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

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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

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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

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                       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

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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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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

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                       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

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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

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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 -'	
                               •-"-ill']/: *-V —.v

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                                          i  ;: I !.';•'  ; i i; i •';;  :'."!'!!;  ;'•;  s,'\\  ' p ';•!,'•
                                          ' i. i' 11 •  •  i j.,!,..,  i:;..!' I'  ..  '\'+  i!!  ; I:;  i! j |

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-------
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

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                 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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                                                     1
                                    CAR 2547
                                    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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                            Figure  10
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                                66

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             I I
                    *—*
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                     !  J.
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                             H
              CAR 2549

              ADDITIVE B

              10,155 MILES 	

              2,077 PILES	

             12,983 MILES r*o.

              BLO'.IBY flEASURED
      . .5
  1                1,5


 CPU AT STANDARD ConnmoNs

67

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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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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.
                             83 ,

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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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-------
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„ FIGURE NO. 19
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__ GRAMS PER MILE PARTICULATE
ON ANDERSEN SEPARATOR PLUS
BACK-UP FILTER

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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

-------
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

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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

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          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

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          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

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              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

-------
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

-------
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

-------
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

-------
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

-------
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

-------
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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