The engine exhaust gas was analyzed for oxygen,
nitrogen, carbon monoxide, carbon dioxide, and total unburned
hydrocarbons. The hydrocarbons were broken down into satur-
ates and unsaturates. These analyses were done by gas chroma-
tography, chemical absorption, and a total hydrocarbon ana-
lyzer. Data reduction was via an IBM 1800 computer through
a Bell Telephone ASR 33 Teletype interface.
a. Analytical Equipment
A Fisher Gas Partitioner was used for th§ analysis of oxygen,
nitrogen, carbon monoxide, and carbon dioxide. The partition
column consisted of a 6-foot section containing hexamethyl
phosphoramide and a 6 1/2-foot section containing 13x molec-
ular sieves in series.
29
-------
Total hydrocarbons were obtained from a Beckman Model 109A
Total Hydrocarbon Analyzer. The concentration of unsaturated
hydrocarbons was determined by passing the sample through
an absorption tube (1/2" x 8") filled with 30-60 mesh pink
Chromosorb impregnated with 50 percent mercuric perchlorate.
The output of the gas chromatograph was coupled with a Hewlett-
Packard Model 3370A Digital Integrator which has an ASCII
coded output to drive an ASR 33 Teletype and punch paper
tape.
b. Sampling
A Neptune Dyna-Pump was used to pull the sample from the
exhaust pipe sampling point through 1/4" OD stainless steel
tubing and transfer it to the total hydrocarbon analyzer
and the gas sampling valve of the gas chromatograph through
1/8" OD stainless steel tubing. A manifold system was pro-
vided to allow the operator to calibrate the equipment with
the appropriate standards.
c. Standardization
A gas mixture containing known concentrations of oxygen,
nitrogen, argon, carbon monoxide, carbon dioxide, and
n-hexane was used as a reference standard for the total
hydrocarbon analyzer and the Fisher Gas Partitioner.
d. Operation
The operator typed the proper computer code and program num-
ber on the teletypewriter, injected the reference standard,
and pressed the integrator start button. As the peaks emerged,
30
-------
the time and area information was encoded and stored on punched
paper tape. Each succeeding exhaust gas was identified along
with the total hydrocarbon level, and run in the same manner
as the standard. When the series was finished, the punched
tape was sent to the computer by teletype over regular tele-
phone lines.
e. Data Reduction
A typical output format for the gas analysis is shown in
Figure 2. Identification of the components in the standard
was based upon each peak size in descending order. Esti-
mated retention time was the updated time of each peak in
the standard. Retention time windows are 4 seconds plus
2 percent of the retention time. Actual percent is a direct
ratio of the area counts in the unknown sample to the area
counts in the standard times the volume percent in the stan-
dard. The total percent actual will normally be 97-98 per-
cent since water is removed from the saturated sample after
the sampling valve.
A correction for the unresolved argon in oxygen was made
based upon response factors and the amount of argon found
in a number of exhaust gas samples by mass spectroscopy.
The actual percent was normalized to 100 percent in the next
column on a moisture-free basis, and an Exhaust Gas Analysis
report was issued (Figure 2). The air-to-fuel ratio was
calculated from this analysis, the total hydrocarbon content,
and the percent carbon in the fuel.
5. Oxides of Nitrogen
a. Equipment
Beckman Ultraviolet Analyzer
Beckman Infrared Analyzer
31
-------
Figure 4
G. C. ANALYSIS - TECHNICAL DATA -
G5V RU!J 23 CCT 16
'CYCLE 2 72.9 KDURS
KC 620.
PEAK TIME
NO. ACT. EST«
PCT. VOL.
ACTUAL t-«'3RH.
10-16-70
IDENTIFICATION
1 £2.
2 59.
3 83.
4 104.
5 107*'
21.
59.
83.
107.
ino.
0.000
12.003
1.493
0.900
81.003
1V626
97.060
2.940
2.940
OoOOO
12-3G6
1.53G
0.927
03.492
1.675
100.000
.. .
COMPOSITE
CARDCN DIOXIDE
CXYGEU
ARG3N
NITROGEN
CARSON 'i:GNOxiDE
TOTALS
DALAKCE BY DIFFERENCE
TOTAL CCi.'TAMINATlCri LEVEL
EXHAUST GAS ANALYSIS
GOV RUM 23 CCT 16
CYCLE 2 72.9 HDURS
KC 620.
TIME PERCENT IDZ»TIFICATICN
G3.
107.
C3.
ICO.
'59V
0.9 A?vG."-l
03 » 5 tJITi-rJG
1.5 OXYI-::)
12.4
CAR20U DIOXIDE
100*0 TOTAL
FRACTION CA^QDN IH FUEL O.C'625
TOTAL HYCROCARDCM COMTEMT" 620. PPM.
AIR/FUEL I1ATIO 14.G
10-16-70
32
-------
Recorder - Texas Instrument Company
The above pieces of equipment were in a single, self-contained
unit built by Scott Research Labs Inc., San Bernardino, Cali-
fornia.
b. Calibrating Gases
Nitric oxide (3545 ppm in nitrogen)
Nitrogen dioxide (862 ppm in nitrogen)
•.
These standard gases were purchased from Scott Research Labs
Inc.
Nitrogen was used as zero calibrating gas.
c. Procedure
Before making NO, NO2 measurements, the paper filters (What-
man #3) to each analyzer were changed and the Drierite dryer
in the exhaust sample line was replaced. Both analyzers
were standardized using the appropriate calibrating gas at
a constant flow. The zero standardizing was done using nitro-
gen as the calibrating gas and using the same flow rate.
After the instrument was standardized, the exhaust gas was
passed through the analyzer using the same flow rate as in
the standardization step. The NO, NO,, values were recorded
by the dual pen Servo-riter recorder. Figure 1 indicates
the source of the exhaust gas sample.
6. Exhaust Particles
The collection and classification techniques employed allow
the calculation of mass emission rates in grams/mile of ex-
33
-------
haust particulate. Additionally, cumulative mass distribu-
tion data can be calculated. Several collection methods
were used, and have been discussed previously in Section
III-B. The specific techniques for chemical analysis of
this particulate matter are discussed in this section.
a. Carbon and Hydrogen
The percentage of carbon and hydrogen in the particulate
was determined by pyrolysis and collection of the combustion
products. An entire 142 mm glass fiber filter containing
the particulate was placed in a large platinum boat. The
boat was then transferred to a combustion tube, and the
sample was combusted at 1100°C for 3/4 hour. Carbon dioxide
and water were absorbed in micro absorption tubes and weighed
in the conventional manner. The C and H values were, then
calculated from the increase in weight using the given weight
of the particulate.
In general, this technique is quite accurate for carbon and
hydrogen analysis. However, the small sample sizes generated
in a 23-minute cycle or 'from vehicles or engines operating
on unleaded fuel make it difficult to obtain precise results.
For example, the 142 mm Gelman glass fiber filters have a
blank of approximately 7 mg for hydrogen and a spread of
nearly 1 mg. For carbon the blanks are over 2 mg with a
spread of 0.5 mg. It is not uncommon to have sample sizes
of less than 2 mg; therefore, the inherent inaccuracy of
weighings (even using a 5-place balance) plus the large blank
size make the results of a small sample only meaningful in
a gross comparative sense.
This technique can be used on samples collected on the Ander-
sen Sampler plates by careful transfer of the particulate
to the combustion chamber. However, even with the best hand-
ling techniques the transfer of particulate is only about
-------
30 percent. In general, engine runs in which very little
sample was collected on-the filter pads also gave very little
on the Andersen Sampler Plates.
Nitrogen can also be determined by pyrolysis, but due to
the small sample size no meaningful results have been ob-
tained in nitrogen content.
b. Benzo-g-pyrene
. • i _ _- :- — r ,i
Samples of exhaust particulate were collected on Gelman
142 mm glass fiber filter pads in a Millipore filter holder
operating at 1 cfrn. Particulate weights gathered in this
fashion ranged from 0.2 to 35 rng. The samples on the glass fiber
filter pads were analyzed for benzo-a-pyrene in the following
manner.
When available a sample of at least 10 mg (on either one
or two filter papers) was used for analysis. The filters
were folded and rolled with the particulates toward the
inside of the roll and tied with copper wire. The rolls
i
were Soxhlet extracted for at least 6 hours (with siphoning
four to six times per hour) with 75 ml of benzene. The
extracts were evaporated under a stream of filtered air at
room temperature to approximately 3 ml. This concentrate
was filtered through a M-fritted glass filter into a tared
vial. The flask and filter were washed three times with
approximately 2 ml of benzene for each wash. The combined
filtrates were evaporated to dryness at room temperature
with a stream of filtered air.
