APTD-1567
MARCH 1973
                CHARACTERIZATION
                  OF PARTICIPATES
      AND  OTHER NON-REGULATED
                           EMISSIONS
            FROM MOBILE SOURCES
                  AND THE EFFECTS
            OF EXHAUST EMISSIONS
                  CONTROL  DEVICES
               ON THESE EMISSIONS
     U.S. ENVIRONMENTAL PROTECTION AGENCY
         Office of Air and Water Programs
     Office of Mobile Source Air Pollution Control
        Emission Control Technology Division
           Ann Arbor, Michigan 48105

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                           11
The APTD (Air Pollution Technical Data) series of reports
is issued by the Office of Air and Water Programs, U.S.
Environmental Protection Agency, to report technical data
of interest to a limited number of readers.  Copies of APTD
reports are available free of charge to Federal employees,
current contractors and grantees, and non-profit organiza-
tions - as supplies permit - from the Air Pollution Technical
Information Center, U.S» Environmental Protection Agency,
Research Triangle Park, North Carolina 27711 or may be
obtained, for a nominal cost, from the National Technical
Information Service, U.S. Department of Commerce, 5285 Port
Royal Road, Springfield, Virginia 22151.
This report was furnished to the U.S. Environmental Protec-
tion Agency by The Dow Chemical Company, Midland, Michigan
48640 in fulfillment of Contract Number EHS-70-101.  The
contents of this report are reproduced herein as received
from The Dow Chemical Company,  The opinions, findings, and
conclusions expressed are those of the author and not
necessarily those of the Environmental Protection Agency.
               Publication Number APTD-1567

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                               Ill
                       TABLE OF CONTENTS
FOREWORD 	    v




ABSTRACT 	   vi




   I.   INTRODUCTION 	    1




  II.   CONCLUSIONS 	    3




 III.   EXPERIMENTAL PROCEDURES	    6




       A.  Particle Generation 	    6




           1.  Engine Dynamometer Studies 	    6




           2.  Chassis Dynamometer Procedures 	    9




       B.  Particle Collection 	   11




           1.  Dilution Tube 	   11



           2.  Sampling Devices 	   13






       C.  Condensate Collection 	   15




       D.  Analytical Methods 	   15




           1.  Fuels 	   16




           2.  Oils 	   17




           3.  Diluent Air 	   17




           4.  Exhaust Gases 	   17




           5.  Oxides of Nitrogen 	   19




           6.  Exhaust Particles 	   21




           7.  Condensate Analyses 	   34




  IV.   EXPERIMENTAL RESULTS 	   41




       A.  Task I 	   44




       B.  Task II 	   81




       C.  Task III 	   92




       D.  Task IV 	„	  135




       E.  Task V 	  189




   APPENDIX A 	  192

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                           FOREWORD

This report was prepared by the Transportation Chemicals Research
Group, Ag-Organics Department, The Dow Chemical Company, Midland,
Michigan, under Contract EHS 70-101.  The work reported herein
was administered under the direction of the Office of Air and
Water Programs, Environmental Protection Agency, with Dr. Robert E.
Sampson and Mr. Chas. L0 Gray, Jr. serving as Project Officers.

The report covers work performed from Sept. 1, 1971, to Dec. 31, 1972,

The authors of this report are James E. Gentel, Otto J. Manasry,
and Joseph C. Valenta.

The authors wish to acknowledge the significant contributions
of the following individuals:
               S. M. Sharp                  R. P. Himes
               W. B. Tower                  M. Y. Kelly
               J. D. McLean                 R. E. Mansell
               R. B. Nunemaker              P. P. North
               C. E. Van Hall               S. M. Richter
               H. H. Gill                   N. J. Smith
               G. E. Stobby                 S.    Stell
               H. D. Woodcock               M.    Griggs
               R.    Matalon                K.    Schmeck
               S. W. McLean                 S.    Love
               J. F. Bartel                 B.    Coleman
               Jc T. Dumler                 M. J. Baldwin
               T. A. Killer

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                              VI
                        ABSTRACT

This report describes work carried out on a research program to
determine the effect of emission control devices on the particulate
emissions of an automotive power plant.  The work was divided into
five tasks as follows:

TASK I was the characterization of a particulate trapping system,
and the determination of what effects, if any, were noted as
conditions within the system were controlably varied.

TASK II was the definition of a particulate baseline for a 1972
Pontiac 400 CID engine, using non-leaded and low lead fuel.  No
emission control devices were used for the baseline runs.

TASK III was the evaluation of the particulate emissions from
a 1972 Pontiac 400 CID engine equipped with the following control
devices: three different oxidation catalysts, one NO  catalyst,
                                                    H
and one exhaust gas recirculation system.

TASK IV involved testing automobiles equipped with control devices
for particulate emissions.  These vehicles were supplied by both
the contractor and the Government.

TASK V was to define a preliminary collection system for diesel
engine particulate sampling.

In all tasks, particulate mass emission rates were measured, as
well as particle mass size distribution, carbon and hydrogen, trace
metal, and benzo-a-pyrene content of the particulate.  Ammonia and
aldehydes were measured in the exhaust gas condensate, and gaseous
emissions were determined as a routine check on engine operating
conditions.

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                            -1-
                     I.   INTRODUCTION

The work presented in this report covers the second half of contract
EHS 70-101.  In the  previous work, reported in a final report
dated July 1971, some preliminary studies were made on the effect
of emission control  devices on unregulated emissions.  The extension
to Contract EHS 70-101,  which is reported here, involved a more
detailed look at specific control devices and the resulting effects
on particulate size  and  mass, particulate composition, and condensate
composition.  The work was divided into five specific tasks in order
to smoothly carry out the technical goals of the contract.

The major objective  of Task I was to study the effect of specific
engine and sampling  variables on certain non-regulated emissions
under highly controlled  conditions.  Studies were made on non-leaded
and low lead fuels.

During the course of some preliminary studies undertaken in the
previous year's work on  Contract EHS 70-101, alarming differences
were noted in the mass of particulate emitted when non-leaded fuel
was used, and when the filtering systems and dilution tube were
operated at different flow rates and temperatures.  In order to
reach an understanding of the above effects, and to define a
meaningful set of sampling parameters, a study was made of a number
of sampling variables and their effect on the mass of particulate
matter collected at a filter.

Task II involved running a 400 CID Pontiac engine, using non-leaded
and low lead (0.5 cc/gal) fuels, to determine a baseline for
subsequent studies.  Operating conditions were varied and included
rich,  standard, and  lean air/fuel ratios, as well as advanced,
standard, and retarded spark timing.  The sampling techniques
settled upon in Task I were used to collect particulate.

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                              -2-
The objective in Task III was to evaluate various emission control
devices with respect to their effect on non-regulated emissions.
The devices tested under this portion of the contract include:
        Three oxidation catalysts
        One reduction catalyst
        One exhaust gas recirculation system

Initially, work was done using both non-leaded and low lead  (0.5
cc/gal) fuels.  The leaded fuel itself caused increases in the
amount of particulate and, after testing one catalyst on leaded
fuel, the rest were run only on non-leaded fuel.  The low lead
fuel poisoned the catalyst sufficiently so that it was felt that
future runs would be more meaningful if only non-leaded fuel was
used.

The devices were obtained from either the manufacturer or an auto-
mobile company under a secrecy agreement, to protect any proprietary
rights involved.  Consequently, the data on the devices are reported
with the only reference to the device being a code letter.

Task IV was an evaluation of the particulate emission levels of
vehicles equipped with various control devices.  Several of these
vehicles were made available to Dow by the manufacturer, while others
were supplied by the Government for testing.  Ten different vehicles
were tested, with 19 runs made on the 10.  Each vehicle is discussed
in detail in the Experimental Section of Task IV.

Task V was a limited diesel engine study to establish baseline data
for emissions present in the exhaust.  Due to an increased emphasis
on the vehicle studies, this task was only partially completed.

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                               -3-
                        II.  CONCLUSIONS

1.  The use of three different oxidation catalysts on an engine
    stand, with non-leaded fuel, increased the amounts of particu-
    late collected at 60 mph by a factor of 2-5, compared to a
    baseline run, except under rich air/fuel ratios.  Two catalysts
    did not generally increase the particulate collected at 30 mph,
    or under cyclic conditions, while an increase was noted with
    one catalyst under both conditions.  The total particulate
    collected from the control devices was less than normally found
    when using 3 cc leaded fuel.

2.  There was no evidence in the particulate of catalyst degrada-
    tion being the cause of the increase in particulate mass.

3.  The mass medium equivalent diameter was shifted significantly
    toward smaller particles, when compared to the baseline, for
    all of the catalysts tested on an engine stand.

4.  In almost all cases, 30 mph at steady-state, on an engine with
    no control devices, gave higher particulate levels than the
    corresponding 60 mph run.

5.  An increase in particulate comparing 30 mph to 60 mph was noted
    during the baseline runs.  This appeared to be reversed when
    running at standard conditions with two of the three oxidation
    catalysts.

6.  The three oxidation catalysts significantly lowered the
    emission of aldehydes, as collected in the condensate, as well
    as lowering the total hydrocarbons.

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                                -4-
 7.   The vehicles on which mileage accumulation tests were made
     exhibited a large degree of fluctuation with respect to
     grams/mile as a function of mileage.   No clear trends have
     been established.

 8.   The precision of measuring particulate mass from a vehicle
     exhaust is substantially lower than that of measuring an engine
     stand run, probably due to differences in operating conditions
     prior to the tests.

 9.   In general, the particulate matter which exhibited higher
     percentages of carbon also exhibited higher parts per million
     of benzo-a-pyrene.

10.   The mass medium equivalent diameter became larger with
     mileage for two of the three mileage accumulation cars,
     while decreasing for the other.

11.   The mass medium equivalent diameter for the device equipped
     vehicles in general correlates well with the numbers obtained
     during the engine stand runs, even though the overall mass of
     particulate changed.

12.   In general, the low lead fuel gave higher particulate levels,
     in grams/mile, than the non-leaded fuel.

13.   Overall, the aldehyde content of the exhaust condensate was
     not significantly different between the non-leaded and low
     lead fuel.

14.   Under rich air to fuel ratio conditions, both the oxidation
     catalysts and the reduction catalyst gave a significant
     increase in NH~ emissions.

lb.   The concentration of benzo-a-pyrene in the particulate
     varied widely with engine conditions, but did not appear
     to be significantly changed by use of leaded vs. unleaded
     fuel.

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                                -5-
16.  Air/Fuel ratio had an effect on particulate with the
     standard setting generally being lower than either rich or
     lean settings.

17.  The effect of particulate due to changes in spark timing
     was sporadic and, therefore, inconclusive based on this data.

18.  Different temperatures at the filter and the sample probe
     caused differences in amounts of particulate collected.

19.  Changes in flow rate through the dilution tube caused slight
     variations in the amounts of particulate collected.

20.  Dilution air temperature proved to be important since a lower
     temperature showed definite increases in the amount of
     particulate collected.

21.  Sample probe location appeared to have only very small effects
     on particulate samples.

22.  Face velocity of a sample stream through a given filter
     was important in that more sample/ comparatively, tended to
     be collected at lower face velocities.

23.  A majority of the sample during a steady-state run was
     collected within the first 25 percent of the time period over
     which the run was made.

24.  Absolute measurements of grams/mile are misleading when
     measured during a steady-state run of long duration for the
     reason given in 23 above.  Comparisons can be made, however,
     between runs of like time periods, and are valid as measure-
     ment of a trend.

25.  The modified Federal cycle cold start gave more particulate
     than the 23 minute Federal cycle.

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                             -6-
                 III.  EXPERIMENTAL PROCEDURES

A.  PARTICLE GENERATION

    1.  Engine Dynamometer Studies
    The engines used in this study were 1972 Pontiacs, 400 CID.
    These engines were mounted on the dynamometer bed plate and
    attached to a fully instrumented Eaton Dynamatic dynamometer.
    Appropriate control and sensing devices were attached to the
    engine.  The following procedure (Table 1) was then employed
    to run-in the new engines, using Indolene low lead (0.5 cc/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 and best 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 (Hr)
              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

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4)  Run Cycle 2
                          -7-
          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
    1.0
    1.0
    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)
    1.0
    1.0
    1.0
    0.5
    0.5
                                                 4.0x4 cycles
                                                     =16 hours
                       *WOT - wide open throttle
7)  While engine is hot, run motoring compression and conduct
    leak-down check.
The engine was removed from the dynamometer, drained, partially
dismantled, cleaned, reassembled, and placed back on the
dynamometer stand.  A manufacturers original standard vehicle
exhaust system for the specific test engine was attached to
one bank of cylinders.  The other bank of cylinders was attached
                                                                j
to the dynamometer cell exhaust system.  Suitable engine monitors

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                          — R —
were attached to the engine in order to provide continuous
monitoring of oil pressure and temperature, coolant temperature,
carburetor air flow rate  (using a Meriam Laminar Flow Element
50MC-2-45F) and temperature, etc.

The engine was then run for 75 hours using the following
"conditioning" sequence (Table 2) employing the specific test
fuel designated for that run.  This sequence of testing was
used for the initial break-in of the- engine, as well as for
certain emission tests.  It was not run prior to evaluation
of each condidate emission control device.  During the
conditioning sequence, total unburned hydrocarbons, oxygen,
nitrogen, carbon monoxide, carbon dioxide, and oxides of
nitrogen were measured at frequent intervals by FID, gas
chromatography, chemical absorption, and a Scott N0/N0_ analyzer,
respectively.  Air/fuel ratios were also calculated based upon
exhaust gas composition.

                        TABLE 2
           TEST ENGINE CONDITIONING SEQUENCE

Cycle     RPM    Time  (Min.)    Vac. (In. Hg)     Decay
  1       800         2              18.8
  2      1070        13              16.4         1/2 min.
  3      1615        20              17.2         1/2 min.
  4      2125        13              14.3         1/2 min.
  5      1070        12              16.4         1/2 min.
Sequence repeats after each five cycles.

Following the conditioning sequence, the engine exhaust system
was attached to the dilution tube inlet pipe and the system
was ready for experimental particulate sampling.  All subsequent
runs were 60 mph or 30 mph 2-hour steady-state runs.

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                        — Q —
2.  Chassis Dynamometer Procedures

A Clayton CT-200-0 chassis dynamometer with a variable inertia

flywheel assembly was used in all tests conducted under this

program.  A Chelsa direct-drive Model PLDUP-300A fan was

located in front of the test vehicle, and operated at 1750 rpm

providing  5,000  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  (old California cycle) and LA-4

procedure driven by a vehicle operator following the cycle on a

strip-chart recorder driver aid.


Table 3 indicates specific procedures employed to prepare

each vehicle for test run.


                        TABLE 3
      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)  Chec1. heat riser  (if applicable) for fullness of operation
    e)  Check automatic choke operation and adjustment, where
        possible

2)  Engine Analysis and Tune-up

    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

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                        -10-
TABLE 3 (continued)

    c)   With engine running at idle, check
            •Dwell
            •Timing
    d)   With engine running at 1500 and 2400 rpm, check
        timing device
    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

3)  Instrumentation and Equipment Installation

    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

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, but not more than
        16 hours.

    c)   Connect vehicle tailpipe to dilution tube.

    d)   Start the vehicle and proceed with the individual test.

    Hot Start

    Continuation of the cold start only after the engine
    temperature has stabilized.

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                             -11-
    TABLE 3  (continued)

        Engine Temperature Stabilization
        Two-hour steady state runs were made only after a cold
        start and one or more hot starts.  Thus, the engine
        and particle collecting system were always at operation
        temperature before the steady state sampling was begun.
        When preparation has been completed, the vehicle is placed
        in gear and the speed is increased to 2250 rpm with the
        intake manifold vacuum is set at 17.0" Hg by controlling
        the amount of load imposed on the drive wheels.  At the
        time when the load and the speed become stabilized, the
        tailpipe is connected to the dilution tube inlet pipe
        and particulate collection is started when dilution tube
        has come to equilibrium.

    The procedures outlined in Table 3 were used whenever possible.
    On certain vehicle tests where the vehicle was equipped with
    proprietary systems, only visual checks were made of the
    components and engine hardware.  In some cases, the vehicles
    were adjusted by personnel from the organization submitting
    the vehicle for testing.

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.
Using EGR, the tests were conducted using full exhaust.

    1.  Dilution Tube
    Air dilution and cooling of the exhaust was accomplished by
    a dilution tube 16 inches in diameter and 27 feet in length
    constructed of extruded polyvinyl chloride (PVC)  pipe 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

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                                            Figure  2
                                    Flow Diogrom  tor  Engine  Exhoust
                                        Particulate Collection
                                                                     Air
                                                                     out
                              Instrument
        Filter
           I
Engine Room  RJ
<            ^
         Mix i ng
Air
  in.
        Eng ine
      Dynamometer
Eng ine—*•
                                                             Flow —>•
                                                            Control
                 Gravimetric Fallout
                                               Sampling Slits
'—Tail Pipe
                             Standard Muffler
                            '5*
                  t
             Exhaust P ipe
         Scott Research  ins,
            NO and N02
             Analysis

         Fisher Gas Partitioner
            CO, C02, N2, 02

         Beckman 109A
         Total Hydrocarbon
         Analyzer
                                                           --»!
                                                                        Anderson
                                                                        Separator
                                                                        M i11ipore
                                                                         F ilter
                                                                        Flow Meter —>
                                             Vacuum
                                              Pump
                                                                   A ir
                                                                   Pump
                                                                                                    to
                                                                                                    i
                                                                                               Manometer

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                         -13-
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 0.3p in size and smaller.  Pressure drop at 600 cfm
flow rate is minimal.

Exhaust was delivered to the tube via a tailpipe extension
which was brought into the bottom of the tube downstream of
the 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
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
15y is located at the exhaust end of the dilution tube.  Four
isokinetic sample probe elbows are located in the exhaust-air
                               i
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 stainless steel tubes
which are located as shown in Fi.gure 1.  A mercury manometer
is connected between the dilutipn tube probe and the exhaust

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                         -14-
side of the filter assembly, to measure 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 sample probes were both 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 either a 293 mm, 4 cfm glass fiber; or a 142 mm,
4 cfm glass fiber, the former being used on engine stand runs
and the latter on vehicles.

Prior to use, all the filters were stored in the instrument
room which is 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 Millipore filter
pads used were 142 mm Type AAWP 0.8y.  The glass fiber filter
pads used were Gelman 0.3y Type A.

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_0 cut-off values for the
Andersen stages are listed in Table 4.  The D5Q 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.

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                              -15-
                            TABLE 4
                D5Q VALUE - ANDERSEN MODEL 0203

                    Stage 1           D5Q  9y
                    Stage 2           DSQ  5.45y
                    Stage 3           DS()  2.95y
                    Stage 4           DSQ  1.55y
                    Stage 5           DS()  0.95y
                    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 ram diameter.  Gelman glass fiber
    filters were routinely used while the Millipore filters
    were used for special analytical applications.

C.  CONDENSATE 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
exhaust 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.

The condensate from the exhaust gas was analyzed for ppm of HCHO and
NH.J.  It was felt desirable to express this analysis in volume
percent to compare to the other components analyzed in the exhaust
gas.  The procedure for this calculation is as follows:

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                              -16-
       The "Ideal Gas Law" was used
               PV = nRT
               PV=
The total liters of exhaust that was put through the condenser is
known.  The liters of the aldehyde can be calculated from the
formula above , so the volume percent can be calculated.  This
volume percent is reported as volume parts per million in the
exhaust.

D.  ANALYTICAL METHODS
Collected exhaust particles have been analyzed for both physical
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.

                           TABLE 5
           ANALYTICAL TECHNIQUES FOR EXHAUST SPECIES

    02, N_, CO, CO_                Fisher Gas Partitioner
    Total Hydrocarbons             Beckman Model 109A Flame lonization
                                   Detector.
    Oxides of Nitrogen             Beckman UV and IR Analyzer
    C, H                           Pyrolysis
    Benzo-ct-pyrene                 Chroma tograph , Fluorescence
    Trace Metals                   Emission Spectroscopy, Atomic
                                   Absorption
    Aldehydes                      Polarography
    NH~                            Steam Distillation, Titration

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                          -17-
1.  Fuels
Each test fuel was analyzed to verify concentrations of
additives under study.  Additionally/ complete physical
analysis were determined on the base stock test fuel.
These analysis include  (distillation, octane numbers,
fluorescence indicating analysis  FIA  composition, and
Reid vapor pressure [RVP] and trace metal).

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 necessary 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 saturates
and unsaturates.  These analyses were done by gas chromatography,
chemical absorption, and a total hydrocarbon analyzer.  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 the 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 molecular sieves in series.

-------
                     -18-
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 Intergrator 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 chromatograpl'
through 1/8" OD stainless steel tubing.   A manifold system
was provided 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
number on the teletypewriter, injected the reference
standard, and pressed the integrator start button.
As the peaks emerged, 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 telephone lines.

-------
                         -19-
    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.  Estimated 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 standard. The total
    percent actual will normally be 97-98 percent 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
        Recorder - Texas Instrument Company

    The above pieces of equipment were in a single, self-
    contained unit built by Scott  Research Labs Inc.,
    San Bernardino, California.

-------
                                   -20-
                                  Figure 2
 G.  C.  A:,'. .LYSIS  -  TEC!:;«'IC;.L DATA -
 CCV RUN £3 CCT  16
'CYCLE  2 72.9 K3UHS
 KC  620.
  PEAK     TIME
   NS.  ACT.   EST.
                         PCT. V3L.
                       ACTUAL   N3RM.
                                                     10-16-70
                                  Cf-r:r>ri:::D
                               IDENTIFICATION
1 22.
2 59.
3 83.

4 104.
5 107.




21.
59.
83.

107.
IRQ.




0*000
12.003
1 •  3
0.900
81.0CG
1.626
97.060
2.940
8.50

0«000
12.366
1.53C
0.9S7
03.452
1.675
1CO.OOO



CCMFC3ITZ
CAnr:.;j DIOXIDE
CXYGI;J
(\~GZti
niTnoGc:.'
CARG^iJ i^NOXIDE
T3TALS
DALA^CE DY DIFFEHZI-'C
TOTAL C':;rr/. :i NATI :;i








* r
LEVZL

          EXKAUST GAS  ANALYSIS

GGV RUi!  23 CCT 15
CYCLE  2  72c9 H3Uf?S
KC 620.

 TIHE  PERCi:;JT  IDir.'TiriCATICM
  83.
  107.
  C3.
  1GC5.
  59.
           0.9  AHCVi!
          C3.5  NIT/. . :~ri
           i e 5  c .'\ V ;.  -
12
                       DIOXIDE
         1C 0.0  TOTAL

FRACTICN  C/.r.-DN IN F
                                          10-16-70
TOTAL
                   C::;:TC::T  620. PPH.
          H.IYIO

-------
                         -21-
    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, NO^ measurements,  the paper filters
    (Whatman #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 nitrogen 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, N02 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
exhaust particulate.  Additionally, cumulative mass distribution
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.

-------
                     -22-
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
Andersen Sampler plates by careful transfer of the particulate
to the combustion chamber.  However, even with the best
handling 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.

-------
                     -23-
Nitrogen can also be determined by pyrolysis, but due  to
the small sample size no meaningful results have been
obtained on nitrogen content.

b)  Benzo(a)pyrene
Samples of exhaust particulate were collected on Gelman
142 mm glass fiber filter pads in a Millipore filter holder
operating at 1 cfm.  Particulate weights gathered in this
fashion ranged from 0.2 to 35 mg.  The samples on the
glass 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
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 approx-
imately 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  yl
aliquot was spotted in 2 yl increments on a pre-conditioned
Alumina TLC plate along with a known standard of benzo(a)-
pyrene in methylene chloride.  The TLC plates were conditioned

-------
                     -24-
by heating at 120°C for 1.5 hours and desiccating overnight
in a 45 percent relative humidity chamber (saturated
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
a F sintered glass filter into a vial, washing the alumina
four times with approximately 2 ml of 5 percent acetone in
n-pentane with a 45-second soak period between each wash.
The combined filtrates were evaporated to dryness at room
temperature 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
procedure.  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
refrigerated when not actually being processed and exposure
of the samples to light was kept at a minimum.

-------
                     -25-
c)  Trace Metals
Both atomic absorption and emission spectrometry 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
    solution is taken to dryness and the residue is taken
    up in a spectroscopic buffer solution containing the
    internal reference 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 photo-
    metrically 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.
        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.  Densi-
        tometer Comparator, Baird Associates Inc., or
        equivalent.

-------
             -26-
5)  Calculating equipment.  A calculating board  is
employed to covert densitometer readings to log
intensity ratios.  Jarrel-Ash Co.
6)  Wet ashing equipment.  A micro Kjeldahl digestion
rack is used for wet ashing the organic solvents.

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 sulfuric or nitric acid.
2)  Sodium nitrate, reagent grade  (NaNO_).
3)  Palladium diamine nitrite, Pd(NH-)„(N02)2.
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.

Calibration
1)  0.2182 gm of palladium diamine nitrite
Pd(NH3)2N02)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 ICu ml volumetric flask.  This solution contains
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.

-------
             — 27 —
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 concen-
trated 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.

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 desiccator until
run.

7)  The samples were excited in water cooled electrode
holders using the following conditions:
     (1) Current, 4.0 amps, a.c. arc.
     (2) Spectral region, 2150-3550 A.
     (3) Slit width, 50y.
     (4) Electrode gap, 2 mm.
     (5) Pre-burn period, 10 seconds.
     (6) Exposure period, 90 seconds.

-------
                             -28-
Conccntration
                              Table  6
                       nl.  of  standard addition impurity solution
Blank
0.00001%
0.000025%
O.CCOG5%
0.0001%
o.oco:,'5%
O.OGO.^
0.00075%
0.001%
O.C02S%
0.005%
0.01 %

0.5 ml.
1.25 nil.
V o «mJ &.*& o
0.5 nl.
1.25 nl.
2.5 til.
0.3715 nl.
O.5 Lil.
.1.23 nl.
2.5 ral.
5.0

0.0001% 8
it
o.coisi
II
II
II
0.01C^
It
II
II
II

10!
ti
it
it
it
it
ti
it
ti
it
ii
Element
Ni
Ni
Pb
Pb
fin
Sn
7n
                             Table 7
                       Analyticr.1 Liao
             Analytical
               Lino A
Al
Ca

Cu
Fe
Fe
£13-
US
l!n
Un
3032.71
3179.33
V
3273. CO
3021.O7
3020.84
XG02.G0
2779. £3
2&33.G3
27P-S.C2
                    Interns!  Standard
                       _ Llc.0  A	
                    3027.91  Pd
                                    ii
                                    it
                                    it
•?rVJ.7 <"•-•
wk/t> 4 . *- V
2873.33
2033.07
31 VS.02
2SG3.33
33':.'i.O,T
                                    it
                                  " cJoround
 Concentration
   Range %
 0.000025-0.OO10
 O.OOO25-0.010
 O.00001-O.00025
 O.OO01-O.O10
 O.O00025-0.0050
 0.000025-O.C010
 O.O005-O.O10
 O.OO05-O.O1O
 O.OOC01-O.CD10
 0.000025-O.0010
 O.OC05-O.OIO
 O.OO10-0.010
 O.OO005-0.005O
 O.00005-O.C05O
O.O0075-O.O1O
O.OOO1-O.O10

-------
                   -29-
    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 Analysis" A.S.T.M. Designation:
    E116, Methods for Emission Spectrochemical Analysis,
    (1964) .

    9)  The emulsion was processed according to the following
    conditions:
          (1) Developer  (D19, 20.5°C), 3 1/2 minutes.
          (2) Stop bath  (SB-4), 1 minute.
          (3) Fixing bath (Kodak Rapid Fixer) , 2 minutes.
          (4) Washing, 3 minutes.
          (5) Drying, in a stream of warm air.

   10)  The relevant analytical line pairs were selected
    from Table 7.  The relative transmittances of the
    internal standard line and each analytical line were
    measured with a densitometer.   The transmittance
    measurements of the analytical 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
    concentration as a function of intensity ratio on log-
    log graph paper.  For best results, the average of
    at least four determinations 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

-------
              -30-
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.  Concentrated 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 solution 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 dryness.  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 concentration
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.