The residues obtained from both sample and blank filters
were weighed and the difference between them designated
"benzene soluble weight" for each sample. The residue was
dissolved in 0.2 ml of methylene chloride and a 10-40 \il
aliquot was spotted in 2 yl increments on a pre-conditioned
Alumina TLC plate along with a known standard of benzo-a-
35
-------
pyrene in methylene chloride. The TLC plates were condi-
tioned by heating at 120°C for 1.5 hours and desiccating
overnight in a 45 percent relative humidity chamber (satu-
rated aqueous zinc nitrate). The TLC plate was developed
in an unsaturated tank containing 20 ml of ethyl ether in
200 ml of n-pentane to a height of 15 cm (approximately 45
minutes).
The benzo-a-pyrene spots were identified by comparison of
Rf's with that of the standard spot under an ultraviolet
lamp. The spots/ marked with a pencil, were circumscribed
with a #15 cork borer and scraped from the plate into vials.
All TLC work was performed as much as possible in a dimly
lighted area to avoid decomposition of the benzo-a-pyrene.
Five ml of 5 percent acetone in n-pentane was added to the
alumina in the vial and it was agitated for 15 minutes on
a mechanical shaker. The slurry was filtered through an F
sintered glass filter into a vial, washing the alumina four
times with approximately 2 ml of 5 percent acetone in n-pen-
tane with a 45-second soak period between each wash. The
combined filtrates were evaporated to dryness at room tem-
perature using a stream of filtered air. The benzo-a-pyrene
residue was taken up in 2.0 ml of concentrated sulfuric acid.
This solution was evacuated for five minutes to remove trapped
air bubbles and its fluorescence was measured in a one-cm
cell at 540 nm while exciting at 470 nm on an Amino-Bowman
Spectrophotofluorometer using a #4 slit arrangement and a
sensitivity of 30.
Standard and blanks were carried through the entire TLC pro-
cedure. The blanks were subtracted from all fluorescence
readings and the net fluorescence values for each sample
were used to calculate the amount of benzo-a-pyrene present.
Throughout all steps in the procedure the samples were refrig-
erated when not actually being processed and exposure of
the samples to light was kept at a minimum.
36
-------
c. Trace Metals
Both emission spectrometry (ES) and atomic absorption (AA)
were used for determination of metals in the particulate.
Atomic absorption was primarily used for lead determination.
Trace metals were determined by ES on Millipore filters while
lead was determined as a percent of the particulate collected
on the 142 mm, 1 cfm fiberglass filter.
1) Emission Spectrometry
-,
a) Principle
Organic matter in the sample is destroyed by wet ashing in
sulfuric, nitric and perchloric acids. The resulting solu-
tion is taken to dryness and the residue is taken up in a
spectroscopic buffer solution containing the internal refer-
ence element, palladium. A portion of the solution is dried
on pure graphite electrodes. The electrodes thus prepared
are excited in an a.c. arc discharge and'the spectrum is
photographed. The intensity ratios of selected lines are
determined photometrically and the concentration of each
element is read from an analytical curve relating intensity
ratio to concentration.
b) Apparatus
(1) Excitation. Excitation is obtained by the use of a
2400 volt a.c. arc discharge - Jarrel-Ash Custom Varisource,
or equivalent.
(2) Spectrograph - Baird 3 meter grating spectrograph.
Reciprocal dispersion is 5.55 A/mm in the first order.
37 ,
-------
(3) Developing equipment - Jarrel-Ash Company. Plates are
developed in a thermostatically controlled developing machine,
washed and dried over heat in a stream of air.
(4) Densitometer. Spectral lines are measured with a non-
recording projection-type densitometer. Densitometer Com-
parator, Baird Associates Inc.
(5) Calculating equipment. A calculating board is employed
to convert densitometer readings to log intensity ratios.
Jarrel-Ash Company.
(6) Wet ashing equipment. A micro Kjeldahl digestion rack
is used for wet ashing the organic solvents.
c) Reagents and Materials
(1) Distilled nitric and perchloric acids. Perchloric acid
is an intense oxidizing agent. Organic matter should not
be heated in perchloric acid unless in the presence of sul-
furic or nitric acid.
(2) Sodium nitrate, reagent grade (NaNO.,) .
(3) Palladium diamine nitrite, Pd (NH-.) , (NO,) , .
•J £• £* £•*
(4) Water soluble salts of the elements Al, Ca, Cu, Fe,
Mg, Mn, Ni, Pb, Sn, and Zn.
(5) Electrodes, high purity graphite, 1/4" diameter by
3/4" length. Ultra Carbon Corporation.
(6) Photographic plates - Eastman Spectrum Analysis No. 3.
(7) Kjeldahl flasks, 10 ml.
38
-------
d) Calibration
(1) 0.2182 gm of palladium diamine nitrite Pd(NH3)2(NO2)2
were dissolved in water. 10 ml of concentrated reagent grade
nitric acid were added and the mixture diluted to volume
with water in a 100 ml volumetric flask. This solution con-
tains 1 mg Pd per ml.
(2) A buffer solution was prepared by dissolving 20 gm of
sodium nitrate in water. 5.0 ml of the palladium solution
above and 7.5 ml of concentrated reagent grade nitric acid
were added and the whole diluted to 100 ml.
(3) A stock solution containing 0.01% (0.1 mg/ml) each of
the elements Al, Ca, Cu, Fe, Mg, Mn, Ni, Pb, Sn, and Zn was
prepared. Two aliquots of this solution were diluted ten-
fold and one hundred-fold to provide 0.001% and 0.0001%
solutions.
(4) Standard additions of the impurity elements were made
to Kjeldahl flasks as shown in Table 6.
(5) 0.5 ml of concentrated reagent grade sulfuric acid was
added to the Kjeldahl flasks and the solution evaporated
to dryness. After cooling, 1 ml of concentrated nitric acid
was added and the mixture was evaporated to dryness again.
The residue was taken up in 5 ml of buffer solution, warming,
if necessary, to put the salts into solution.
39
-------
Concentration
Table 6
ial. of standard addition impurity solution
Blank
o.cooo:.^
O.OCGCS'o*
O.CCGG5"
O.COOl^j
O.OGO:-::%
O.OOO-C •>
O.OC.375%
0.001%
O.CO2i%
O.C05%
0.01 %
•
0.5 nl!
1.25 nl.
O.T.5 L-.1.
O.5 ni.
1.25 nl.
2rt ... t
. U I..U. .
0.375 :•:!.
0.5 til.
1.25 nl.
2.5 ial.
5.O
O.CG01% t
it
O.C01SS
II
II
II
o.oiss
If
II
II
tl
JOl
II
II
tt
It
11
II
II
II
tt
II
Element
Analytical
Lino A
Table 7
•Analytical Liuo Fairo
Internal Standard
LiD.o A
Al
Ca
Cu
Fe
Fo
i!g
KS
Kn
Kn
Ni
Ni
Pb
Pb
Sn
Sn
Zn
3032.71
3179.33
3273.93
3021>O7
3020. 84
XGO2.C9
2770. £3
2033.03
2VP-S.C2
3-11-1.77
303 7. C-l .
2O *vO o o
o /O , «J»j
2033.07
3175.02
2£63.33
33':S.03
3027.01
M
•I.
II
II
II
It
tl
tt
II
IJ
II
tl
II
u
Pd
Concentration
0.000025-0.OOlc
O.OO025-0.010
O.O0001-O.OC32;
O.OO01-0.010
0.000025-O.G05C
O.OOG025-O.C01C
O.OO05-O.010
O.OC05-0.010
O.OOC01-O.CD10
.O.COG025-O.OO1C
O.OO05-O.OIO
O.OO10-0.010
O.OO005-O.OC5O
O.00005-0.COGO
O.OO075-O.01O
O.OOO1-0.010
40
-------
(6) The end of the 3/4" graphite electrodes was polished
on filter paper and placed in a stainless steel drying tray.
A drop of kerosene was placed on the top of each electrode
to seal the porosity and the electrode allowed to dry. One
pair of electrodes was prepared for each of the standard
addition solutions by pipetting 0.03 ml of the solution onto
the end of each electrode. The electrodes were dried slowly
over micro burners in a gas drying oven and stored in a desic-
cator until run.
(7) The samples were excited in water cooled electrode
holders using the following conditions:
(a) Current, 4.0 amps, a.c. arc.
(b) Spectral region, 2150-3550 A.
(c) Slit width, 50y
(d) Electrode gap, 2 mm.