-------
                   -31-
    f.  Calculations
The intensity ratios were converted to concentration by
use of the analytical curves.

    g.  Precision and Accuracy
Representative precision and accuracy of the method are
given in Table 80  Each of the twelve samples A.. , A«, A_ ,
B, , B2, B.,, C, , €„, 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 samples were analyzed on an atomic absorption spectro-
photometer (Perkin-Elmer Model 303) using a hollow cathode
lamp with a lead cathode filament.  Operating conditions
were as follows: 10 milliamps tube current, light path
slit opening - 4, ultraviolet light range, acetylene-
air oxidizing flame, one-slot burner head, wavelength -
2170 angstroms.  The sample 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 concentration 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 determine the concentration of

-------
                                           TABLE  8
0>
1-1
D.
E
a
w
Al
A.
A2

A3

El
JL
B2

E3

Cl
«L
C2

C3

Dl
JL
»2

D3



% Al
O.OOO044
O.OOOO52
0.000045
O.OOOO52
O . OCGO-1
O.OOOO52
O.OOO12
O.CC0097
O.OC0097
O.OCCO94
O.CCCG32
O.CC011
O.O0023
O.COD2O
O.O032O
o.cco::;3
O CC.'J24
0.00028
O.OCO74
O.OOOS4
O . CC053
O.COOGS
O.OO059
O.O0053
A. , A3, ted A3
070001% of Al
and O.O025% of
_ ^
KtPKtb

% Ca
0.00043
0.00050
0.00043
O.CC037
O.OCXM3
O.OO050
O.OO1O5
O.OOC33
O.OOOC5
O.OQOG3
O.COOS2
O.CC074
O.O023
O.0018
0. 00223
O.C02C3
O.O023-
O.OO275
O.C07O
O.CC'5'1
O.C019
O.G057
0.00-13
O.OO30
contain.
tN 1 A 1 1 Vt V

% Cu
O.OOOO48
O.OOO054
O.OOOO46
0.000047
O.OOOO50
O.OOOO48
O.OO012
O.OO010
O.OO0099
O.O30O95
0.000025
O.OOOOS6
O.O0023
O.O0020
O.OC023
0.00025
O.COO26
O.OOO28
__
__
__
__
—
—
0. 00005% of
KtLlblUIN

% Fe
O.OOO43
O.OO055
O. 00044
0.00043
O.OOO46
O.OOO46
O.OO1O
0.00094
0.00030
O.CO1O5
O.OO10
0.0010
O.O025
O.CO3O
O.C023
O.OO235
O.C0275
O. 00235
O.CDG5
O.G023
O.CO57
O.OO59
O.OO5O
O.OO55
Al and Cu
AINU AL

% Kg
0.00049
O.OOO52
O . OO04 7
O.OOO50
O.OOO53
O.OOO49
O.001O5
O.O0095
0. 00092
O.QOQ91
O.OO10
O.COO90
O.0023
O.OO23
O.C023
O.0024
0.0023
0.0024
O.0057
O.O051
O.0048
O.OO-17
O.O045
O.O055
, and 0
LUKALY (J

% Mn
O.OOO46
O.O0057
O.OO051
O.OO050
O.OOO49
O.OOO46
0.0010
O.OO12
O.OO11
O.OOO66
O.OOO86
O.OO092
O.002G5
O. 00195
O.CO2S5
O.OO275
0.00245
O.OO25
O.OO59
O.O058
0.0045
O.OO48
0.0047
O.0054
.OOO5% of
h bniSblU

r.- NI
O.OOO47
0.00055
' 0.000-15
0.00051
O . OOO4 7
O.OOO48
O.OO10
0.00096
O.0010
O.OO105'
O.OO10
O.OO105
O. 0024 5
O.C02S5
O.OO23
O.OO245
O.0026
0.00255
0.0035
O.OO58
O.OO56
O.O057
O.OO50
O.O055
each other
and Cu, and O.COIOJ of each other element. C-, , Cfi, and Ca
each other element.
Dlf DB aad D3 contain 6.OO65% of Al
N bPhU 1 H

% Pb
O.OOO56
O. OOO 59
O.OO050
0.00051
O.OOO52
0.00053
O.OO1O5
O.OO098
0.0010
O.OO105
O.OO10
O.OO1O
0.00235
0.00255
0.00245
O.CO26
O.0025
O.OO245
O.OO53
O.OO45
O.OO45
0.0043
0.0043
O.OO49
element
contain*
tUbUUPY

% Sn
O.OOO52
O. 00059
O.OOO53
O.OOO50
O.OOO5O
O.OOO46
0.0011
O.OOO94
O. 00105
0.00105
O.O0099
O.OO10
O. 00255
0.0027
O. 00215
O.OO23
0.0025
0.00265
O.OO54
O.OO59
O.OO53
O.O057
O.OO54
O.OO49
• BI f B g »
o. 60025%
and Cu and O.OO5O%


%Zn 	
O.COO4O
0.00045
O.OOO54
O.OOO4O
O.OOO52
O.O0042
O.OOO94
0.0012
O.OO125
O.OO1O
O.OOO96
O.OO115
O.OO14
O.OO215
O.O0225
O.OO3O
O.OO3O
O.OO2O
O.OO58
O.005O
O.O050
O.OO3O
O.OO37
O.CXM1



























and B3 contain
of Al and
of each "
Cu
»her
                                                                                                       ro
                                                                                                       i
elenent.

-------
                  -33-
lead in the samples.  The sensitivity for the lead deter-
mination in an air-acetylene flame is about 0.25 yg Pb/ml
at 1 percent absorption.  The detection limit is 0.1 yg
Pb/ml.

    b.   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
absorption.  A portion of the sample solution was also used
in the determination of iron.  Iron is reduced with
hydroxylamine to the ferrous state, and reacted with
1,10-phenanthroline in an acetate buffered solution  (pll 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 nm, 40 mm optical
cells.   The concentration 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
± 1 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.

-------
                        -34-
        d.  Determination of Lead and Other Metals in Fiberglass
            Filters
    The fiberglass 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.

7.  Coriden sate Analyses
Condensate was collected from the raw exhaust as described in
Section III-C.  The condensate was analyzed for aldehydes and
NH3 using the procedures outlined below.

    a)   Aldehydes
    The analytical method for the determination of carbonyl
    compounds in automotive exhaust emissions employed
    polarographic techniques.  Samples for analysis were collected
    from undiluted 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 Electrochemistry System was used as the monitoring
    device.  The derivative pulse polarographic mode yielded
    the best combination of resolution and sensitivity for
    the classification 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 eliminating
    many possible interferences.

-------
                    -35-
An acetate buffer of approximately pH 4 (an equimolar mixture
of acetic acid and sodium acetate, 0.1M in water) was used
to control pH for hydrazone formation and also acted as
supporting electrolyte.  Hydrazine was added as a 2 percent
aqueous solution.  In this system formaldehyde gave a peak
potential (half-wave potential) of -0.92v vs. a saturated
calomel reference electrode.  A platinum wire was employed
as the auxiliary electrode.

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 3.

Since aromatic ketones, e.g. benzophenone, give polarographic
response in pH 4 buffer without hydrazine, it is also possible
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 4 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 5 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
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

-------
                                     -36-
                       Figure


H ; H H-Polarographic Determination  of Aldehydes

                                                   -----i-
                                             -
                                                              6v • ivs ;SCF
                                                                          i I . .; ....: I  ,
                                                                            . . , j.   i
i i" i'LPT1
 .1 ,.,. | .......

-------

-:''••"'                Figure

; ; _-_;_p<>larograph1c Determination of Aldehydes:}^"
                                                                              Polarographlc Determination of Aldehydes
—_as•above;with•nydrazine
                                                                                                          .
                                                                                                                                                 I
                                                                                                                                                U>

-------
                     -38-
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
obtained without hydrazine at the peak potentials listed
above.  Formaldehyde/ higher aliphatic aldehydes, aromatic
aldehydes, and aliphatic ketones can be determined from
the second polarogram with hydrazine present.

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
Ammonia is present in the exhaust gas condensate and is
analyzed in the following manner.

-------
                                                5/1.
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                                                FIGURE 6
                                    .APPARATUS FOR DETERMINATIONOF NH,

-------
                            -40-
        A 5-10 cc aliquot of condensate is added to a 50 percent
        potassium hydroxide solution.  This mixture is then steam
        distilled into an excess of 0.010 N hydrochloric acid.
        The excess acid is determined by adding potassium iodide
        and iodate and titrating the liberated iodine with 0.010 N
        sodium thiosulfate.

        This technique is capable of determining ammonia as low
        as 0.3 ppm.  Figure 6 is a sketch of the apparatus used
        for the determination.

The analytical procedures given herein have been adapted from
literature sources or developed upon the basis of experimental
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.

-------
                             -41-
                     IV.  EXPERIMENTAL RESULTS

The current extention to contract EHS 70-101 was outlined  into
five basic tasks.  These tasks are presented in Table  9 with a
brief description of the objective of each task and the approach
used to accomplish the objective.
                           TABLE 9
                    TASKS AND OBJECTIVES

TASK I - Evaluation of Particulate Sampling Parameters

Objective:  To evaluate the relative significance of various sampling
parameters on the collection of particulate matter and to identify
therefrom a set of sampling conditions which will afford reliable
and meaningful data for the remainder of the work program.

Approach;  Particulate matter from air diluted automotive exhaust
was sampled and the effect of changes in the following sampling
variables was monitored:  sample line temperature, dilution ratio,
sample probe location, filter flow rate, and sampling time.  This
work was performed using non-leaded fuel.  Grams/mile of particulate
was measured.

TASK II - Determination of Baseline Data from Engine Dynamometer
          Tests

Objective: To establish baseline data for particulate emissions ,
aldehydes, ammonia and benzo-a-pyrene present in the exhaust
effluent of an internal combustion engine operating on non-leaded
and low-lead gasoline under controlled conditions on an engine
dynamometer.

-------
                             -42-
Approach; A 1972 Pontiac 400 CID V-8 engine was procured and a
reference set of tests were run on this engine using non-lead
and low-lead fuels.  The above emission data was generated under
the following test conditions:
             Road load    60 mph
             Road load    30 mph
             Mild cycling (Dow cycle) to include cold start

For each of these conditions, the effect of the following variables
on such emissions were evaluated.

             Air/fuel ratio  (three different values at road
                             load 30 and 60, 1 value under
                             cycling)
             Ignition timing  (two different settings)

TASK III - Evaluation of Emission Control Devices by Engine
           Dynamometer Tests

Objective; To evaluate the effect of various exhaust emission
control devices on the non-regulated emissions identified in
Task II.

Approach;   For each emission control device to be considered the
tests outlined in Task II were repeated as applicable.  The devices
tested included:
    Sub-task IIIA   Three HC-Co oxidation catalysts
    Sub-task IIIB   One NO  reduction catalyst
                          X
    Sub-task IIIC   Exhaust gas recirculation

-------
                             -43-
TASK  IV - Evaluation of the Effect of  Emission Control Devices
          on Non-Regulated Emissions by Vehicle  Testing

Objective; To characterize the non-regulated  emissions outlined
in Task II for vehicles equipped with  emission control devices.

Approach:  Vehicles equipped with emission control devices were
tested periodically  (as a function of  mileage accumulation) and
the above non-regulated emissions measured using the  1975-76
Federal Test Procedure on a chassis dynamometer.  Four of these
vehicles were made available from automotive company  durability
programs.  Where possible, each vehicle was tested on at least three
separate occasions.  Additional vehicles equipped by  the Office
of Air Programs, Environmental Protection Agency (EPA), were tested
as scheduled by the Contract Officer.

TASK V  - Diesel Engine Characterization

Objective:  To initiate a limited diesel engine  study to establish
baseline data foa^-emissions present in the exhaust stream.

Approach;  A single cylinder Labeco diesel engine was used to study
sampling parameters and the effect of  a dilution tube on the diesel
exhaust.
The data and conclusions for each task are presented separately, as
well as any discussion of operating parameters, analyses, or effects
of devices.

-------
                             -44-
A.  TASK I
    1.  Introduction
    The major objective of the first task outlined in the current
    extension to the subject contract was to study the effect of
    specific engine variables on certain non-regulated exhaust
    emissions under highly controlled conditions.  The emissions
    defined for study included particulate matter (organic and
    inorganic), aldehydes, ammonia and benzo-a-pyrene.  Studies
    were made on engines operating on non-leaded and low-lead fuels.

    During the course of some preliminary studies undertaken in our
    previous years work, alarming differences were noted when
    particulate matter emitted in the exhaust stream of an engine
    operating on non-leaded gasoline was collected on filters
    operating at different flow rates and temperatures.

    In order to reach an understanding of the above effects and
    to allow the definition of a meaningful set of particulate
    sampling parameters which could be used throughout the current
    contract efforts, a study had been made of a number of sampling
    variables and their effect on the mass of particulate matter
    collected at a filter.

    2.  Experimental Procedure
    All of the studies described herein were conducted using either
    a 1971 Chevrolet Impala fitted with a 350 CID V-8 engine and
    operated on a Clayton Model chassis dynamometer,  or a 1972
    Pontiac 400 CID V-8 engine operated on a General Electric Model
    dynamometer.  Both the vehicle and the engine were run on
    Indolene 0 non-leaded fuel, except where noted.   The exhaust
    effluents from both the vehicle and engine were fed to similar
    polyvinyl chloride (PVC)  dilution tubes which have been described
    in Section III-B.  Separate dilution tubes were used for the

-------
                         -45-
vehicle and engine studies.  Unless otherwise specified,
stainless steel sampling probes were located in the dilution
tube at the end remote from the air and exhaust inlets.  All
tests were made with the vehicle or engine operating under 60
mph road load, steady-state conditions.

Appendix A is a report on work carried out at Dow's expense
prior to the current contract extension.  This work led to
the identification of the parameters being studied in Task I.

Experiments for Task I were run to evaluate the effects of
various operating parameters as outlined below:

    1.  Effect of Dilution Tube Velocity
    2.  Effect of Filter Temperature
    3.  Effect of Dilution Air Temperature
                                           \
    4.  Effect of Sample Probe Temperature
    5.  Effect of Sample Probe Location
    6.  Effect of Face Velocity Through the Filter Media
    7.  Effect of Sample Collection Time
    8.  Effect of Test Mode

It must be noted that in determining the effect of any one
variable, it was extremely difficult to hold all other
variables constant.  Therefore, a complete analysis of the
effect of each variable by itself can only be made by inference.
In many cases, the same runs were used to try to evaluate several
parameters.  For example, the effect of the sample probe location
was done on the same runs that were used to determine the effect
of filter temperature.

-------
                         -46-
3.   Conclusions for Non-Leaded Fuel Particulate Sampling

    a.   A change in the temperature differential between the
        filter and the sample probe caused differences in
        amounts of collected particulate.

    b.   Changes in rate through the dilution tube caused slight
        variations in the amounts of particulate collected.

    c.   Dilution air temperature proved to be important since
        a lower temperature showed definite increases in the
        amount of particulate collected.

    d.   Sample probe location appeared to  have only very small
        effects on particulate samples.

    e.   Face velocity of a sample stream through a given filter
        was important in that more sample, comparatively, tended
        to be collected at lower face velocities.

    f.   A majority of the sample, during a steady-state run, was
        collected within the first 25 percent of the time period
        over which the run was made.

    g.   Absolute measurements of grams/mile are misleading
        when measured during a steady-state run of long duration
        for the reason given in f above.   Comparisons can be
        made, however, between runs of like time periods, and
        are valid as measurements of a trend.

    h.   The modified Federal cycle cold start gave more
        particulate than the 23 minute Federal cycle.

-------
                         -47-
    i.  Most future work will be done at the following
        conditions?
        Filter temperature controlled to 100°F.
        Dilution tube velocity controlled to 400 ft/min.
        Inside dilution air used at all times.
        Sample will be collected on 142 mm filters.
        Steady-state runs will be 2 hours in duration.
        Filter rate will be 1 cfm.
        Sample probes will be used only at the end of
        the dilution tube.

4.  Effects of Various Operating Parameters

Dilution Tube Velocity - The effect of velocity of the diluted
exhaust in the dilution tube was studied in relation to the
effect it might have on the amount of particulate collected.
The raw data for this study is presented in Tables 10, 11, 12,
and 13.

The dilution tube flow rate was varied from 300, 400, and 500
ft/min by using increased amounts of dilution air.  Table 10
is a study of the true velocity effect in the tube at the
three rates just mentioned.  The flow rate would be expected
to show some side wall effect and, in fact, does.  Gas flow
through the dilution tube was measured with an Anemotherm air
meter manufactured by Anemostat Corporation of America.  The
general increase in measured flow as the velocity measuring
device was inserted can be attributed to the turbulence created
by the sampling probe itself, as well as some leakage at the
lower end,,  The three sampling zones are described in Figure 7.
The first sample zone was 9 feet from the point of entry of the
exhaust; sample zone 2 was 16 feet;  and, sample zone 3 was
23 feet.

-------
                         -48-


                              Table 10
                   DILUTION TUBE FLOW RATE PROFILE
  Inches  from
Bottom of Tube

      2
      4
      6
      8
      10
      12
      14
      15
                       400 feet/min
      2
      4
      6
      8
      10
      12
      14
      15
      2
      4
      6
      8
      10
      12
      14
      15
Sample Location
1
360 ft/min
360 ft/min
380 ft/min
380 ft/min
400 ft/min
400 ft/min
420 ft/min
420 ft/min
500 feet/mi

1
450 ft/min
470 ft/min
490 ft/min
500 ft/min
500 ft/min
500 ft/min
520 ft/min
500 ft/min
300 feet/mi

1
270 ft/min
280 ft/min
290 ft/min
280 ft/min
300 ft/min
300 ft/min
300 ft/min
330 ft/min
2
390 ft/min
410 ft/min
410 ft/min
400 ft/min
400 ft/min
400 ft/min
400 ft/min
410 ft/min
n
Sample Location
2
490 ft/min
500 ft/min
500 ft/min
500 ft/min
500 ft/min
510 ft/min
510 ft/min
530 ft/min
n
Sample Location
2
280 ft/min
300 ft/min
300 ft/min
300 ft/min
300 ft/min
300 ft/min
320 ft/min
320 ft/min '
3
400 ft/min
410 ft/min
400 ft/min
400 ft/min
400 ft/min
410 ft/min
410 ft/min
430 ft/min


3
460 ft/min
500 ft/min
510 ft/min
510 ft/min
500 ft/min
500 ft/min
510 ft/min
510 ft/min


3
300 ft/min
300 ft/min
295 ft/min
290 ft/min
300 ft/min
305 ft/min
310 ft/min
350 ft/min

-------
                          FIGURE 7
                 DILUTION TUBE SAMPLE POINTS
                  16" diameter Dilution Tube
        A

        A
Exhaust from Engine
Sample #1
                                                      -t—
                     	t
Sample #2  Sample #3


   J          -i
" -- j— "7«o"
                                                                                  i
                                                                                  *.
                                                                                  vo

-------
                         -50-
All the sampling of particulate to be analyzed was taken from
the center of the tube  (between 6 and 8 inches from the
walls).  The flow rates in this zone were quite constant at
all three sampling points, indicating that complete mixing
of the air and exhaust was taking place as close as 9 feet
from the entry of the exhaust.  Since the amount of exhaust
remained constant while the amount of dilution air was varied,
the temperature at various dilution rates also varied.  Table 11
shows the effect of increased flow rate as well as the effect
of temperature differences on the amounts of particulate
collected.  In all cases, except in the study of sample probe
location, all samples were collected 23 feet from the exhaust
inlet.

The following data, extracted from Table 11, shows that the
rate of flow through the tube has a small effect on the
grams/mile of particulate mass, independent of the temperature.

    Flow Rate    Temperature  (°F)    Grams    Grams/Mile
       300
       300
       400
       400
       500
       500

The grams/mile of particulate collected varied from a high
of .0060 to a low of .0043, with the high point being
400 ft/min; 500 ft/min shows only a small decrease, which
is within experimental deviation.

Table 12 shows the particulate collected using .5 cc/gal
lead fuel at the same three flow rates.  The low lead fuel
was used to generate much higher amounts of particulate in
126
106
117
99
108
96
.0044
.0046
.0045
.0045
.0031
.0033
.0043
.0045
.0060
.0060
.0054
.0057

-------
                                                            TAFLE  11
                                   DILUTION TUBE  FLOW  RATE  COMPARISON,  UNLEADED FUEL
Air-Fuel  Ratio  (15.5)
Chassis  Dynamometer
1971  Chevrolet  350 CID
No TEL  Fuel
50 MPH  -  SS  - Run 90

Air-Fuel  Ratio  (15.3)
Chassis  Dynamometer
1971  Chevrolet  350 CID
No TEL  Fuel
60 "MPH  -  SS  - Run 91

Air-Fuel  Ratio  (15.4)
Chassis  Dynamometer
1971  Chevrolet  350 CID
Ko TEL  Fuel
60 MPH  -  SS  - Run 92
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.0054 4 i-.
.OlfBT Avg. '

1
.0043 2
.0045 3
4
.OTJ4T Avg.

1
.0054 2
.0057 3
.0062 4
.0~OTT Avg.
 *NG =  no  good,  moisture on filter paper
 Key: Filter  #1  = Sample line  water-cooled
             #2  = Sample line  insulated
             #3  = Safnple'line  water  jacketed only
             #4  = Sample line  air-cooled

-------
                                TABLE  12

                  DILUTION  TUBE  FLOW  RATE  COMPARISON
                             Low Lead  Fuel
                                                          Grams
Flow
ft/mi n
400
300
500
Flow in Tube
cfm
445
330
580
Exhaust Dilution
Ratio
4.49:1
3.24:1
6.59:1
Temperature at
Filter Surface
114°F
116°F
104°F
Parti cul ate
on Filter
.0087
.0095
.0072
Grams/Mi
.0322
.0261
.0348
le



                                                                                    Ul
                                                                                    to
Runs 100A,  100B,  100C

All runs on chassis  dynamometer,  1971  Chevrolet 350 CID
0.5 cc TEL  fuel,  60  mph  Steady-state,  6  hour sampling time,
142 mm, 1  cfm fi1ter

-------
                         -53-
order to help minimize any deviations due to experimental
error.  The temperature effects were minimized also.  The
grams/mile of particulate mass increased from 0.0261 g to
0.0348 g as the flow went from 300 to 500 ft/min.  This
data is shown graphically in Figure 8.

Comparing Runs 90, 91, and 92  (Table 11) to Runs 100A, 10OB,
and 100C (Table 12) shows an increase of 24 percent in grams/mile
of particulate mass in the first case, and an increase of 25
percent in the second, going from 300 ft/min to 500 ft/min.  All
of the runs in Table 12 were done on the same day, thus
minimizing any ambient temperature or humidity differences.

Table 13 shows again the effect of flow rate versus particulate
collected.   In this experiment, temperature differences between
flow rates, at the same sample points, were small.  In each
case, the grams/mile of particulate mass appeared somewhat
higher at 500 ft/min, but some of the effect was probably due
to the small difference in temperature.

    Conclusions
    The differences in the amount of particulate collected
    at the three flow rates studies were small enough so
    that a flow rate of 400 ft/min was settled on as the rate
    for future work.  The differences between the flow rates
    were attributed more to the temperature differences than
    to any fundamental change due to the exhaust dilution.

Effect of Filter Temperature - Earlier attempts at defining
some of the variables in the dilution tube method of
collecting particulate samples indicated that the temperature
of the gas  stream being sampled, at the filter, had an effect
on the amount of particulate collected.  The data shown in
Tables 14 and 15 were generated as an attempt to further
characterize the filter temperature effect.

-------
  .04
                                   JE^
                                       14
                                                            n
                                                                           _4_
   ,03
to
3
0
s_
D_
O)
E
s_
            tl
frS
   02
   01
               300                  400                 500
                          Flow  Through Tube, ft/min
                       Dilution  Tube  Velocity vs. Grams/Mile Particulate
                                        4,   Figure 8

-------
                                  TABLE 13
               DILUTION TUBE FLOW RATE COMPARISON, NON-LEADED FUEL

                                         SAMPLE LINE
Ft/Min
Flow in
Tube
300
500
Sampling
Point
Temperature
132.8°F
109. 4°F
Heated
Temp . @
Filter
125°F
111°F
g/Mile
Collected
.0049
.0055
Ambient
Temp . @
Filter
108°F
97°F
g/Mile
Collected
.0060
.0070
Cooled
Temp . @
Filter
82°F
81°F
g/Mile
Collected
= 0064
.0070
Runs 113B and 113C
All runs made on 1972 Pontiac 400 CID engine dynamometer.

No lead fuel, 60 mph steady-state, 2 hour sample time.

142 mm, 1 cfm filter.

-------
                         -56-
                       TABLE 14

        FILTER TEMPERATURE EFFECT ON PARTICULATE
Temperature
 at Filter
Flow Rate in Tube
   Feet/Minute
Grams/Particulate
    on Filter      Grams/Mile
106
126
94
99
117
88
96
109
300
300
400
400
400
500
500
500
.0046
.0044
.0040
.0045
.0045
.0036
.0033
.0031
.0043
.0045
.0054
.0060
.0060
.0062
.0057
.0054
Run on 1971 Chevrolet, 350 CID

Non-leaded fuel, 5.75 hours, 60 mph

Steady-state

-------
                            TABLE 15

              FILTER TEMPERATURE EFFECT ON PARTICULATE
          Sample Zone I
Run No .
107
105
102
106
Flow
Rate
300
400
400
500
Temp . Before
Filter
122°F
106°F
86°F
100°F
Grams
Collected
.0087
*
.0094
.0075
.0065
	Sample Zone 2	
Temp. Before    Grams
   Filter     Collected
                .0085

                .0095

                .0073

                .0065
                                    102°F

                                    100°F

                                    100°F
	Sample Zone 3	

Temp. Before    Grams
    Filter    Collected
     113°F

     100°F

     104°F

     100°F
.0092

.0098

.0086

.0061
                                                                                    i
Runs 102, 105, 106, 107

All runs made on 1972 Pontiac 400 CID engine dynamometer

Non-leaded fuel, 60 mph steady-state, sample time 4 hours

142 mm, 1 cfm filter

-------
                         -58-
At 400 ft/min flow, a change in temperature from 117°F in an
insulated sample line to 99 °F in a water-jacketed line showed
no change in grams/mile of particulate mass collected.  A change
from 126°F to 106°F showed a change of only 0.0002 grams out of
0.0045 grams collected.  Changes from 109°F to 96°F to 88.5°F
showed weights of 0.0054 g, 0.0057 g, and 0.0062 g.  These
changes are quite small, although it is felt that they are
meaningful.  In all cases, the higher temperatures tended to
give the least amount of sample collected.  However, grams/mile
of particulate mass tended to stay close to being constant with
temperature change.  This effect is shown in Figure 9.

Table 15 shows a reversal of the above observation, however.
Note that in sample Zone 1 (not normally used in particulate
samplings), at 400 ft/min an increase in temperature from
86°F to 106°F gave an increase of 0.0019 g particulate.  It
is felt that the results of Run 105 (ambient conditions,
etc.) were, for some reason,  not comparable to Run 102.  In
both cases, the runs were consistent with themselves with
respect to sample probe location.  The data is plotted as a
function of temperature versus particulate mass in Figure 10.
There does not appear to be a clear trend in particulate
collected based on temperature effects.

Past experience on particulate sampling has shown that
approaching the dew point of the diluted exhaust stream has
a definite effect on the particulate picked up by the
filters.  These runs were all sampled above the dew point.

    Conclusions
    Available data indicate that the higher filter
    temperatures are likely to lead to lower amounts
    of particulate collected.  For that reason, the
    filter probe temperature was maintained at 100°F

-------
£  .006
(O
S-
es
(O
3
O
S-
(O
Q.
   .005
    ,004
    ,003
                 85
95
    TOO       105
Temperature at Filter
110
115
120
125
                               EFFECT  OF  FILTER  TEMPERATURE CHANGE ON GRAMS/MILE
                                                   Figure. 9

-------
   ,01
to
E

-------
                         -61-
    by water jacketing the probes.  This temperature was at
    least 20°F above the dew point of a run at 400 ft/min.
    The temperature of the diluted exhaust at 400 ft/min,
    using indoor diluent air, is generally above 100°F with
    no external controls.  Cooling was almost always necessary
    to give an average of 100°F.  Under conditions of the
    Federal cycle cold start, the sample probes were warmed
    to keep them at 100°F during the first part of the run.

Effect of Dilution Air Temperature - Table 16 contains a
tabulation of data generated to assess the effect of using
cooler outside air as a dilution for the exhaust rather than
warmer inside air.  During the course of these runs, the ambient
air being used for dilution was about 40°F, or roughly 35-40°F
cooler than internal air.

Under comparable conditions of flow rate, the grams/mile of par-
ticulate mass collected showed a 23 percent and a 17 percent
increase using cool air compared to warm air.  This effect was
expected since previous experience had shown that some percentage
of the particulate component was due to condensed material, which
increased in amount as temperatures were lowered.

Since the ambient air was uncontrollable and since the tempera-
ture of the total diluted exhaust stream was difficult to
change except by changing the temperature of the diluent, all
additional work was done using room air for a diluent.  However,
since the temperature effect is real, any condition of cold
starting can be expected to give larger amounts of particulate
than would the corresponding hot start, since the total
diluted exhaust stream is lower in temperature until the engine
reaches operating temperature.

-------
                   TABLE 16


EFFECT OF DILUTION AIR TEMPERATURE ON GRAMS/MILE
Ft/Min
Flow in
Run Tube
109A
109B
110A
HOB
400
400
400
400
Corrected
Flow, cfm
479
509
506
477
Dilution Tube
Temperature
120°F
92 °F
95 °F
122°F
Grams
Collected
.0066
.0077
.0085
.0077
g/Mile
Collected
.0351
.0432
.0478
.0408
Dilution Air
Inside
Outside
Outside
Inside
                                                                           to
                                                                            I
   All runs made on 1972 Pontiac 400 CID engine dynamometer

   Non-leaded fuel, 60 mph steady-state, 3 hour runs

   Average of three filters

-------
                         -63-
    Conclusions
    A lower diluted exhaust stream temperature results in
    higher amounts of collected particulate.  Attempts to
    control this variable will be made by using only inside
    air for a diluent,

Effect of Sample Probe Temperature - Table 17 contains the
results of several tests to determine the effect of varying
the temperature of the sample probe.  Water jackets were
installed on the tubes used as sample probes allowing either
cooling or heating to determine any differences.  Runs were
made at 300, 400, and 500 ft/min.  The 400 ft/min run was not
good since the sample collection temperature dropped below the
dew point, giving meaningless results.

In comparing the effect of a drop in sample probe temperature
at constant flow through the dilution chamber, it was shown
that a cooler sample probe, resulting in cooler temperatures
at the filter, does cause an increase in collected particulate.
This experiment is very closely related to the determination
of the effect of filter temperature previously discussed, and
further verifies the conclusions drawn from those runs.  The
data is plotted in Figure 11.

Although the increase in collected particulate continues to
temperatures below 100°F, this temperature was felt to be the
lower limit of confidence with respect to maintaining an
adequate spread between dew point and filter temperature.
Most future work was done with the sample lines jacketed and
controlled to about 100°F filter temperature.

Effect of Sample Probe Location - The Dow dilution tube is
23 feet long from where the exhaust enters the tube to where
the majority of the sampling has been done.  It was felt that
there might be an effect on the amount of particulate collected
due to sample probe location.