(e) Pre-burn period, 10 seconds.
(f) Exposure period, 90 seconds.
(8) The emulsion was calibrated by use of a stepped filter
or by other recommended methods described in the "Recommended
Practice of Photographic Photometry in Spectrochemical Anal-
ysis" A.S.T.M. Designation: E116, Methods for Emission
Spectrochemical Analysis, (1964).
-------
(9) The emulsion was processed according to the following
conditions:
(a) Developer (D19, 20.5°C)/ 3 1/2 minutes.
(b) Stop bath (SB-4), 1 minute.
(c) Fixing bath (Kodak Rapid Fixer), 2 minutes.
(d) Washing, 3 minutes.
^
(e) Drying, in a stream of warm air.
(10) The relevant analytical line pairs were selected from
Table 7. The relative transmittances of the internal stan-
dard line and each analytical line were measured with a den-
sitometer. The transmittance measurements of the ancilytical
line pairs were converted to intensity ratios by the use
of an emulsion calibration curve and a calculating board.
(11) Analytical curves were constructed by plotting con-
centration as a function of intensity ratio on log-log graph
paper. For best results, the average of at least four deter-
minations recorded on two plates were plotted.
e) Procedure
(1) The available sample was weighed directly into a Kjeldahl
flask. Sulfuric acid was not used in the wet ash procedure
because test samples usually contained a large amount of
lead which would form the insoluble sulfate. Wet oxidation
was carried out with nitric and perchloric acid only. Extreme
-------
caution was exercised in the use of this technique. Concen-
trated nitric acid was added dropwise, a few tenths ml at
a time, to the hot mixture to aid in oxidation. A few drops
of concentrated perchloric acid may be added to the hot solu-
tion after most of the free carbon has been destroyed, to
hasten complete oxidation. When the solution became water
clear, it was evaporated to dryness. After cooling, 0.5
ml of nitric acid was added and the mixture evaporated to
drynesst The addition of 0.5 ml of nitric acid was repeated
and the solution evaporated to dryness again. The inorganic
residue was dissolved in dilute nitric acid and the volume
adjusted to a known concentration, usually 10 mg/ml. If
the original sample size was below 30 mg, a less concentrated
solution was usually made up. Aliquots of this solution
were taken to dryness and then the buffer solution (d2) added
in an amount to give a dilution factor of lOOx. One sample
was analyzed by the direct reader while a second was examined
photographically. Some samples had to be run at factors
larger than lOOx in order to get the concentration for some
elements to fall within the range of the'analytical curves.
By varying the sample to buffer ratio any number of concen-
tration or dilution factors could be achieved. A blank of
the acids used was carried through in the same manner as
the sample.
(2) Proceed as in d(6), (7), (8), (9), and (10) of the
calibration procedure. Duplicate spectra were recorded for
each sample.
f) Calculations
The intensity ratios were converted to concentration by use
of the analytical curves.
43
-------
g) Precision and Accuracy
Representative precision and accuracy of the method are
given in Table 8. Each of the twelve samples A,, A?, A^,
B,, B-, B3, C,, C-r C~, D,, D~, D., , was analyzed by means
of duplicate excitation.
2) Atomic Absorption
a) Method for Lead Determination
Following nitric acid digestion, particulate samples were
washed into 50-ml volumetric flasks and diluted to mark.
This normally put the concentration of lead in the flasks
between 20 and 200 yg Pb/ml. If the concentration was higher
than 200 yg Pb/ml, the sample required redilution. The sam-
ples were analyzed on an atomic absorption spectrophotometer
(Perkin-Elmer Model 303) using, a hollow cathode lamp with
a lead cathode filament. Operating conditions were as fol-
lows: 10 milliamps tube current, light path slit opening -
4, ultraviolet light range, acetylene-air oxidizing flame,
one-slot burner head, wavelength - 2170 angstroms. The sam-
ple solution is aspirated into the flame where lead atoms
present absorb the light from the lead cathode filament.
The amount of absorbed light is proportional to the concen-
tration of lead. The samples were analyzed in conjunction
with the following series of lead standards: 10, 20, 40,
60, 80, 100, 150, and 200 yg Pb/ml. The concentration of
the standards was plotted versus their absorbance values
giving a standard curve. With the absorbance values for
the samples and the standard curve, it was possible to deter-
mine the concentration of lead in the samples. The sensi-
-------
TABLE 8
»j REPRESENTATIVE PRECISION AND ACCURACY OF EMISSION SPECTROSCOPY
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-------
tivity for the lead determination in an air-acetylene flame
is about 0.25 yg Pb/ml at 1 percent absorption. The detec-
tion limit is 0.1 pg Pb/ml.
k) Determination of Lead and Iron in Engine Combustion
Chamber Deposits
These samples were thoroughly ground in a mortar prior to
analysis to obtain uniform samples. The ground sample was
dissolved in nitric acid and lead determined by atomic absorp-
tion. A portion of the sample solution was also used in
the determination of iron. Iron is reduced with hydroxyl-
amine to the ferrous state, and reacted with 1,10-phenan-
throline in an acetate buffered solution (pH 5) to form an
orange-red complex. Photometric measurements were made using
a Beckman DU-2 spectrophotometer. Operating conditions were
as follows: sensitivity setting - 2, slit opening - 0.10
mm, wavelength - 510 mm, 40 mm optical cells. The concen-
tration of iron was determined from a standard curve. For
a one gram sample diluted to 100 ml, the detection limit
is about 1 ppm and the sensitivity +_! ppm.
c) Gravimetric Method for Lead Determination in Millipore
Filters
Following nitric acid digestion, concentrated sulfuric acid
was added to the sample to precipitate lead sulfate. The
solution was filtered, and the precipitate dried and weighed
to determine the amount of lead percent. In addition, the
filtrate was analyzed by atomic absorption for trace amounts
of lead. This analysis is included in the total amount of
lead reported for the sample.
-------
d) Determination of Lead and Other Metals in Glass fiber
Filters
The glass fiber filters cannot be digested completely with
nitric acid. They were cooked with concentrated nitric acid
for two hours to leach out the metals. The pulp was filtered
and washed and the filtrate analyzed by atomic absorption
for lead, and by emission spectroscopy for other metals.
3) Scanning Electron Microscopy (SEM) and X-ray Fluorescence
The Scanning Electron Microscope (SEM) was used to identify
(X-ray spectrometer) the collected exhaust particles from
the Andersen Sampler and the Millipore backup filter.
a) Instrumentation
Cambridge Stereoscan Mark 2A
Ortec Non-dispersive X-ray Detector
i
Nuclear Data Analyzer
Varian Vacuum Evaporator
Kinney Vacuum Evaporator
b) Work Outline
(1) Particle characterization (SEM) on plates of Andersen
Sampler
(2) Particle identification (X-ray)
47
-------
(3) Single element X-ray scan
(4) X-ray spectra on impingement area of Andersen plates
and spectra on backup filter
c) Techniques and Methods
(1) Substrates for sample collection: The most satisfactory
substrates for photomicrography were micro cover glasses,
while where X-ray analysis was employed, ultra pure carbon
strips proved best. Silica interference from micro cover
glasses, halogens in epoxy, and thermal instability in mylar
film reduced the desirability for using these materials as
substrates where X-ray analysis was to be carried out.
(2) Storage and sample preparation: All samples were main-
tained in a dry atmosphere from collection to examination.
Both the glass cover slip and the carbon strip substratum
were attached to SEM sample stubs with conducting silver
paint. Samples for SEM characterization were made conductive
o
with a thin layer (~200 A) of gold or gold-palladium evapo-
rated. Graphite carbon was sputtered on the samples used
for X-ray diffraction.
(3) Normal operation for the Stereoscan:
(a) Gun potential - 20 to 30 kV (depending on sample degra-
dation and resolution needed).
(b) Vacuum - -10 Torr.
(c) Sample angle - 20°.
(d) Working distance - 11 mm.
-------
(e) Polaroid P/N Type 55 film with 100 sec exposure.
(4) Normal operations for X-ray Spectrometer (warranted
215 ev FWHM resolution):
(a) Gun potential - 30 kV
(b) 1024 channel - Series 2100 Nuclear Data Multichannel
Analyzer
(c) Collection time - 200 sec
(d) Count rate - ~60 c.p.s.
(e) Spectra recorded on Moseley 7035B X-Y Recorder
(f) Single channel recording
(g) Polaroid P/N Type 55 film 400 sec or 800 sec exposure
depending on concentration
d) Analysis
(1) Particle characterization and photomicrographical docu-
mentation was done with the scanning electron microscope
employing standard operational procedures.