-------
                    TABLE 17
        EFFECT OF SAMPLE PROBE TEMPERATURE

                              SAMPLE ZONE
Ft/Min
Flow in
Tube
300
500
Sampl ing
Point
Temperature
132. 8°F
109. 4°F
Heated
Temp . @
Filter
125°F
111°F
g/Mile
Collected
.0049
.0056
Ambient
Temp . @
Filter
108°F
97°F
g/Mile
Collected
.0060
.0070
Cooled
Temp . @
Filter
82°F
81°F
g/Mile
Collected
.0064
.0070
Runs 113B and 113C
All runs made on 1972 Pontiac 400 CID engine dynamometer
Non-leaded fuel, 60 mph steady-state, 2 hour sample  time
142 mm, 1 cfm filter

-------
   0070
   0065
tQ
i.
CD
o
s_
(O
a.
  ,0060
0055
   ,005
                 85
                        90
                                     5CO
                                      ft"
                                                      :**•
                                                                  i
                                                                       —1—
                                                                                 &
                                                                                               TT
                                                                                                     I
                                                                                                     
-------
                         -66-
Figure 7 is a schematic diagram of the dilution tube and
the three sample zones tested.  In Table 18, the data for
each of the zones at a specific flow rate is tabulated.
In general, the effect of sample probe location is shown to
be slight; for example, Run 105 at 400 ft/min shows a range
of .0094 g to .0098 g of particulate collected across the
three sample zones.  There was a slight temperature decrease
across the three zones which was felt to be more likely the
cause of the slight sample size increase than was any effect
due to location.  Run 106 shows again a very slight decrease
in collected sample at essentially constant temperature.  The
data is graphed in Figure 12.

    Conclusions
    There appeared to be no large effect in particulate
    sample size due to sample probe location.  In all
    further work, samples will be taken only at Zone 3,
    which is 23 feet from the point of entry of the
    exhaust.

Effect of Face Velocity Through the Filter Media - Table 19
is a tabulation of the data collected using a 142 mm glass
fiber filter at varying flow rates.  As is clearly shown,
the gross amount of raw sample collected increases as the
flow increases.  However, when the data was calculated on a
grams/mile basis, the slower rate of collection gives much
higher numbers.  Figures 13 and 14 show this graphically.

Although no attempt was made to keep the sample probe or
filter temperature constant, and although we have noted a
temperature effect on sample size in previous work, it was
felt that the effect noticed in this instance was much
greater than would be expected from the temperature differences
noted.

-------
                  TABLE 18
       EFFECT OF SAMPLE PROBE LOCATION
Sample Zone 1
Sample Zone 2
Sample Zone 3
Run No.
107
105
102
106
Flow
Rate
300
400
400
500
Temp. Before
Filter
122°F
106 °F
86°F
100°F
Grams
Collected
.0087
.0094
.0075
.0065
Temp . Before
Filter
lll'F
102°F
100°F
100°F
Grams
Collected
.0085
.0095
.0073
.0065
Temp. Before
Filter
113°F
100°F
104°F
100°F
Grams
Collected
.0092
.0098
.0086
.0061


i
en
 All runs made on 1972 Pontiac 400 CID engine dynamometer
 Non-leaded fuel, 60 mph steady-state, sample time 4 hours
 142 mm,  1 cfm filter

-------
                TABLE 19
EFFECT OF FLOW RATES THROUGH FILTER MEDIA
Run
96
96
96
96
98
98
98
98
Grams
Collected
.0045
.0053
.0057
.0066
.0051
.0051
.0054
.0072
Flow at
Filter
0.5
1
2
4
0.5
1
2
4
cfm
cfm
cfm
cfm
cfm
cfm
cfm
cfm
Temperature
at Filter
81°F
104°F
115°F
125°F
91°F
100°F
117°F
126°F
Grams Equilibrated
to 1 cfm
.0090
.0053
.0028
.0016
.0102
.0051
.0027
.0018
Grams/Mile
.0394
.0232
.0125
.0072
.0446
.0223
.0118
.0079
                                                                         00
                                                                         I
All runs on 1971 Chevrolet 350 CID chassis dynamometer
Non-leaded fuel, 60 mph steady-state, 2 hours
142 mm glass filter

-------
O)
O
(1)
O
C_5
O)
3

O
s-
(O
o.
  ,006
I
CTi
vo
I
                                         Sample  Location


                                  EFFECT OF  SAMPLE PROBE LOCATION

                                             Figure 12

-------
                           -70-
  .0400
O)
ID
S-
O)
+J
IO

3
O
  .0300
S-
(C
0.
  .0200
  0100
                             2          3

                      Flow Past Filter,  cfm

-------
                           -71-
    040
to
i.
CD
OJ

to


o
S-
ta
Q.
   ,030
   ,020
   ,010
                              234

                            Flow Past Filter,  cfm

-------
                         -72-
Table 20 is a measure of the effect of face velocity through
the filter obtained by varying filter diameter.

The collection of particulate sample at 1 cfm through the 142
mm filter was felt to be the best operating rate since the
additional amount of sample collected at the higher rates was
offset by the difficulty of maintaining these flow rates at a
temperature near 100°F.  In addition, when calculated on a
grams/mile basis, the higher flow rates show a much lower number,

    Conclusions
    High face velocity through the filter media leads
    to comparatively less sample collected.  A rate
    of 1 cfm through the 142 mm filter will be used
    in future work.

Effect of Sample Collection Time - Table 21 is a tabulation
of several runs made to determine the effect of sample
collection time on the amount of particulate collected.  As
would be expected, the longer collection times did result in
more sample collected.  However, the rate of sample collection
was much higher in the initial few minutes of the collection
period than in the final few minutes.  The data from Runs 99,
101, 104, and 108  (calculated in grams/mile) are presented
graphically in Figures 15, 16, 17, and 18.

The raw data from Run 108 shows about 22 percent of a 2-hour
sampling period being collected in the first 5 minutes.  It
was obvious, therefore, that any attempt to attach quantitative
significance to the particulate mass grams/mile figure must be
done with extreme caution.  If all sampling parameters are held
constant except one, comparative significance can be inferred
from a grams/mile calculation.

-------
                                TABLE 20


                 EFFECT OF FACE VELOCITY  THROUGH FILTER
Filter Diameter
Flow Through

   Filter
142 mm
47 mm
293 mm
1 cfm
1 cfm
1 cfn
   Grams

Particulate


   .0022


   .0007


   .0045
Face Velocity


 7.346 ft/min


96.8   ft/min


 0.5208 ft/min
                    Run made on 1971 Chevrolet,  350 CID chassis dynamometer

                    Non-leaded fuel, 60 mph steady-state,  3 hours
                                                                                      co
                                                                                       I

-------
                      -74-
                     TABLE 21
   EFFECT OF SAMPLE COLLECTION TIME ON GRAMS/MILE
Run
99
99
99
99
99
99
101
101
101
101
104
104
104
104
104
104
104
104
108
108
108
108
108
108
108
Filter Time
0.5 hr
1.0 hr
1.5 hr
2.0 hr
1.0 hr
0.5 hr
0.5 hr
1.0 hr
1.5 hr
2.0 hr
5 min
10 min
20 min
30 min
5 min
10 min
20 min
30 min
5 min
10 min
20 min
30 min
1.0 hr
1.5 hr
2.0 hr
Grams
Collected
.0039
.0056
.0070
.0081
.0055
.0036
.0048
.0070
.0072
.0089
.0013
.0023
.0046
.0058
.0015
.0026
.0044
.0061
.0013
.0022
.0034
.0037
.0047
.0054
.0060
Grams/Mile
.0682
.0470
.0408
.0354
.0481
.0630
.0840
.0612
.0420
.0389
.1356
.1206
.1206
.1014
.1572
.1362
.1155
.1066
.1365
.1152
.0891
.0646
.0411
.0314
.0263
All runs on 1971 Chevrolet 350 CID chassis dynamometer
0.5 cc lead fuel except Run 108 which was non-leaded fuel
60 mph steady-state
142 mm, 1 cfm filter

-------
                           -75-
   ,0700

-------
                            -76-
    0900
    0800
Ol
1/1
E
a)
s_
03
O)
4->
(T3
0700
1  .0600
s-.
(O
Q-
    0500
   ,0400
                               1                    2
                                Collection  Time, Hours

-------
                           -77-

(O
3
O
s_
(O
Q.
    1600
    1500
                   .	L
•^  . 1 400
1300
    1200
    1100
    1000
                     r
                         N<—>-
                           \
                    \   ;  ;	
J.MJH1
                                    .11.5.
                                    S/
                                         f i
                                    £1
                                    LE FlOR
                                        .—4—

                                        	;	T—
01
M
                                                    	H-
                     1104  i
                                                   -t-t-t

                            10        15         20

                              Collection Time, Minutes
                                                       25
                    30

-------
                            -78-
   .1400
   ,1200
O)
Z  .1000

-------
                         -79-
In order to obtain sufficient raw sample for analysis,
future work will generally be done using a 2-hour steady-
state collection period, except where a Federal or other
cycle is noted.

    Conclusions
    The sample collection period has a definite effect
    on sample size, with a large amount of the sample
    being collected in the first few minutes.  Grams/
    mile figures of particulate mass are, therefore,
    misleading unless used only in a comparative sense.

Effect of Test Mode - A series of tests were made to deter-
mine the amount of particulate collected during the 23 minute
Federal cycle versus the 41.4 minute modified Federal cycle.
In previous runs it was noted that similar weights were
obtained in both the 23 minute and the modified cycle.

Table 22 is a tabulation of the results and outline of the
procedure used to verify any differences.  The tests were
run on the same day and with all variables essentially constant.
After a 23 minute cold start, 0.0014 g of particulate mass were
collected and after the additional run of 505 seconds, a total
of 0.0020 g were collected.  This verified that somewhat more
sample was collected during the latter part of the modified run.

Tube air (filtered) was drawn through the dilution chamber
and the filter during part of the test to determine the
effect, if any, of the additional time of flow past the
filter surface.  It appears that this effect was negligible.

-------
                                          TABLE  22

                         EFFECT OF  TEST MODE  ON  PARTICULATE COLLECTED


                                 Procedure for  Run  111
                            Federal Cycle  Cold Start Modified
    Filter #1
    Filter #2
   Filter #3
    Filter #4
Cold start 23 min

       4-
10 min tube air

       4-
505 sec hot start

       4-

Stop - weigh paper

       4-

END


.0020 grams
Cold start 23 min
Filter OFF during
10 min shutdown
Filter ON again.
505 sec hot start
Stop - weigh paper
END
                        .0020  grams
Cold start 23 min

       4-

10 min tube air

       4-

Stop - weigh paper

       4-

END


.0014 grams
            Run made on 1971  Chevrolet  350  CID
            chassis dynamometer

            Non-leaded fuel
            142 mm filter, 1  cfm
Cold start 23 min
       4-

Stop - weigh paper
.0014 grams
Replace used paper  into
filter.  Using pre-
filtered air, draw  1  cfm
room air through  filter
for 10 min
.0014 grams
                                                Stop - re-weigh paper
                                                If paper  is  not damaged
                                                replace in filter.
                                                Continue  room air  for
                                                30 min
                                                .0012 grams
                                                Stop - re-weigh  paper
                                                                           i
                                                                          oo
                                                                          o
                                                                           I
                                                                        END

-------
                             -81-
B.  TASK II
    1.  Introduction
    The major objective in Task II was to establish the baseline
    data for the Pontiac 400 CID engine using low lead (0.5 cc/gal)
    and unleaded fuel.

    The data for the non-leaded fuel runs are presented in
    Table 23 and for leaded fuel in Table 24.

    2.  Conclusions
        a.  In general, the low lead fuel gave higher particulate
            levels, in grams/mile of particulate mass, than the
            non-leaded fuel.

        b.  Overall, the aldehyde content of the exhaust condensate
            was not significantly different between the non-leaded
            and low lead fuel.

        c.  The concentration of benzo-a-pyrene in the particulate
            varied widely with engine conditions, but did not
            appear to be significantly changed by use of leaded
            versus unleaded fuel.

        d.  Air/fuel ratio had an effect on particulate with the
            standard setting generally being lower than either rich
            or lean settings.

        e.  The effect on particulate due to changes in spark
            timing is sporadic and, therefore, inconclusive
            based on this data.

        f.  In almost all cases, 30 mph at steady-state gave
            50-100 percent higher particulate mass levels than
            the corresponding 60 mph run.

-------
                                                   TABLE 23

                            ENGINE DYNAMOMETER TEST OF CONVERTER EQUIPPED  ENGINES
Engine Type:    1972  Pontiac  400  CID

Fuel Used:      Indolene #15214 - No  lead  91 octane

Converter Type: None
Run
No.
155A
128A
128B
158C
126A
158A
156A
130C
130A
130B
126B
126B
JL2 6B
126B
129A
129B
Air to Fuel
Range
L
L
L
S
S
S
S
S
S
S
S
S
S
S
R
R
Actual
17.1
15.0
16.7
14.7
14.7
14.5
15.5
15.1
15.1
15.1
-
""
-
13.7
12.7
Test Mode
30 mph CS
30 mph HS
60 mph HS
30 mph HS
30 mph HS
30 mph HS
30 mph CS
60 mph HS
60 mph HS
60 mph HS
Dow Cycle 2
Dow Cycle 3
Dow Cycle 4
Dow Cycle 5
30 mph HS
60 mph HS
Spark
Timing
Std
Std
Std
Adv
Std
Ret
Std
Adv
Std
Ret
Std
Std
Std
Std
Std
Std
Grams /Mile
Particulate Converter
T cfm Filter Temp. (°F)
.0757
.0338
.0218
.0284
.0238
.0260
.0445
.0420
.0167
.0117
.0209
.0209
.0209
.0209
.0387
.0255
Dilution
Tube
Temp. (°F)
93.0
9 3'. 2
147
91.4
95.0
91.0
87.8
140
143
149

91.4

91.4
136.4
Filter
Temp. (°F)
100-102
100-102
93-96
102-105
100-105
10'0-107
97-100
88-96
86-100
90-100

96-100.