(2) Particle identification involved elemental analysis
using the X-ray spectrometer on the scanning electron micro-
scope. This included, for multiple particles, full spectrum
elemental scan, and single element scan. Spot scans were
carried out on single particles or in specific regions of
particles.
-------
7. Condensate Analyses
Condensate was collected from the raw exhaust as described
in Section III-C. The Condensate was analyzed for aldehydes
and NH., using the procedures outlined below.
a. Aldehydes
The analytical method for the determination of carbonyl com-
pounds in automotive exhaust emissions employed polarographic
-.
techniques. Samples for analysis were collected from undi-
luted exhaust effluent using ice-water cooled cold traps
and via a sample probe welded into the engine or vehicle
exhaust system. A Princeton Applied Research Model 170 Elec-
trochemistry System was used as the monitoring device. The
derivative pulse polarographic mode yielded the best combin-
ation of carbonyl compounds. A dropping mercury electrode
with a Princeton Model 172 Drop Timer was employed as the
working electrode.
Hydrazine derivatives (hydrazones) were employed for the
determination of the carbonyl compounds, since hydrazones
are easier to reduce than the free compounds', thus elimi-
nating many possible interferences.
An acetate buffer of approximately pH 4 (an equimolar mixture
of acetic acid and sodium acetate, 0.1 M in water) was used
to control pH for hydrazone formation and also acted as sup-
porting electrolyte. Hydrazine was added as a 2 percent
aqueous solution. In this system formaldehyde gave a peak
potential (half-wave potential) of -0.92 v vs. a saturated
calomel reference electrode. A platinum wire was employed
as the auxiliary electrode.
50
-------
With the above system, it is possible to distinguish between
and simultaneously determine aromatic aldehydes, formaldehyde,
higher aliphatic aldehydes, and aliphatic ketones as shown
in Figure 5.
Since aromatic ketones, e.g. benzophenone, give polarographic
response in pH 4 buffer without hydrazine, it is also pos-
sible to detect aromatic ketones. Lead and zinc could also
be determined from the samples under these conditions.
Since formaldehyde was the main carbonyl component of the
condensate samples, all results were calibrated against and
reported as formaldehyde. The upper curve in Figure 6 shows
an actual sample without hydrazine present and demonstrates
the lack of interference in the carbonyl region. The lower
curve shows the same sample after the addition of hydrazine.
Figure 7 shows the same solution after the addition of a
formaldehyde standard. These two figures clearly establish
the presence of formaldehyde in the exhaust samples.
Procedure:
i
Pipet 2 ml of methanol sample into a 25-ml volumetric flask.
Add 10 ml of pH 4 acetate buffer and dilute to volume with
water. Transfer this solution to a polarographic cell and
deaerate with oxygen-free nitrogen for ten minutes. Record
a derivative pulse polarogram from 0 to -1.6 v vs. SCE.
Add 2 ml of hydrazine reagent to the polarographic cell and
deaerate for 5 minutes. Again, record the polarogram from
0 to 1.6 v vs. SCE.
Lead and aromatic ketones are determined from the waves ob-
tained without hydrazine at the peak potentials listed above.
Formaldehyde, higher aliphatic aldehydes, aromatic aldehydes,
and aliphatic ketones can be determined from the second polar-
ogram with hydrazine present.
51
-------
: i-H-i rH-Tf
;——!—-Polarographi c Determination of Aldehydes^
• u - Jj "I -'
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-------
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: I
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' i. i' 11 • • i j.,!,.., i:;..!' I' .. '\'+ i!! ; I:; i! j |
i.li|iins 'lent OAOjIiut'OJJJjiu i' I i ! ! i ! I i5-.""i ! ' | i ! Li ! t'! !
L • ! i' i 1- 1 • . . 1 • . i : • :. i • • • •-•—-^- • :; • i' i. • i
-------
All responses should be calibrated by addition of known amounts
of standard compounds to actual runs. Peak heights are linear
with concentration.
In this system, zinc has a peak potential of -1.00 v vs.
SCE, but it can be differentiated from benzophenone by the
fact that it possesses only one polarographic wave.
A blind comparison of the polarographic technique vs. the
MBTH technique was made, and the results were as follows,
expressed as formaldehyde:
MBTH Polarographic
340 ppm 300 ppm
1500 ppm 1530 ppm
430 ppm 480 ppm
105 ppm 110 ppm
150 ppm ' 110 ppm
b. Ammonia
i
Ammonia was present in the exhaust gas condensate and was ana-
lyzed in the following manner.
A 5-10 cc aliquot of condensate was added to a 50 percent
potassium hydroxide solution. This mixture was then steam
distilled into an excess of 0.010 N hydrochloric acid. The
excess acid was determined by adding potassium iodide and
iodate and titrating the liberated iodine with 0.010 W sodium
thiosulfate.
This technique is capable of determining ammonia as low as
0.3 ppm. Figure 8 is a sketch of the apparatus used for
the determination.
-------
55
-------
•rne anaxyricai proceaures given Herein nave been adapted
from literature sources or developed upon the basis of exper-
imental data which are believed to be reliable. In the hands
of a qualified analyst they are expected to yield results
of sufficient accuracy for their intended purposes. However,
The Dow Chemical Company makes no representation or warranty
whatsoever concerning the procedures or results to be obtained
and assumes no liability in connection with their use. Users
are cautioned to confirm the suitability of the methods by
appropriate tests.
56
-------
V. EXPERIMENTAL RESULTS
The primary goal of this contract was to develop a test pro-
cedure which would be reproducible, reasonably inexpensive,
and which could be performed in other test facilities with
a minimum of modifications to existing equipment, for the
purpose of evaluating any negative or positive effects of
a given fuel additive on particulate exhaust emissions.
Included in this section will be the data generated while
trying to establish a consistent testing method. The basic
method was generally described in section III.
A. SPECIFIC CONCLUSIONS
1. Additive B, at the then manufacturer's recommended
level, increased particulate emissions in both engine
stand and vehicle test runs, from 50% to 100% above the
baseline (Figures 12, 13, 18) when collected on the 142 mm
glass fiber filters. Increases in particulate with the use
of Additive B fuel were also noted in the Andersen separator
and back-up filter, but the increases were not as pronounced,
2. Additive A, at the manufacturer's recommended level,
did not significantly increase or decrease the particulate
emission levels in the vehicle test runs (Figures 12
through 15) .
3. Additive A, at the manufacturer's recommended level,
slightly decreased the particulate emissions under 23-minute
Federal cycle cold start and hot start conditions, when
tested on the engine stand (Figures 18, 19).
4. Additive B increased unburned hydrocarbons in the raw
exhaust under both steady-state and 23-minute Federal
cycle cold start conditions, when tested in the vehicles
(Figures 16, 17) .
57
-------
5. Additive A did not significantly increase or decrease
unburned hydrocarbons under either steady-state or cyclic
conditions when tested in the vehicles (Figures 16, 17).
6. The use of Additive B, at three times the manufacturer's
recommended level, gave particulate emission increases
varying from 8 times greater than the baseline and 5 times
greater than the particulate measured at the recommended
dosage level, when tested under Federal cycle cold start
conditions (Figures 18, 19) and collected on 142 mm glass
filters. The respective increases for the Andersen plus
back up filters are 3 times the baseline and 9 times the
IX concentration.
7. The use of Additive A at three times the manufacturer's
recommended level gave no significant increase in particulate
emissions compared to the baseline or to the recommended
dosage level (Figures 18, 19).
8. Increasing the additive dosage to three times the manu-
facturer's recommended level caused the same general effect
on particulate emissions after a 75-hour cyclic conditioning
period on the engine stand, as was noted after approximately
17,000 miles of vehicle testing (Figures 12, 13, 18, 19).
9. The increase in particulate and hydrocarbon emissions
noted with Additive B in the vehicle tests was a function
of mileage and did not appear to level off until after
10,000 miles (Figures 12 through 17).
10. The particulate emissions measured after a 75-hour
cyclic conditioning period on the engine stand using the
manufacturer's recommended dosage correlates well with the
measured particulate after 5,000 miles (break-in period
plus 1,500 miles) of vehicle testing. A 75-hour sequence
of 23-minute cycles equates to about 1,500 vehicle miles
(Figures 12, 13, 18, 19) .
58
-------
11. Examination of the particulate by the scanning
electron microscope showed differences in size distribution
and particle shape between the baseline and the two
additives tested.
B. FUEL AND ADDITIVES
The fuel used in all of the tests was Indolene 0, to which
the additives were added in the desired amounts. Table 9
is a listing of the pertinent physical and chemical data
on the base stock fuel, as well as the physical and chemical
analyses of the fuel after the additives were blended.
The additives which were used as references for the develop-
ment of the methodology are described in Table 9. Both addi-
tives were blended into the fuel in two different concen-
trations. Additive A was used at 1.87 grams/gal., which
was the level recommended by the manufacturer, and at 3 times
the recommended level, or 5.61 grams/gal. Additive B was
used at .9988 grams/gal., which is equivalent to .25 grams/gal,
of manganese. At the time of the tests, this was also the
level recommended by the manufacturer. The recommended
usage rate has since been reduced. Engine runs were
also made with 3 times the recommended level, or .75
g/gal. of manganese.
The vehicle tests were carried out using only the recommended
levels of additives, while engine dynamometer studies were
carried out with both concentrations.
C. TEST PROCEDURES
1. Engine Dynamometer
The engine was broken in according to the procedures outlined
in Section III-A 1. After break-in, the engine was run 19
59 '
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hours a day, with a 5-hour shut-down period, until approxi-
mately 75 hours had been accumulated. At the start of each
19-hour segment a gaseous exhaust analysis was run to deter-
mine the point at which the engine stabilized. Based on
prior particulate loads, it was felt that in all cases, full
stabilization was reached prior to 75 hours.
The 75-hour runs consisted of repeated 23-minute Federal
cycles. These cycles were controlled by the mode monitor
system described in Section III-A 1. At the end of 75 hours,
particulate measurements were made using a single 23-minute
Federal cycle. Both cold starts (12-hour room temperature
soak period) and hot starts were run for particulate collec-
tion. The procedures used for collection and analyses are
described in Section III-B, C, and D.
The engine tests were run in the following sequence:
1. Additive A at 1.87 g/gal. .
2. Additive A at 5.61 g/gal.
3. The engine was then disassembled, deposits were cleaned
out, new exhaust was installed.
4. Additive B at .25 g/gal. of manganese. The engine was
again dissambled, deposits were removed, and new exhaust
system installed.
5. Baseline fuel, with no additives. Engine disassembled,
deposits cleaned, and new exhaust installed.
6. Additive B .75 g/gal. of manganese
62
-------
It was felt that the baseline run would be more meaningful
if it were run at some point in the middle of the tests,
rather than at the beginning, since any changes in the engine
due to the use of the additive at 3 times the concentration
would be noted. The use of additive A at recommended levels
was not expected to have any negative effects on the engine,
while the 3x effect was unknown. Additive B, containing
an inorganic functional group, was expected to give more
engine deposits, and therefore the 3x concentration was run
iast.
2. Vehicle Tests
Three 1972 Chevrolets, equipped with an automatic transmis-
sion, air conditioning, and a 350 CID engine, were used for
mileage accumulation studies for each additive and a baseline.
The additive concentrations used in the vehicle fuels were
at the manufacturer's recommended level, or .25 g/gal. of
manganese for Additive B and 1.87 g/gal. of Additive B.
All of the vehicles were operated on baseline fuel for 2,000
miles, after which the two additive cars were switched to
their respective fuels.
Blowby tests (Section III-A) were run every 1,000 miles until
it was determined that the engine had stablilized. Figures
9, 10, 11 show the measured blowby at three different points
in each vehicle's life. It is apparent that all three vehi-
cles stabilized relatively quickly, with no abnormalities
showing up in the blowby results.
The vehicles were driven by Dow employees in normal driving
situations, which included a combination of urban and high-
way driving. Some care was exercised in ascertaining that
the vehicles were not driven for prolonged periods of time
above 70 mph, the maximum posted speed limit on Michigan
highways. The vehicles were periodically rotated between
drivers so that each vehicle had a similar operating
history.
63
-------
J.T: was rext tnat me oasexine run WOUO.Q De more rneaning±ui
if it were run at some point in the middle of the tests/
rather than at the beginning, since any changes in the engine
due to the use of the additive at 3 times the concentration
would be noted. The use of additive A at recommended levels
was not expected to have any negative effects on the engine,
while the 3x effect was unknown. Additive B, containing
an inorganic functional group, was expected to give more
engine deposits, and therefore the 3x concentration was run
last.
^
2. Vehicle Tests
Three 1972 Chevrolets, equipped with -an automatic transmis-
sion, air conditioning, and a 350 CID engine, were used for
mileage accumulation studies for each additive and a baseline.
The additive concentrations used in the vehicle fuels were
at the manufacturer's recommended level, or .25 g/gal. of
manganese for Additive B and 1.87 g/gal. of Additive B.
All of the vehicles were operated on baseline fuel for 2,000
miles, after which the two additive cars were switched to
their respective fuels.
Blowby tests (Section III-A) were run every 1,000 miles until
it was determined that the engine had stablilized. Figures
9, 10, 11 show the measured blowby at three different points
in each vehicle's life. It is apparent that all three vehi-
cles stabilized relatively quickly, with no abnormalities
showing up in the blowby results.
The vehicles were driven by Dow employees in normal driving
situations. Some care was exercised in ascertaining that
the vehicles were not driven for prolonged periods of time
above 70 mph, the maximum posted speed limit on Michigan
highways. The vehicles were periodically rotated between
drivers so that each vehicle had a somewhat similar opera-
ting history.
64
-------
Figure 9
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IriDOLENC 0 BASELIt.'E
10,660 MILES -
1,783 MILES ----
13., ,710 MILES-*? •••• <> o «
BLO'.IBY .'l
1 1,5
CFM AT STANDARD CONDITION;
65
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66
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2,077 PILES
12,983 MILES r*o.
BLO'.IBY flEASURED
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CPU AT STANDARD ConnmoNs
67
-------
D. DATA
Tables 11, 12, 13 are a compilation of the data generated
during the 75-hour engine runs. The particulate measure-
ments and analyses were made on individual 23-minute Federal
cycles at the conclusion of the 75-hour conditioning. Tables
14, 15, and 16 are compilations of the data generated over
the lifetime of the vehicles under test.
The mass distribution plots, from which the mass medium equiv-
alent diameters in Tables 17 and 18 were determined, are
found in Appendix A, in order of run number.
E. DISCUSSION OF RESULTS
The primary purpose of this contract was to develop an engine
stand method which would determine any effect of a given
additive on the particulate phenomena noted in a vehicle
operating on fuel using that additive. The purpose was not
to determine whether the two additives under test were good
or bad. Any conclusions drawn from the data presented herein
are done so solely for the purpose of validating the proposed
method.
1. Vehicle Particulate Emissions
By approximately 17,000 miles, the vehicles began to show
a definite pattern as to the grams/mile emission measured
from each one. Figures 12 and 13 show graphically the par-
ticulate emission rate as a function of miles. Additive
B appeared to cause a substantial increase in particulate
emissions, while Additive A caused neither an increase nor
decrease compared to the baseline. The 142 mm, 1 cfm filter
68
-------
gave the most consistant results, while the Andersen impactor
plus Millipore (Figures 14 and 15) gave more scatter.
2. Engine Stand Particulate Emissions
The particulate emissions measured at the conclusion of the
75-hour conditioning sequence are shown graphically in Fig-
ures 18 and 19.
The 23-minute Federal cycle is equivalent to about 7.5 miles
of driving. Therefore, 75 hours of continuous 23-minute
cycles represent only about 1,500 miles of vehicle operation.
The particulate emission increases noted using Additive B
at recommended levels in the vehicles showed up to a lesser
degree in the engine runs, as was to be expected. However,
when the additive concentration was tripled, the increased
particulate which showed up with Additive B in the vehicle
tests was duplicated in the engine runs, v/hile the particu-
late levels of Additive A were not significantly different
from the baseline.
3. Particulate Composition
The particulate emissions generated under both the engine
and vehicle test programs were analyzed for trace metals,
C, H, N, Benzo-a-pyrene, and benzene solubles. This data
is included in Tables 11 through 16. Some significant con-
clusions from the analyses are as follows:
a. As might be expected, the manganese containing Additive
B gave particulate high in manganese. Additive B showed
a lower percentage of C, H, and N in the particulate, and
in general, lower benzene solubles, than the baseline or
the Additive A. However, in total there appeared to be more
organic particulate present using Additive B since the total
mass was larger.
69
-------
b. Additive A showed higher Benzo-a-pyrene in the particu-
late from the engine runs and from the engine deposits taken
from the vehicles, while the exhaust particulate Benzo-a-
pyrene compared to the baseline vehicle run was inconclusive.