99-100
102-104
ppm in
Exhaust Condensate
HCHO
613
300
400
660
210
410
591
1530
360
150

230

250
150
NH0
	 j
5
16
-
6
1
CO
_ NJ
13
10
10

12

6
14
Spark setting:
Adv = Std -10°
Ret = Std +10°

-------
                       -83-
Continuation of Table 23
                         ANALYSIS OF EXHAUST GAS
              % by Volume
Parts per Million
Run
No.
155A
128A
128B
158C
126A
158A
156A
130C
130A
130B
126B
126B
126B
126B
129A
129B
C02
9.0
11.1
12.0
13.8
11.7
13.7
12.2
11.3
12.9
12.7
10.3
11.2
9.4
11.1
13.4
11.9
°2
10.35
7.0
5.7
3.2
4.5
3.4
5.2
6.5
3.5
4.3
7.6
6.1
9.3
6.0
2.9
3.5
N2
79.7
80.9
81.4
82.3
82.8
82.2
81.5
81.1
82.3
82.0
81.2
81.7
80.4
82.0
82.4
81.7
CO
.03
.03
.03
.03
.03
.03
.05
.17
.43
.03
.03
.03
.03
.03
.31
1.95
Total
H.C.
115
189
78
210
275
150
316
830
145
43
265
145
218
300
268
305
NO_
200
850
850
56
850
32
65
1300
850
900
-
-
-
-
400
360
NO
425
270
330
2100
260
650
960
650
575
340
-
-
-
-
1100
1500
NO

-
-
-
-
-
-
-
-
-
-
-
-
-
-
-

-------
Continuation of Table 23
                                       ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate
Run
No.
155A
128A
128B
158C
126A
158A
156A
130C
130A
130B
126B
126B
126B
126B
129A
129B
Trace Metals on Millipore Filter (% of particulate)
Fe Ni Cu Al
- - - -
_
.277 <.055 .250 .250
.538 <.153 .230 <.153
.416 <.166 .416 <.166
_
-
_
- - - -
_
_ _ — —
Ca Mg Mn Cr Sn Zn Ti
_______
_______
1.75 .388 <.027 <.055 <.055 <.166 X.055
3.0 1.0 <.07 <.153 <.153 <.46 <.153
6.0 1.5 <.08 <.168 <.166 <.50 <.166
_______

_______
_"_____-
_______
_______
% Pb
Atomic
Absorp
0.7
0.7
1.2
0.9
0.3
1.6
1.9
.009
1.9
1.2
.05
-
-
-
1.2
1.1
% C on
Glass
Filter
47.6
104.5
58.8
72
76.9
65.7
78
59.4
53.4
151.0
-
-
-
50.2
65.4
ppm
BaP
22
146
14
33
112
69
148
192
12
94
71
-
-
-
113
161


1
00
1







-------
                                                   TABLE 24
                            ENGINE DYNAMOMETER TEST OF CONVERTER EQUIPPED ENGINES
Engine Type:    1972 Pontiac 400 CID
Fuel Used:      Indolene #15473 - 0.5 cc lead 91 octane
Converter Type: None
Run
No.
168A
135A
168B
170B
132A
170C
170A
176C
176A
176B
132B
132B
132B
132B
171A
171B
136B
Air
Range
L
L
L
S
S
S
S
S
S
S
S
S
S
S
R
R
R
to Fuel
Actual
16.0
16.0
16.0
15.8
14.6
15.9
15.8
14.6
15.0
14.8
-
-•
- -
-
12.4
12.3
12.9
Test Mode
30 raph CS
30 mph CS
60 mph CS
30 mph HS
30 mph HS
30 mph HS
30 mph CS
60 mph HS
60 mph HS
60 mph HS
Dow Cycle 2
Dow Cycle 3
Dow Cycle 4
Dow Cycle 5
30 mph CS
30 mph HS
60 mph HS
Spark
Timing
Std
Std
Std
Adv
Std
Ret
Std
Adv
-Std
Ret
Std
Std
Std
Std
Std
Std
Std
Grams/Mile
Particulate Converter
1 cfm Filter Temp. (°F)
.0650
.0378
.0275
.0363
.0423
.0404
.0433
.0268
.0239
.0255
.0390
.0390
.0390
.0390
.0602
.0431
.0299
Dilution
Tube
Temp. (°F)
89.6
98.0
114.8
91.4
93.0
91.4
89.6
119
120
123
93-134
-
-
-
89.6
89.6
136
Filter
Temp. (°F)
97-100
100-
100-102
100-102
93-97
99-102
97-100
99-102
103-105
100-103
93-96
-
-
-
97-100
95-102
98-100
ppm in
Exhaust Condensate
HCHO
600
550
440
340
300
570
510
440
330
250
370
-
-
-
190
300
250
NH3
-
31
-
-
8
-
~ o>
en
-
.
13
.
-
-
-
-
-
Spark setting:
Adv = Std -10°
Ret = Std +10°

-------
                      -86-
Continuation of Table 24
                    ANALYSIS  OF  EXHAUST  GAS
              % by Volume
Parts per Million
Run
No.
168A
135A
168B
170B
132A
170C
170A
176C
176A
176B
132B
132B
132B
132B
171A
171B
136B
co2
12.2
11.8
12.8
13.0
12.7
12.9
12.7
13.1
13.0
13.4
12.2
11.8
12.5
11.8
9.8
10.1
13.0
°2
3.4
6.1
4.1
3.4
4.3
3.6
3.8
2.8
3.4
3.0
5.6
5.7
4.7
5.7
1.55
1.6
2.2
*2
82.6
81.2
81.8
82.0
81.7
81.8
81.7
82.4
82.0
82.1
81.4
81.2
81.6
81.2
79.8
80.4
82.2
CO
.64
.02
.31
.75
.17
.83
.95
.75
.61
.64
.03
.37
.25
.14
9.8
6.9
1.57
Total
H.C.
385
170
167
272
175
397
360
230
205
180
150
137
125
145
775
710
280
N02
40
500
40
33
550
33
33
23
2.3
13
-
-
-
-
7
15
1150
NO NO
1050
450
1400
505
380
1100
810
1800
1150
850
- -
- -
- -
- -
1050
1100
580

-------
Continuation of Table 24
                                        ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate
Trace Metals on Millipore Filter (%)
Run
No. Fe Ni Cu Al Ca Mg Mn Cr Sn Zn
168A - - - - --
135A __________
168B __________
170B - - --
132A - - - - - - - - --
170C __________
170A - - - - ' - - --
176C - - --
176A __________
176B - - - - - - . -
132B - - - -.-
132B - - - . -
132B - - - - - - - - - ' -
132B _--_-_____
171A - - - - -- - --
171B _ -_
136B
% Pb
Atomic
Ti Absorp
6.4
4.7
10.4
4.2
7.2
5.6
6.7
-
^ ^
14.4
-
'
-
8.4
12.1
12.8
% C on
Glass
Filter
68.4
-
41.0
66.1
-
57.4
57.0

— m
-
-
-
-
58.0
51.0
32.1
ppm
BaP
424
63
<8
<13
<11
19
30
127
98 I
00
88 ^J
21
-
-
-
615
225
62

-------
                         -88-
    g.  Standard spark setting gave a higher percentage
        of larger particles than either advanced or retarded
        spark.

3.  Discussion
This baseline data will have absolute significance only
when used as a comparison to the same engine equipped with
various converters.  However, several interesting points
can be noted when looking at the differences in particulate
as a function of engine operating conditions.

As noted in the conclusions, low lead fuel seems to give
higher particulates than non-leaded.  This was also the
conclusion of the work done under Contract CPA-22-69-145,
and reported by Moran et al.  This data is presented
graphically in Figures 19, 20, and 21.  The amounts of aldehyde
and benzo-a-pyrene did not appear to be significantly changed
by the use of 0.5 cc leaded fuel.  This was not unexpected.
A more meaningful comparison will be the levels of these
compounds after the use of a converter.  This data will be
discussed in a later section.

The air/fuel ratio of the engine had an effect on particulate
as shown in Figure 19.  The important point to note here is
that the standard air/fuel ratio did seem to give the lowest
particulate.  Figures 19, 20, and 21 show the effect of 60 mph
versus 30 mph.  In almost every instance, regardless of the
air/fuel ratio or spark setting, the equivalent 30 mph run was
higher in particulate.  This may in part be explained by the
difference in dilution tube temperature.  Although the filter
temperature as shown in Tables 23 and 24 was held within 10°F
of 100°F, the dilution tube itself was 40-50°F higher at 60 mph
than at 30 mph.

-------
                            -89-
    ,04
o>
ISI
E

03
3
CJ
ra
a.
                 Lean
Standard
                                                                Rich

-------
                           -90-
E
10
i.

(O
s-

-------
                          -91-
   ,05
   .04





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3
,03
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         CO to


         Std
               O O
               CO tO


               Lean
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 co to


Rich
O O
co to


 Std
O O
CO to


 Lean
O O
co to

Rich
               Unleaded  Fuel
                                       Leaded  Fuel

-------
                             -92-
    The mass medium equivalent diameter (MMED) can be determined from
    the mass distribution charts in Figures 22-27.  Mass medium
    equivalent diameter is the diameter of the particle, in microns,
    of which 50 percent are smaller and 50 percent are larger.
    The mass distribution plots show the percent of particles
    less than a given diameter.

    In comparing the baseline data with MMED, it is apparent that
    the standard spark setting gives larger particles than either
    advanced or retarded spark setting.  The MMED for standard
    spark was approximately 0.6 microns, approximately 0.2 microns
    for retarded spark, and less than 0.1 for advanced spark.
    For leaded fuel, at standard spark and standard A/F, the MMED
    was less than 0.5 microns, which was smaller than that seen
    with non-leaded fuel.

C.  TASK III

    1.  Introduction
    The objective in Task III was to evaluate various emission
    control devices with respect to their effect on non-regulated
    emissions.  The devices tested under this portion of the
    contract include:
                    •Three oxidation catalysts
                    •One reduction catalyst
                    •One exhaust gas recirculation system

    Initially, work was done using both non-leaded and low lead
    (0.5 cc/gal) fuel.  The leaded fuel itself caused increases in
    the amount of particulate and, after testing one catalyst on
    leaded fuel, the rest were run only on non-leaded fuel.

    The devices were obtained from either the manufacturer or an
    automobile company under a secrecy agreement, to protect any
    proprietary rights involved.  Consequently, the data on the

-------
                          PROBABILITY     46 SO43

                          X 2 LOG CYCLES   HADE IN U.S.A. .

                            KEUFFELa ESSCR CO.
99.99
                                                                                              0.2  0.1  0.05
                                                                                                         0.01
            Figure  22

       MASS DISTRIBUTION

 Baseline,  Std  Spark,  Std A/F

            Run No.  130A
                                   Total  in  Particles  of Diameter  
-------
                                              46 8043
                                              MADf IN U.S.». •
                                   KEUFFEL & CSSER CO.
PROBABILITY
X 2 LOG CYCLES
       99.99
                                                                                                       0.2  O.J 0.05
                                                                                                                   0.01
O
s_
U

-------
                                              46 8043
                                              NADF IN U.S.A. •
                                   KEUFFEL a ESSER CO.
PROBABILITY
X 2 LOG CYCLES
       99.99
               99.9 99.8
                                                                                                                 0.01
 c
 o
 s-
 o
0)
•!->
0)
E
10
T-
o

01

o
                 Figure  24
              MASS DISTRIBUTION
         Baseline Adv  Spark,  Std A/F

                   Run No.  130C
                                          Total in  Particles  of Diameter  
-------
                                               46 SO43
                                               NAOF IN U.S.A. •
                                    KEUFFEL & ESSER CO.
PROBABILITY
X 2 LOG CYCLES
       99.99
                                                                                                                     0.01
 V)
 E
 O
 s_
 O
(V
4->
CD
E
(O
•r—
O

V

O
S-
 ; i -; «.-	r—i
                                            Total  in  Particles  of Diameter 
-------
                                PROBABILITY
                                X 2 LOG CYCLES
           46 8O43
           MADE IN U. i.A. •

KEUFPEL » ESSER CO.
       99.99
                                                                                                               0.01
 to
 C
 o
 J-
 o
o>
E
(0
o
•r"
4->
S-


Q.
                Figure 26

              MASS  DISTRIBUTION
        Baseline  Adv Spark, Std  A/F   ^
                   0.5 cc  Lead
                   Run No.  134C  (176C)
                                          Total  in Particles of  Diameter 
-------
                                               46 8043
                                               MAOf IN U.S. A.

                                    KEUPFEL a ESSER CO.
                         PROBABIUITY
                         X 2 LOG CYCLES
   10-


    9.


    8.


    7.



    6..




    5.
       99.99
               99.9  99.8
                           99   98
                                     95    90
                                                 80    70
                                                                                                                     0.01
                                           Total  in Particles of  Diameter  
-------
                         -99-
devices are reported with the only reference to the device being
a code letter.  The code letters and general description of the
devices are as follows:

    A.  Monolith, noble metal oxidation catalyst
    B.  Beaded, base metal oxidation catalyst
    C.  Beaded, base metal oxidation catalyst
    D.  Monolith reduction catalyst
    E.  Exhaust gas recirculation system

The data from these runs is shown in Tables 25 -31.

2.   Conclusions

    a.  The use of three different oxidation catalysts on an
        engine stand, with non-leaded fuel, increased the amounts
        of particulate collected at 60 mph by a factor of 2-5,
        compared to a baseline run, except under rich air/fuel
        ratios.  Two catalysts did not generally increase the
        particulate collected at 30 mph, or under cyclic condi-
        tions.  The total particulate collected from the control
        devices was less than normally found when using 3 cc
        leaded fuel.

    b.  The three oxidation catalysts significantly lowered
        the emission of aldehydes, as collected in the
        condensate.

    c.  There was no evidence in the particulate of catalyst
        degradation being the cause of the increase in
        particulate mass.

    d.  An increase in particulate comparing 30 mph to 60 mph
        was noted during the baseline runs.  This appeared to
        be reversed when running at standard conditions with
        two of the three oxidation catalysts.

-------
                                                   TABLE 25

                            ENGINE DYNAMOMETER TEST OP CONVERTER EQUIPPED ENGINES
Engine Types 1972 Pontiac 400 CID

Fuel Used:   Indolene #1.5214

Converter Type: "A" with 1975 Hardware, Monolith, Noble Metal

Run
No.
142B
142A
143B
140C
140A
140B
143A
143A

143A
143A
141B
141A

Air
Range
L
L
S
S
S
S
S
S

S
S
R
R

to Fuel
Actual
15.3
16.8
14.1
14.2
14.8
14.9
-
-

-
-
13.1
12.4


Test Mode
30 mph
60 mph
30 mph
60 mph
60 mph
60 mph
Dow Cycle 2
Dow Cycle 3

Dow Cycle 4
Dow Cycle 5
30 mph
60 mph

Spark
Timing
Std
Std
Std
Adv
Std
Ret
Std
Std

Std
Std
Std
Std
Grams/Mile
Particulate
1 cfm Filter
.1078
.1193
.0968
.0866
.0905
.0733
.0913
.0913

.0913
.0913
.0092
.0207

Converter
Temp. (°F)
825
1160
865
1210
1205
1240
820
940

1220
825
910
1180
Dilution
Tube
Temp. (°F)
87.7
127.4
91.4
131.0
131.0
132.8


_


91.4
131
ppm in
Filter
Temp. (°F)
96-100
100-102
98-100
100-102
100-102
102-103


_


100-102
100-102
Exhaust
HCHO
26
65
14
35
12
7.5


29


9.3
71
Condensate
NH,

-
'
7
4
2


M


.
-


M
O
O
1










Spark setting:
Adv = Std -10°
Ret = Std +10°

-------
Continuation of Table 25
                                            ANALYSIS OF EXHAUST GAS
                         Before Converter
After Converter
% by Volume
Run
No.
142B
14 2 A
143B
140C
140A
140B
143 A
143A
14 3 A
143A
141B
141A
co2
11.7
9.9
6.9
12.0
12.3
12.6
8.4
11.1
11.8
10.8
12.3
12.3
°2
6.2
9.0
13.9
4.6
4.0
3.7
11.5
7.1
5.6
7.7
4.1
3.5
N2
81.2
80.1
78.3
81.9
82.4
82.2
. 79.1
80.8
81.3
80.6
81.7
81.4
CO
.03
.07
.07
.51
.37
.39
.08
.04
.34
.11
.82
2.2
Parts per
Total
H.C. N00
165
255
215
215
100
61
200
140
130
230
303
310
Million
NO NO^ CO.,
11.8
11.0
10.5
13.7
13.4
12.1
10.1
10.0
12.1
9.7
- . 13.7
12.3
% by Volume
°2
6.1
7.3
8.1
2.9
3.3
5.0
8.9
9.1
5.7
9.2
2.3
2.3
N2
81.2
80.8
80.5
82.5
82.4
82.0
80.1
80.0
81.4
80.2
81.6
81.9
CO
.03
.03
.03
.03
.03
.03
.03
.03
.03
.03
.21
2.3
Parts per Million
Total
H«C.
17
35
27
23
14
7
30
14
25
39
140
260
NO2
275
430
450
570
330
285
— m
-
-
200
390
NO
590
600
570
850
1250
850
—
-
' -
320
1650
NO