Additive B showed lower ppm of Benzo-a-pyrene, as would be
expected since the total mass was larger.
c. In general, the analyses for C, H, and N showed wide
variations. It is difficult to make any meaningful conclu-
sion, per se, since the precision of the technique used is
•.
so dependent on sample size, and since the sample sizes in
general were so small.
d. The carbon content of the particulate collected from
the 60 mph steady state vehicle runs decreased from 36%
to 8% for the baseline fuel over the 17,000 mile test
period, while remaining virtually constant at around 20%
for Additive b over the same mileage. Additive A showed
an initial increase from 40% to 78% carbon, with a subse-
quent decrease to 25%. Although the carbon content decreased
for the baseline, the total particulate mass emissions under
these conditions remained relatively constant. The Additive
i
B mass emissions increased, while the carbon content
remained constant.
e. The correlation between the engine runs and the vehicle
tests with respect to C, H, and N analyses of the particulate
is not good. The most important factor contributing to
this is the small sample size collected under the Federal
Cycle. The steady state collection on the vehicles gave
enough sample for relatively precise analyses, but the
23 minute cycle generally produced such small amounts of
collected particulate that analytical precision was low.
No steady state collections were made on the engine runs.
> 70 ;
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IX (41
C -H
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Date: 7/9/73
Vehicle No. = D-2547
Fuel Used = Base Fuel No Additive
TABLE 14 Con't.
ENGINE DEPOSITS RATING SHEET
1) Carburetor No deposits but a very light coating
that was black in color.
Throat
Butterfly
2) Intake Manifold No deposits but black in color.
3) Exhaust Manifold Normal deposits black to gray in
color.
4) Intake Valves Back side of valve had heavy black
deposit above normal.
5) Exhaust Valves No deposit but dark brown in color.
6) Combustion Chamber Very few deposits. Surface was
dark tan to black in color.
7) Spark Plugs Very few deposits. Surface' was dark tan
to black in color.
NOTES: The only thing that seemed to be abnormal was the amount
of deposit on the back side of the intake valve. Other-
wise a very clean engine.
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-------
Date: 7/12/73
Vehicle No. = D-2548
Fuel Used = Additive A
TABLE 15 Con't.
ENGINE DEPOSITS RATING SHEET
1) Carburetor Clean, bare metal. No deposits or
discoloration.
Throat
Butte --f ly
2) Intake Manifold Clean with no deposits or discoloration
but the surface was wet with a film
coating.
3) Exhaust Manifold Light coating of black carbon with no
buildup of deposits.
4) Intake Valves Some buildup of a black deposit that had
a gooey consistancy was present on the
back side of all valves.
5) Exhaust Valves A thin reddish coating was present on
the back side of valve while the tops
were whiteish.
6) Combustion Chamber Thin deposit brown to black in color.
Coating was equal on all cylinders.
7) Spark Plugs No deposits with a dark brown color.
Appeared cleaner than normal.
NOTES: In general it appeared to be the cleanest engine of
the three with no heavy deposit buildup.
87
-------
Date: 7/12/73
Vehicle No. = D-2548
Fuel Used = Additive A
TABLE 15 Con't.
ENGINE DEPOSITS RATING SHEET
1) Carburetor Clean, bare metal. No deposits or
discoloration.
Throat
Butterfly
2) Intake Manifold Clean with no deposits or discoloration
but the surface was wet with a film
coating.
3) Exhaust Manifold Light coating of black carbon with no
buildup of deposits.
4) Intake Valves Some buildup of a black deposit that had
a gooey consistancy was present on the
back side of all valves.
5) Exhaust Valves A thin reddish coating was present on
the back side of valve while the tops
were whiteish.
6) Combustion Chamber Thin deposit browfi to black in color.
Coating was equal on all cylinders.
7) Spark Plugs No deposits with a dark brown color.
Appeared cleaner than normal.
NOTES: In general it appeared to be the cleanest engine of
the three with no heavy deposit buildup.
88
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-------
Date: 7/11/73
Vehicle No. = D-2549
Fuel Used = Additive B
TABLE 16 Con't.
ENGINE DEPOSITS RATING SHEET
1) Carburetor Dark gray color, clean with no deposit
buildup, considered normal.
Throat
Buttcifly
2) Intake Manifold Black color, clean and dry with no
deposits, considered normal.
3) Exhaust Manifold Black color, carbon coated but dry,
considered normal.
4) Intake Valves Considerable buildup. Black deposit
was present on the back side of all
intake valves.
5) Exhaust Valves Were tan in color with a thin black
coating. There were no deposits as
such.
6) Combustion Chamber The quantity of deposits appeared
to be normal although some cylinders
had more deposits than others.
7) Spark Plugs The deposits were tan in color and below
normal in amount.
NOTES: Deposits in the combustion chamber were tan in color.
When the deposits were scraped from the piston tops,
most of the deposit or coating would come off, leaving
the bare aluminum.
Some spark plug fouling was noted.
93
-------
TABLE 17
MASS MEDIUM EQUIVALENT DIAMETER ENGINE STAND RUNS
cutoff %
Run #
239 A
239 B
239 C
241 A
241 B
'241 C
240 A
240 C
234 A
234 B
234 C
238 A
238 B
238 C
Additive
B
B
B
B
B
B
Baseline
Baseline
A
A
A
A
Cone,
IX
IX
IX
3X
3X
3X
IX
IX
IX
IX
3X
3X
3X
Mode*
CS
HS
HS
CS
HS
HS
CS
HS
CS
HS
HS
CS
HS
HS
50%
1.5
< .5
< .5
.9
< .5
< .5
1.1
< .5
1.0
1.6
1.0
.9
.55
< .5
80%
3.7
1.4
1.0
2.3
1.0
.7
1.6
2.3
4.3
4.0
3.2
3.0
4.1
2.2
* CS = Cold Start, 23 minute Federal cycle
HS = Hot Start, 23 minute Federal cycle
All % cutoff values in microns
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4. Particulate Mass-Size Distribution
The mass medium equivalent diameter (MMED) for the engine
stand and vehicle tests are summarized in Tables 17 and 18.
Cut-off values of both 50% and 80% are used. In general,
the particulate mass-size distributions range from Additive
B, giving the smallest particles while Additive A gave the
largest, with the baseline in between. The 50% cut-off was
quite inconclusive since most 50% values fell below the
smallest measured separation (,55y). The 80% cut-off showed
much more of a trend toward the conclusion drawn above.
It does not appear that using the additive at 3 times the
recommended levels caused any noticeable difference in MMED.
The complete set of MMED graphs are in Appendix A.
5. Particulate Morphology as Studied by Scanning Electron
Microscope
Samples collected from the vehicles were studied using the
scanning electron microscope to determine if there were dif-
ferences in the physical or chemical nature of the indivi-
dual particles. Several conclusions were drawn, as follows:
a. Additive B tends to produce a very fine particle size
with no evidence of flakes, rods, crystals, or flower-like
material.
b. The base fuel tends to produce more spherical particles
and little crystalline or rod-like material.
c. Additive A tends to produce more crystalline material,
porous rod-like material, and flower-like clumps.
d. 'A flake-like material, never previously encountered in
exhaust particulate photographs, was observed in the base
fuel and with Additive A.
104
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e. The particulate encountered using Additive A was high
in sulfur, while Additive B gave particulate high in manganese,
The data reported as a result of the SEM work must be con-
sidered incomplete because of a lack of individual particu-
late identification. In order to chemically identify the
individual particles and correlate chemistry with morphology,
it is essential that the material be collected on a substrate
that will interfere neither with the chemical nor morpholog-
ical analyses. The most appropriate substrate for use in
\
the Andersen sampler is thin, flat, polished, and pure graph-
ite. Unfortunately, the irregular topography of the graphite
substrates used prevented the measurement of representative
particle morphology. As a consequence, the morphological
studies were carried out on Au-Pd coated particulate collected
on glass cover slips which precluded accurate chemical anal-
yses. The chemical analyses were carried out on aggregates
of particles scraped from the collection plates onto the
graphite substrates, a process which prevents chemical identi-
fication of individual particles.
The complete results of the qualitative chemical analyses
of the aggregates of particulate are summarized in the at-
tached table and the predominant differences in chemistry
are as follows:
TABLE 19
Element Base Fuel Additive A Additive B
Pb high none high
Br low none none
Zn none low low
Ca low low low
S low high low
Mn none low high
105
-------
The data implies that Additive A somehow reduces or eliminates
Pb from the auto exhaust particulate, since the base fuel
in all series contained Pb. The Additive B does not produce
this effect. Br was only found in the base fuel particulate.
Both additives lead to low Zn content in the particulate
(none in base fuel particulate). Additive A gives particulate
relatively high in S, while Additive B produces particulate
high in Mn. Mn was not found in the base fuel particulate
and was only present at a low level in one other sample.
•
The only difference in chemistry between plates would appear
to be a slight tendancy for higher concentrations of some
elements (Si, S, Ca) to be found in the particulate on Plate
5. Another nebulous effect is an apparent increase in Pb
and S when progressing from a cold to a 60 mph start.
The morphological variations are so large within a particu-
lar sample that it is somewhat hazardous to compare samples
and generalize. The scanning electron micrographs are at-
tached and documented in Figures 20 through 33. Compared
to the base fuel sample Additive A appears to produce more
crystalline material, more of the porous rod-like material,
and perhaps more of the flower-like clumps. The base fuel
sample appears to produce more spherical particles and some
crystalline or rod-like material. The 60 mph steady-state
baseline exhibits a small particle size with a relatively
uniform particle distribution. Additive A and the baseline
both contain some thin, flake-like material not previously
encountered. The series of Additive B samples exhibit a
finer particle size than the baseline or Additive A with
no evidence of flakes, flower-like material, crystalline
material, or rods. Additive B Federal cycle cold start par-
ticulate appears more electron-transparent than the other
samples.
106
-------
Figure 20
Baseline, Cold Start, 500Ox
Plate 2, Andersen Separator
Figure 21
Baseline, Cold Start, SOOOx
Plate 2, Andersen Separator
-------
Baseline, Cold Start, 2000x
Plate 2 Andersen Separator
Figure 23
Baseline, Cold Start, 2000x
Plate 2 Andersen Separator
108
-------
Figure 24
Additive A, Cold Start, 2000x
Plate 2 Andersen Separator
Figure 25
Additive A, Cold Start, 2000x
Plate 2 Andersen Separator
-------
Figure 26
Additive A, Cold Start, 10,000x
Plate 2 Andersen Separator
Figure 27
Additive A, Cold Start, 10,000x
Plate 2 Andersen Separator
-------
Additive A, Cold Start, 10,000x
Plate 2 Andersen Separator
111
-------
Figure 29
Additive B, Cold Start, 2000x
Plate 5 Andersen Separator
Figure 30
Additive B, Cold Start, 10,000x
Plate 5 Andersen Separator
-------
Additive B, Cost Start, 2000x
Plate 5 Andersen Separator
Figure 32
Additive B, Cold Start, 200Ox
Plate 5 Andersen Separator
113
-------
Figure 33
Additive B, Cold Start, 5000x
Plate 5 Andersen Separator
114
-------
VI. FUEL-ADDITIVE SURVEY
Part of the effort in this contract involved a study of the
trends which might be apparent concerning the type and usage
rate of future fuel additives. Bay refineries, Leonard
Oil Co., American Oil, Phillips Petroleum, and Union Oil
Co. were contacted in April, 1972, and the subject of new
additives was discussed in detail. In addition, a survey
of the available current literature was made. Most sources
were quite reluctant to discuss additives other than those
currently available, in any but the most general terms.
It appears that most research in this area is guarded
quite closely, since any development of a new additive can
be of more benefit to the developer if it remains propri-
etary as long as possible. Questions concerning trends of
future additive research were invariably met with the
response "we really don't know".
Following is a summary of discussions on currently used
fuel additives, segregated by functionality of the additive.
None of the companies contacted were willing to speculate
on the future of antiknock additives,- assuming that lead
alkyls will be prohibited. No discussion of antiknocks
is made for that reason.
A. DYES
Dyes have for years been added to gasoline at the recommen-
dation of the Surgeon General. The color serves as a warning
that the gasoline contains lead. Oil soluble solid dyes
are generally azo compounds and amino and oxygenated aro-
ma tics, such as benzene, naphthalene or anthracene deriva-
tives. Thus, other than carbon and hydrogen, the only other
115
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elements present in gasoline dyes are oxygen and nitrogen.
Liquid dyes are currently becoming more popular because of
their ease of handling in automatic in-line gasoline blending,
We are not familiar with the chemistry of liquid dyes but
believe that they are quite similar to the solid dyes. Dyes
are added to gasoline at the 1-6 ppm range. Suppliers are
Morton Chemicals, Du Pont and Ethyl. Some examples are
Du Pont Red B Liquid and Du Pont Orange Liquid. In the
future dyes may well be used to a lesser extent than they
are currently. In an EPA proposal for removing lead from
gasoline (Federal Register, February 23, 1972) refiners would
be required to supply by 7/1/74, an unleaded gasoline which
contains no dye. Even though dyes are expensive, people
in the petroleum industry, especially those in Marketing
and Transportation, have gotten accustomed to having gasoline
dyed. The color is helpful as a means to distinguish between
the different grades of gasoline and midbarrel products.
Thus, barring legislation against them, dyes will probably
continue to be used.
B. ANTIOXIPANTS
i
Other than lead alkyls, antioxidants were the first addi-
tives used in gasoline. Antioxidants became necessary when
cracking methods were introduced into refining. Olefins,
which are formed during the cracking process, are suscep-
tible to liquid-phase oxidation. One of the products of
the oxidation process is an insoluble gum. The gum can clog
fuel filters and lines, carburetor jets, intake manifolds,
and valve ports and can add to intake valve tulip area de-
posits. As this oxidation takes place via a free radical
mechanism, materials which donate a hydrogen atom can ter-
minate the formation of the intermediate peroxy radicals.
116
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Thus aromatic amines and phenols are good gasoline anti-
oxidants. The most commonly used materials are W,N'-di-
sec-butyl-p-phenylenediamine, N-n-butyl-p-aminophenol, and
2,6-di-tert-butyl-4-methylphenol. Antioxidant dosages range
from 8-40 ppm. The phenylenediamine type inhibitor is pop-
ular because it also acts as a catalyst for sweetening gaso-
line. Over the years the percentage of olefins in gasoline
has decreased and thus the amount of antioxidants required
has decreased. However, as the olefin content has gone down
the percentage of higher octane aromatics has gone up. Aro-
matics can also form peroxides. Although the aromatic per-
oxides do not contribute to gum formation, they do react
with the lead alkyls. The result is hazy fuel and sometimes
precipitates of lead salts. Thus antioxidants are still
required, although at lower concentrations than for gum pre-
vention. In the future as lead alkyls are removed from
gasolines, the need for antioxidants will be even less.
There are many suppliers of antioxidants such as Du Pont,
Hercules, Productol, Ethyl, Koppers, Shell, and Eastman.
C. METAL DEACTIVATGRS
Trace quantities of metals in gasoline, especially copper,
catalyze the oxidation of the fuel. As little as 0.1 pprn
copper can be troublesome. Copper gets into the gasoline
through either a copper sweetening process or merely from
copper or brass fittings used in refining and distribution.
Copper can be deactivated by the use of a chelating agent.
The most common chelating agent is N,N'-disalicylidene-
1,2-diaminopropane. This material is sold by several addi-
tive suppliers under as many different trade names. Examples
are Du Pont DMD-2, Ethyl MDA, Tretolite Kuplex 60, and East-
man Tenemene 60. Another metal deactivator which is used
is Du Pont Metal Suppressor, a carboxylic acid salt of
117
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1-salicylalaminoquanidene. Metal deactivators are used at
concentrations of 1-12 ppm in conjunction with antioxidants.
Many refiners no longer use metal deactivators, as the trace
metals content of their gasolines may be below the level
necessary to act as a catalyst. Also, as with antioxidants,
as the olefins content of gasoline decreases, the need for
a metal deactivator diminishes.
D. SURFACE-ACTIVE AGENTS
Surface-active agents (surfactants) are the newest type of
additives to be used in gasoline. At very low concentra-
tions these additives can prevent fuel system corrosion,
prevent and remove carburetor deposits, prevent and remove
intake manifold deposits, and prevent carburetor icing.
1) Rust Preventing Additives
Extremely low concentrations of certain surfactants are very
effective in preventing corrosion in wet gasoline systems.
Water, the result of tank breathing, is almost always present
in gasoline terminal storage tanks, gas station tanks and
vehicle fuel tanks. Materials which contain a polar group
and a long hydrocarbon chain can be absorbed in a close-
packed monomolecular layer on metal surfaces. If the film
is impervious to water, then rust protection is achieved.
Carboxylic acids, alcohols, amines, sulfonates, and phos-
phoric acid salts of amines are all effective rust inhibitors.