-
-
-
-
-
1
(-•
~ o
M
~ 1
-
-
-

-------
Continuation of Table  25
                                       ANALYSIS OF EXHAUST PARTICULATE
                                                                                            Measured in  Particulate
Run
No.
142B
14 2A
143B
14 OC
140A
140B
143A
143A
143A
14 3 A
141B
14 1A
Trace Metals on Millipore Filter (%)
Fe Ni Cu
_ _ _
_
_
_
.06 .02 .09
.09 .02 0.1
.08 .02 0.1
_
_
: : :
_ — —
Al
-
-
-
-
.05
.04
.04
-
-
—
_
Ca
-
-
-
-
.60
.77
.83
-
-
—
_
Mg
-
-
-
.10
.16
.14
-
-
—
_
Mn Cr Sn
_
_
_
_
<.01 <.02 <.02
<.01 <.02 <.02
<.01 <.02 <.02
_
_
m. _ —
_ _ _
Zn
-
-
-
-
<.05
<.05
<.05
-
-
^
—
Ti
-
-
-
-
<.02
<.02
<.02
-
-
^
-
% Pb
Atomic
Absorp
0.2
0.2
0.1
0.1
0.2
<0.1
0.2
-
-
0.2
0.9
% C on
Glass
Filter
<1
3.1
<1
3.2
0.6
0.4
1.5
-
-
43.2
60.9
ppm
BaP
<5
21
35
6
17
<6
8
-
-
<53
17








1
o
NJ


-------
                                                   TABLE 26
                            ENGINE DYNAMOMETER TEST OF CONVERTER EQUIPPED ENGINES
Engine Type:    1972 Pontiac 400 CID
Fuel Used:      Indolene #15473, 0.5 cc lead 91 octane
Converter Type: "A" with 1975 Hardware, Monolith, Noble Metal
Run
No.
167A
15 IB
151A
166C
146A
166B
166A
145C
14 5A
145B
14 6B
146B
146B
146B
165A
150A
150B
Air to Fuel
Range
L
L
L
S
S
S
S
S
S
S
S
S
S
S
R
R
R
Actual
16.0
15.4
15.6
15.1
14.5
15.1
15.2
15.5
15.6
15.6
-.
—
-
12.0
14.2
13.3
Test Mode
30 mph CS
30 mph HS
60 mph HS
30 mph HS
30 mph HS
30 mph HS
30 mph CS
60 mph HS
60 mph HS
60 mph HS
Dow Cycle 2
Dow Cycle 3
Dow Cycle 4
Dow Cycle 5
30 mph CS
30 mph HS
60 mph HS
Spark
Timing
Std
Std
Std
Adv
Std
Ret
Std
Adv
Std
Ret
Std
Std
Std
Std
Std
Std
Std
Grams/Mile
Particulate
. 1 cfm Filter
.0388
.0364
.0742
.0256
.0245
.0222
.0257
.1268
.1130
.1001
.0580
.0580
.0580
.0580
.0592
.0354
.0305
Converter
Temp. (°F)
910
960
1250
950
920
1000
1000
1200
1210
1260
800
1075
1240
870
1150
1070
1250
Dilution
Tube
Temp. (°F)
8.9.6
93.2
127.4
93.2
93.2
89.6
87.0
127
140
127

-

98.6
95.0
129
Filter
Temp. (°F)
99-102
100-104
100-102
98-102
98-102
99-102
99-100
100-102
100-104
95-97

-

102-104
100-105
100-102
ppm in
Exhaust Condensate
HCHO NH_3
180
100
118
110
100
66
170 -
97 6
61 2
30 5
-
100

26
72
<10
Spark setting:
Adv = Std -10°
Ret = Std +10°

-------
Continuation of Table 26
                                            ANALYSIS  OF  EXHAUST GAS
                         Before  Converter
After Converter
% by Volume
Run
No.
167A
151B
15 LA
165C
14 6A
166B
166A
145C
14 3 A
14 3B
14 ',B
14 -SB
14 oB
14 5B
165A
150A
150B

co2
12.7
9.6
10.9
12.7
11.5
13.1
12.5
12.2
12.0
11.1
10.8
11.9
11.4
11.0
11.4
8.0
10.8

°2
4.3
9.2
7.1
4.1
6.5
3.4
4.0
5.1
5.8
6.8
7.4
4.9
6.3
7.3
2.6
11.5
4.8

81.8
80.0
80.8
81.6
81.3
82.0
81.7
81.6
81.2
80.4
80.8
81.3
80.9
80.8
81.0
79.0
80.7

CO
.32
.34
.38
.52
.06
.64
.70
.20
.11
.16
.04
.95
.38
.06
3.9
.61
2.79
Parts per
Total
H.C. NO0
298
260
178
375
200
225
315
170
140
175
200
288
190
165
496
280
425
Million

NO NO.. CO.,
13.2
9.8
8.9
13.6
11.6
13.9
14.0
11.5
10.6
11.2
_
_
_
- -
13.2
9.9
10.9
% by

°2
4.15
9.2
10.4 -
3.3
6.3
2.8
2.7
6.5
5.9
6.9
-
-
-
-
0.6
9.2
6.4
Volume

81.7
80.1
79.5
82.0
81.1
82.3
82.3
81.0
81.2
80.9
-
-
-
-
82.6
80.0
80.9
Parts per Million

CO
.03
.03
.03
.03
.03
.03
.03
.03
.29
.03
-
-
-
-
2.78
.06
.86
Total
H~C.
75
84
40
100
75
65
120
37
20
8
-
-
-
_
480
145
220

NO
40
' 200
650
33
240
33
10
625
555
250
-
-
-
-
40
240
460

NO
1100
500
520
1100
575
600
850
975
850
690
-
-
-
-
900
450
930

N0x

-
-
-
-
-
I
~ o
£».
1
-
-
-
-
-
-
-
-

-------
Continuation of Table 26





                                        ANALYSIS OF EXHAUST PARTICULATE
                                                                                             Measured in Particulate

No. Fe Ni Cu
167A -
151B -
151A -
166C -
146A -
166B
166A -
145C .036 <.007 .056
145A .075 <.008 .058
145B 2.9 <.05 3.2
146B _ _ -
146B
146B - - - .
146B -
165A -
150A -
150B -
Trace Metals on Millipore Filter (%) A* 	 .„
Al Ca Mg Mn Cr Sn Zn Ti Absorp
___----- 1.4
-0.9
-------- 0.9
-- -2.5
--------1.8
- .- _ _ _ 2.3
----- -- -2.5
.020 .40 .040 X.004 <.007 <.007 <.020 <.007 0.7
.026 .41 .052 <.004 .015 <.008 <.021 <.008 0.7
.90 .21 2.2 <.25 .53 .50 <1.5 <.50 0.7
_'_ - - - - - -1.5
_•-
__ _ _ _ _ _._
_-_ _ _._
------- - 11.9
-.-
— — — — — — ' — — —
% C on
Glass
Filter
7.3
12.1
12.3
12.0
5.3
8.3
20
3.9
3.1
3.9
3.4

-
-
41.2
20.4
20.2
ppm
BaP
90
19
22
<19
-
<21
62
«4
<4
-
<6
-
-
-
374
<13
24
                                                                                                                     cn

-------
                                                  TABLE 27
                            ENGINE DYNAMOMETER TEST OF CONVERTER EQUIPPED  ENGINES
                1972 Pontiac 400 CID
                Indolene f15214, No lead.91 octane
Converter Type: "B" with 1975 Hardware,  Beaded, Base Metal
Engine Type:
Fuel Used:
Run
No.
183A
182B
181A
181C
182A
182A
182A
182A
18 QA
179A
179B
Air to Fuel
Range
L
S
S
S
S
S
S
S
R
R
R
Actual
16.6
15.4
14.9
15.2
-
—
•"
13.7
13.8
Test Mode
60 mph
60 mph
30 mph
60 mph
Dow Cycle 2
Dow Cycle 3
Dow Cycle 4
Dow Cycle 5
30 mph
60 mph
60 mph
Spark
Timing
Std
Ret
Std
Std
Std
Std
Std
Std
•Std
Std
Std
Grams/Mile
Particulate
1 cfm Filter
.1165
.1134
.0048
.1052
.0256
.0256
.0256
.0256
Nil
.0522
.0183
Converter
Temp. (°F)
1140
1200
795
1235
825
1100
1190
975
950
1290
1235
Dilution
Tube
Temp. (°F)
129
129
92
131

112
89
130
122
Filter-
Temp . ( °F )
102-105
104-107
100-104
103-106

99-100
99-103
104-107
98-100
ppm in
Exhaust Condensate
HCHO
3.8
2.1
19
5.9

6.5
6.0
3.5
0.7
NH3
1.0
3.0
36
7
-
10.0
87
35
1700





1
h->
o

-------
Continuation of Table 27
                                            ANALYSIS OF EXHAUST GAS
                         Before Converter
After Converter
Run
No.
183A
182B
18 1A
18 1C
182A
182A
182A
182A
18 OA
179A
179B

CO
11.2
12.5
12.0 .
12.7
12.5
12.7
12.5
12.3
14.5
12.9
14.4
% by
°2
7.0
4.7
5.7
3.8
4.8
4.7
5.8 '
5.1
0.9
3.4
1.1
Volume
N2
80.9
81.7
81.4
82.0
81.7
81.5
81.6
81.6
82.9
81.9
82.7

CO
.03
.03
.03
.27
.08
.15
.03
.06
.79
.03
.03
Parts per
Total
H.C. NO0
40
25
150
40
180
125
65
160
350
50
220
Million
NO NO,, CO,
11.4
12.8
12.4
13.1
13.0
13.1
13.0
13.0
14.9
14.8
15.1
% by
°2
6.7
4.3
5.2
3.3
4.3
4.0
4.2
4.1
0.4
2.5
0.5
Volume
N2
80.9
81.9
81.5
82.2
81.8
81.4
81.8
81.9
83.2
81.6
82.8
Parts per Million
CO
.03
.03
.03
.03
.03
.03
.03
.03
.55
.03
.40
Tptal
. H.C.
5
5
40
5
35
25
10
10
150
8
90
NO
. 85
55
-
65
-
65
75
72
7
37
17
NO
500
975
-
1600
-
920
1800
1000
930
1500
1600
—X
-
-
-
-
-
I
I— i
_ o
I
-
" -

-------
Continuation of Table  27
                                       ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate

No . Fe Ni
183A
182B
181A
181C .21 .016
182A
182A
182A
18 2A
180A
179A
179B
Trace Metals
Cu Al Ca
_ _ _
_
_
.050 .240 .240
_
_
_
_
_
on Millipore Filter (%)
Mcj Mn Cr Sn Zn
_
- - - - -
_
.055 <.008 <.008 <.008 .058
_
_
_
-----
_
% Pb
Ti Absorp
-
-
-
<.008
-
-
-
-
-
% C on
Glass
Filter
5.0
5.1
7.9
2.9
48.5
-
-
-
•;::
ppm
BaP
4
24
145
10
-
-
-
-
11 t-
o
39 «,

-------
                       TABLE 28


ENGINE DYNAMOMETER TEST OF CONVERTER EQUIPPED ENGINES
Engine Type: 1972 Pontiac 400 CID
Fuel Used: Indolene 115214, No lead 91 octane
Converter
Run
No.
184A
185A
186D
18CA
185D
185B
185B
185B
187C
187B
187A
Air
Rang
L
S
S
S
S
S
S
S
R
R
R
Type: "C"
to Fuel
e Actual
16.6
14.9
15.0
14.7
14.5
14.7
14.8
14.8
13.4
13.4
13.3
with 1975 Hardware, Beaded, Base Metal
Test Mode
60 mph
60 mph
30 mph
60 mph
Dow Cycle 2
Dow Cycle 3
Dow Cycle 4
Dow Cycle 5
30 raph
60 mph
60 mph
Spark
Timing
Std
Ret
Std
Std
Std
Std
Std
Std
Std
Std
Std
Grams /Mile
Particulate
1 cfm Filter
.0052
.0533
Nil
.0554
.0383
.0383
.0383
.0383
.0117
.0360
.0171
Converter
Temp. (°F)
1140
1190
810
1150
750
975
1175
840
875
1440
1175
Dilution
Tube
Temp. («F)
134
126
92.0
125

115

95.0
142
115
Filter
Temp. (°F)
107-110
105-107
104-105
104-105

106-107

103-105
109-112
100-101
ppm in
Exhaust Condensate
HCIIO
0.8
0.3
28
5.3

4.8

1.5
0.2
0.2
NH
3.4
1.0
3.9
1.2

3.2

740.0
15.3
2180.0
ppm in
Exhaust Gas
HCHO
0.023
0.009
0.95
0.17

-

0.068
0.006
0.008
NH-
j
0.18
0.06
0.23
0.068

-

38.8
0.88
154.66
                                                                                                                              o
                                                                                                                              vo
                                                                                                                               I

-------
Continuation of  Table 28
ANAL1
Before Converter

Run
No.
184A
185A
1EI6B
1H6A
1N5B
18 5B
1K5B
105B
187C
1H7B
1H7A


co2
12.0
12.8
12.2
12.6
12.4
11.8
12.9
12.2
14.3
13.1
14.2
% by

°2
5.5
4.4
5.2
4.8
4.8
5.9
4.1 '
5.2
1.0
2.3
0.7
Volume

N2
81.6
81.8
81.6
81.7
81.8
81.3
82.0
81.6
82.7
82.5
82.5
fSIS OF EXHA
Parts per Million

CO
.03
.03
.10
.03
.32
.11
.09
.03
.06
.95
.53
Total
H.C. NO.,
45
20
142
45
160
90
50
170
250
65
226

NO N0v

-
-
-
-
-
-
-
- -
-
- - •
                                                             co2
                                                             12.5
                                                             13.2
                                                             12.5
                                                             13.1
                                                             12.7
                                                             12.3
                                                             13.1
                                                             12.4
                                                             15.0
                                                             14.9
                                                             15.1
                                                                               After Converter
                                                                    % by Volume
                        Parts per Million
 °2
4.6
4.1
4.8
4.1
4.7
5.3
3.9
5.0
0.35
1.2
0.27
 "2
81.6
81.8
81.8
81.9
81.7
81.5
82.1
81.5
83.1
83.0
83.0
CO
.03
.03
.03
.03
.03
.03
.03
.03
.41
.03
.20
93
33
 7
65
 8
58
65
33
15
10
 8
 NO
1500
1000
1100
1500
 900
 900
1850
1000
 560
 425
 380
I
o
I