Commercial rust inhibitors include Du Pont AFA-1, Apollo
PRI-19, Nalco 5400, Vanderbilt Nasul LP, Tretolite Tolad
T-245, UPO Unicor PL, Edwin Cooper Hitec E-534, and Lubrizol
541. These surfactants are quite effective in the range
4-40 ppm. As it is almost impossible to completely elimi-
nate water from liquid fuel systems it is most likely that
the use of surfactant type rust inhibitors will continue
for some time.
118
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2) Gasoline Detergents
Some surfactants are very effective in preventing and removing
deposits which form in the throttle bore area of a carburetor.
Such deposits have been a problem since the widespread use
of 2-barrel carburetor V-8 engines began in 1955. In current
automobiles with their many emission control devices the
accumulation of deposits has become even more severe. Deter-
gent additives have been in use for almost 20 years. The
most effective ones are amines and amine phosphate salts.
Extensive research efforts have been directed toward finding
more effective detergents. The recent trend has been to
higher concentrations of polyamine materials. Unless legis-
lation forces the removal of nitrogen containing additives
from use in gasoline, it appears that because these types
of additives are so effective they will continue to be used.
Current highly effective detergent additives include: alkyl
amine phosphates, e.g. Du Pont DMA-4, Ethyl MPA-90, and Gulf
Agent 724; alkyl amines, e.g. Union Oil NR-76, Enjay Para-
dyne 55, and Humble HTA-71; polybutene polyamines, e.g. Amoco
575, Lubrizol 8101, and Oronite OGA-472. Detergent concen-
trations range from 15 to 150 ppm.
3) Intake Manifold Deposits
Some surfactants, primarily the high molecular weight polymer
dispersants, are effective in preventing and removing intake
system deposits. In this case the cleaning action of the
surfactant is not a result of coating the metal surface but
appears to be the result of softening the deposits so that
they then slough off. A more effective means of removing
and preventing the formation of these deposits is through
the use of an effective dispersant plus a high concentration
(0.05-0.5 volume %) of a low volatility lubricating oil.
In this case the dispersant softens the deposits and the
top cylinder oil serves as a flux to "wash" the metal surface
119
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clean. Examples of dispersant gasoline additives are:
Lubrizol 580 and 8101, Enjay Paradyne 501, Amoco 575, and
Oronite OGA-472. In the past two years there has been a
trend towards the use of dispersant additives and a smaller
yet significant trend towards the use of top cylinder oils.
4) Deicing Additives
Two types of icing occur in automobiles; freezing of water
-in the fuel and carburetor icing. Ice formation in the fuel
can be eliminated through the use of freeze point depressants
such as alcohols, glycols or dimethylf ormarnide. These mater-
ials are added to the gasoline. However, because they are
more soluble in water they move into the aqueous phase and
lower its freezing point. Freeze point depressants are used
at concentrations up to 2 volume %.
Carburetor icing occurs in cool, damp weather when moisture
in the air freezes on metal surfaces in the carburetor throat
and on the throttle blade. Stalling because of carburetor
icing can be reduced through the use of surfactant additives.
Such materials coat the throttle plate and carburetor walls
so that ice crystals will not adhere. The surfactants can
also interfere with ice crystal growth causing a snow-like
ice which is easily blown off of the metal surfaces. Effec-
tive surfactant deicers included Du Pont DMA-4 and Ethyl
MPA-90. These deicers are effective in the 20-100 ppm range.
Because engines in late model cars are designed to heat the
intake air rapidly, the problem of stalling because of car-
buretor icing will not be as critical in the future as it
has been in the past. Thus, additives which function only
as deicers will probably not be used much in the future.
E. "CANNED" ADDITIVES
"Canned" additives, those which are offered for sale in
service stations and retail stores, are a multi-million
120
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dollar per year business. Though many of these additives
claim reduced pollution, increased mileage, higher horse-
power, etc., in most cases these claims are unfounded. The
majority of "canned" additives are top cylinder oils or sol-
vents or both. Those which contain surfactant materials
are similar to the additives mentioned above, although gen-
erally surfactants, if present at all, are present at ex-
tremely low concentrations. However, because there is obvi-
ously a market for these additives, it seems reasonable to
assume that their use will continue.
F. 2-CYCLE ENGINES
Lubrication of 2-cycle engines takes place via the gasoline.
Therefore, gasolines for 2-cycle engines contain the lubri-
cating oil additives. These additives are a combination
of materials which consist mostly of either a calcium sul-
fonate cr amine-type dispersant. Examples are Lubrizol 981
and Oronite 340K, respectively. The concentration of lubri-
cating oil in gasoline varies from 2 to 4 percent. The con-
centration of additive in the gasoline is in the 0.1 to 0.4
percent range. Because of recent water pollution legisla-
tion the lubricating oil concentration will soon be reduced
to 1%. Also in the future the calcium sulfonates may be
replaced dtltogether by the amine-type ashless dispersants.
G. SUMMARY AND CONCLUSION
Extensive research efforts by several companies over many
years have resulted in the gasoline additives which are
currently in use. Research is continuing in an effort to
find even more effective additives. However, current tech-
nology still indicates that the amine, amine phosphate and
amine polymer surfactants are the most effective additives
for controlling many of the problems associated with today's
internal combustion engines. As new applications for addi-
tives are sought possibly a new and different type of addi-
tive will be found. An example of a new use for additives
121
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is Humble's IITA-71. This additive is claimed to control
surge, a problem which is becoming more common in today's
leaner running engines. Here again HTA-71 is an alkyl amine
surfactant. Thus for the naturally aspirated internal com-
bustion engine, we believe that gasoline additive types
currently in use will remain in use for some time.
122
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VII. CONDENSATE COLLECTION AND ANALYSES
A modification to Contract 68-01-0332 included the genera-
tion and collection of exhaust gas condensate samples for
use in biological studies. The condensate was collected
and analyzed using techniques discussed in Sections III-C,
and III-I 7 a,b, respectively. A 1972 350 CID Chevrolet
engine was used. This engine had previously been broken
in and operated on continuous 23-minute Federal cycles.
The conditions of operation for the collection of the con-
-
densate samples was identical to that used for the particu-
late studies. Half of the samples were taken using both
cold start and hot start 23-minute cycles, while half were
taken at 60 mph steady-state conditions. The runs were made
using the Indolene baseline fuel and fuel containing 1.87
g/gal. of Additive A, and .25 g/gal. of Additive B, based
on manganese. Standard gaseous analyses were made, as well
as particulate measurements and analyses. The condensate
analyses data is reported in Table 20, and the particulate
data is in Table 21. Mass size distribution is shown in
Figures 34 through 39.
The samples were sent to the University of Nebraska
•
for use in animal health studies.
123
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U'A-600/3-/b-QlOe
III E AND SUOTITLE
ANNUAL CATALYST RESEARCH PROGRAM REPORT
Appendices, Volume IV
5. REPORT DATE
September 1975
C. PERFORMING ORGANIZATION CODE
UTHORIS)
Criteria and Special Studies Office
0. PEAfORMING ORGANIZATION REPORT NO.
RFORVHNG ORGANIZATION NAME AND ADDRESS
Health Effects Research Laboratory
Office of Research & Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
PONSORING AGENCY NAME AND ADDRESS
Same as above
to. PROGRAM ELEMENT NO.
1AA002
11. CONTRACT/GRANT NO.
13. TYPE OF RE PORT AND PERIOD COVERED
Annu a Program Status 1/74-9/7
AGENCY CODE
EPA-ORD
JPPLEMENfARY NOTES
This is the Summary Report of a set (9 volumes plus Summary).
See EPA-600/3-75-010a thru OlOd, & OlOf thru OlOj. Report to Congress.
BSTRACT
This report constitutes the first Annual Report of the ORU Catalyst Research
Program required by the Administrator as noted in his testimony before the
Senate PUblic Works Committee on November 6, 1973. It includes all research
aspects of this broad multi-disciplinary program including: emissions charac-
terization, measurement method development, monitoring, fuels analysis,
toxicology, biology, epidemiology, human studies, and unregulated emissions
control options. Principal focus is upon catalyst-generated sulfuric acid
and noble metal particulate emissions.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
M
Catalytic converters
ulfuric' acid
esulfurization
atalysts
ul fates
ulfur
=a 1th
RIQUriON STATEMENT
/ailable to public
ll.lDENTIFIEflS/OPEN ENDED TERMS
Automotive emissions
Unregulated automotive
emissions
Health effects (public)
•
19. SECURITY CLASS ( 1 IH.I lirportf
Unc 1 assi f ipd
jo MsEtOTiTfV CLASS fh»i r-fl
Unclassified
t. COSATI 1 njil/dmup
21. NO. OF PAGES
226
72. PRICE
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