-------
Continuation of Table 28






                                        ANALYSIS OF EXHAUST PARTICULATE
                                                                                             Measured in Particulate

No. Fe Ni
184A
185A
18 6B
186A .21 <.024
185B
185B
185B
185B
187C
187B
187A
Trace Metals on Millipore Filter (%)
Cu Al Ca Mg Mn Cr Sn
_______
_ •
_
.16 .093 .98 .25 <.024 .057 .045.
• _
_ _
_______
_______
_______
_______
_ _ ' _ _ _ _ _
% Pb
Zn Ti Absorg.
_
-
_ _
.086 .024
_
_
_
_
_
_
_ _ _
% C on
Glass
Filter
57.9
7.6
_
11.1
31.6
-
-
-
91.0
20.0
43.4
ppm
BaP
36
13
-
16
<9
-
-
-
145
36
<13

-------
                                                   TABLE 29
                            ENGINE DYNAMOMETER TEST OF CONVERTER EQUIPPED ENGINES
Engine Type:    1972 Pontiac 400 CID
Fuel Used:      Indolene 115214, Ho lead 91 octane
Converter Type: NOx - "D", Monolith
Run
No.
201A
202A
202B
202C
202D
Spark
Air to
Fuel
Range Actual
R
R
R
R
R
setting:
13.9
13.9
13.8
13.8
13.8
Adv
Ret
Test Mode
60 mph
60 mph
60 mph
60 mph
30 mph
=> Std -10°
= Std +10°
Spark
Timing
Std
Std
Adv
Rtd
Std

Grams/Mile
Particulate
1 cfm Filter
.0052
.0126
.0129
.0036
.0031

Converter
Temp. (°F)
1090
1100
1105
-
"

Dilution
Tube
Temp. (°F)
125
111
113
-
"

Filter
Temp. (°F)
104-107
98-100
97-99
-
"

ppm in
Exhaust Condensate
HCHO NH3
33 310
32 320
13
13
"

ppm in
Exhaust Gas
HCHO NH
1.27 23.
1.33 23.
0.600
0.62
— —


3
3
5




N)
 I

-------
Continuation of Table 29
                                            ANALYSIS OF EXHAUST GAS
                         Before Converter
After Converter
% by Volume
Run
No.
201A
202A
202B
13.7
14.0
13.3 ,
°2
0.9
0.73
0.75
82.8
83.2
83.8
CO
1.63
1.16
1.11
Parts per Million
Total
H . C .
250
240
250
7
16
10
NO NOX
1400
1600
1750
co2
13.8
14.1
13.7
% by Volume
5-2
0.7
0.56
0.6
83.0
83.6
84.1
CO .
1.5
0.72
0.67
Parts per Million
Total
H.C.
220
200
170
. 7
5
10
NO
1050
1150
1100
NO
-
-
                                                                                                                     u>
                                                                                                                     I

-------
                                                 TABLE 30
                           ENGINE DYNAMOMETER TEST OF CONVERTER EQUIPPED  ENGINES
Engine Type:
Fuel Used:
Converter Type
Run Air to
1972
Pontiac 400
Indolene #15214,
: EGR
Fuel
No. Range Actual
228G L .
228F S
228A S •
228B S
228C S
22SC S -
228C S
228C S
228E R
228D R
16.7
15.0
15.7
15.6
15.3
15.3
15.3
15.3
13.5
13.5
- ON-
Test Mode
60 mph
60 mph
30 mph
60 mph
Dow Cycle 2
Dow Cycle 3
Dow Cycle 4
Dow Cycle 5
30 mph
60 mph
CID
No lead 91

Spark
Timing
Std
Ret
Std
Std
Std
Std
Std
Std
Std
Std

octane

Grams /Mile
Particulate
1 cfm Filter
.0124
.0071
.0314
.0097
.0183
-
-
-
.0227
• .0079
                                                           Converter
                                                           Temp.(°F)
                                                       Dilution
                                                         Tube
                                                       Temp.(°F)
                                                         185
                                                         210
                                                         109
                                                         185
                                                                          95-215
 Filter
Temp.(°F)
 100-120
 125-130
  92-98
 110-118
                                                                    100-125


                                                                     85-90
                                                                    225-245
      ppm in
Exhaust Condensate
  HCHO       NH3
 460.46     41.25
 108.9       4.9
 569.2      35.9
 342.8      29.9
             889.6

             461.9
             282.44
                                                                                                           12.7

                                                                                                           15.4
                                                                                                           20.4
                                                                                                                          ppm  in
                                                                                                                        Exhaust Gas
HCHO
21.0
 5.2
31.4
 7.5
41.9
27.1
                                                                                                                                  3.3
                                                                                                                                  0.4
                                                                                                                                  3.5
                                                                                                                                  1.2
                                   2.4
                                   3.4
Spark setting:
Adv = Std -10°
Ret = Std +10°

-------
                            -115-
Continuation of Table 30
                          EXHAUST GAS  ANALYSIS
                 % by Volume	      Parts per Million
™2
14.4
12.4-
10.9
11.4
11.3
11.7
11.9
11.4
11.6
12.4
0 2
7.3
4.8
6.8
6.0
6.6
5.6
5.4
6.5
4.9
2.7
N2
80.3
81.7
81.2
81.6
81.3
81.3
81.6
81.2
81.2
82.2
CO
.03
.03
.03
.03
.03
.03
.03
.03
1.20
1.67
Total
H.C.
80
40
206
110
160
135
75
135
175
75
NO,
65
45
50
65
48
48
72
48
30
32
NO NOX
600
650
100
1000
200
600
1220
275
150
940

-------
Continuation of Table  30






                                       ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate

No. Fe Ni
228G
228G
228A
228B 14 <2
228C
228C
228C
228C
228E
228D
Trace Metals on Millipore Filter (%)
Cu Al Ca Mg Mn Cr Sn Zn
_._
________
_______
8 10 54 14 <2 <2 <2 14
_______
---
_______
_____ ___•
_____ ___
________
% Pb
Ti Absorp
-
-
-
<2
-
-
-
-
T
-
% C on
Glass
Filter
36.7
49.8
55.6
47.3
50.8
-
-
-
46.0
46.4
ppm
BaP
21
33
120
28
68
-
-

230 £
120 °

-------
                                                   TABLE 31
                            ENGINE DYNAMOMETER TEST OF CONVERTER EQUIPPED ENGINES
Engine Type:
Fuel Used:
Converter Type:
1972 Pontiac 400 CID
Indolene #15214, Ho lead 91 octane
EGR - Off
Run
No.
229A
229D
229F
229C
229E
229E
229E
229E
229G
229B
Spark
Air to
Fuel
Range Actual
L
S
S
S
S
_
-
R
R
setting:
16.7
15.0
15.7
15.6
15.3
™
-
13.5
13.5
Adv
Ret
Test Mode
60 mph
60 mph
30 mph
60 mph
Dow Cycle 2
Dow Cycle 3
Dow Cycle 4
Dow Cycle 5
30 mph
60 mph
= Std -10°
= Std +10°
Spark
Timing
Std
Ret
Std
Std
Std
Std
Std
Std
Std
Std

Grams /Mile
Particulate Converter
T cfm Filter Temp. (°F)
.0019
.0087
.0021
.0105
-
.0208
-
.0231
.0056

Dilution
Tube
Temp. (°F)
185
200
105
195

100-230

110
225

Filter
Temp. (°F)
110-120
110-125
85-90
120-130

110-130

90-95
120-140

ppm in
Exhaust Condensate
HCHO
398'. 85
146.5
518.6
40.6

529.2

406.2
89.2

NH3
32.6
38.2
41.1
60.3

23.2

16.0
62,5

ppm 4-n
Exhaust Gas
HCHO NH3
12.8 1.8
6.4 2.9
20.8 2.9
18.9 4.9

-

-
5.1 6.3


-------
                    -118-
Continuation of Table 31
                    ANALYSIS OF EXHAUST GAS
              % by Volume
Parts per Million
Run
No.
229A
229D
229F
229C
229E
229E
229E
229E
229G
229B
co2
11.3
17.2
11.5
11.9
11.7
11.7
12.2
11.6
11.0
12.9
°2
6.3
4.8
6.3
5.0
5.8
5.1
4.5
5.8
5.2
2.5
*2
81.6
81.6
81.3
81.3
81.4
82.2
82.3
81.6
81.9
81.8
CO
.03
.53
.03
.83
.03
.03
.03
.03
1.05
1.86
Total
H.C.
75
55
120
75
130
100
95
120
200
45
N09
^
100
72
50
80
55
55
120
55
10
30
NO NO
1400
1400
950
2000
850
1100
2500
1000
650
1100

-------
Continuation of Table 31
                                       ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate
„„_ Trace Metals on Millipore Filter (%)
No. Fe Ni Cu Al Ca Mg Mn Cr Sn
229A - - - - - - ' -
229D ___-_--_-
229F _________
229C 12 <2 14 4 54 12 <2 <2 <2
229E _--__----
229E _--------
229E - - - --
229E - - --
229G ___-_--_-
229B _____----
% Pb
Zn Ti Absorp
_
- - -
_
10 <2
_ _ _
_
_
_
_
_ _ _
% C on
Glass
Filter
0.9
0.5
0.8
2.7
1.2
-
-
-
1.3
3.0
ppm
BaP
<13
<17
<17
21
39
-
-
-
48 !
<24

-------
                         -120-
    e.  The mass medium equivalent diameter was shifted
        significantly toward smaller particles, when
        compared to the baseline, for all of the devices
        tested.

3.  Discussion
The converters tested seemed to have a definite effect on
particulate in several ways.  First, as mentioned in the
conclusions, the three oxidation catalysts all showed higher
grams/mile of particulate mass at 60 mph than did the baseline,
This is shown graphically in Figure 28.  At standard air/fuel
ratio, the increase of particulate mass was significant.  As
the engine was operated richer, however, the difference became
small enough to be considered less significant, although real.

The effect at 30 mph showed a reversal of the 60 mph effect
for two of the three oxidation catalysts.  The two which show
a reduced particulate emission at 30 mph (Figure 29) are both
base metal beaded catalysts.  The EGR system,  (Converter E),
showed an increase at 30 mph, but was unchanged at 60 mph
compared to its own baseline.  It is perhaps significant that
the same engine, when modified for EGR, showed a decrease in
particulate mass compared to the previous baseline.

The particulate mass collected during the Dow cycle  (Table 2)
for the various converters showed little significant change,
although Converter A was quite high.  This data is shown
graphically in Figure 30.

The increase noted in the particulate mass when using the
oxidation catalysts was not accounted for by anything which
was routinely measured as part of this contract.

-------
                            -121-
    1200
    100.0
    0800
to
i-
CD
0)
-(->
(O

^
£

4->
s_
(O-
Q.
,0600
    0400
   ,0200
                  Lean
                                    Standard

                             Air/Fuel  Ratio
Rich

-------
                            -122-
    1200
           "T
          —4-
    1000
           j	I	i  !
           NTT
0)
to
O)
    0800
-  .0600

-------
                            -123-
    1200
    1000
cu
ri  .0800
(O
i.
 - .0600
(O
(J
S-
ra
Q.
0400
   ,0200



































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E
Baseline

-------
                                 X 2 LOG CYCLES   BADE IN U.S.A.

                                    KEUFFEL » ESSER CO.
       99.99
               99.9 99.8
                                                                                                                  0.01
 CO
 C
 o
 
 i.

 EL.
                  Figure 31

              MASS DISTRIBUTION
                 Converter A
              Std Spark, Std  A/F
                   Run  No, 140A
                                           Total  in  Particles of  Diameter 
-------
                                   PROBABILITY     46 8O43
                                   X 2 LOG CYCLES   K.OE IN u.i.A. .

                                     KEUPFEL & ESSER CO.
       99.99
                                                                                                           0.2 0.1 0.05    0.01
 to
 c
 o
 j_
 o
•r—
 £

-------
                                  PROBABILITY     46 8O43

                                  X 2 LOG CYCLES   MADE IH u.>.>. .

                                    KEUFFEL & ESSER CO.
       99.99
               99.9 99.8
                           99   98
                                     95    90
                                                 80    70   60
                                                                                                                    0.01


                                           Total  in Particles of  Diameter  
-------
                                 PROBABILITY
                                 X 2 LOG CYCLES
           46 8O43
           HADE IN U.S.A.
KEUPFEL ft ESSER CO.
       99.99
                                                                                                     0.2  0.1  0.05    0.01
 to
 c
 o
 j-
 o

O)
E
o

0)

o
S-
03
D.
                 Figure 34
              MASS  DISTRIBUTION
         Converter  A,  0.5  cc Lead  Fue"E
              Ret Spark, Std A/F
                  Run No.  145B
                                          Total  in Particles  of Diameter  
-------
                                              46 8O43
                                              MADE IN U. S. A. •
                                   KEUFFEL & ESSER CO.
PROBABILITY
X 2 LOG CYCLES
       99.99
               99.9 99.8
                          99  98
                                                                                                       0.2  0.1  0.05   0.01
to
E
O
j_
o

i
(O
•r—
O

(U

O
•r™
4J
S-

                  Figure 35
              MASS  DISTRIBUTION
         Converter A,  0.5 cc  Lead  Fuel iT^l^i
             Adv  Spark,  Std  A/F
                   Run  No.  145C

                                           Total  in Particles  of Diameter 
-------
                                PROBABILITY     46 6O43
                                X 2 LOG CYCLES   HADE IH U.S.A. .
                                  KEUFFEL ft ESSER CO.
       99.99
                                                                                                   0.2  0.1 0.05    0.01
 J_
 U
(U
E
(O
T-
o

0)

U
i.
to
CL.
                 Figure 36
              MASS DISTRIBUTION
                Converter B
             Std Spark, Std A/F
                  Run  No. 181C
                                         Total  in Particles  of  Diameter 
-------
                            PROBABILITY     46 8O43
                            X 2 LOG CYCLES   M.DI IN U.S.A. .
                               KEUPFEL a ERSER CO,
  99.99
          99.9 99.8
                                                                                                  0.2 O.I 0.05
                                                                                                             0.01
             Figure 37
         MASS DISTRIBUTION
            Converter  C
          Std Spark, Std A/F
                        186A
                                      Total  in  Particles of  Diameter  
-------
                                               46 8O43
                                               HIDE IN U.S.A. •

                                    KEUFFEL. A ESSER CO.
PROBABILITY
X 2 LOG CYCLES
       99.99
                                                                                                       0.2  0.1  0.05   0.01
 1/1
 c
 o

 o
•i"
 E
 s_
 a>
-!->
 
?—
 o
                 Figure  38

              MASS DISTRIBUTION
              Baseline Converter E
               Std  Spark,  Std  A/F
                   Run  No. 229C
                                           Total  in  Particles of  Diameter 
-------
                                  PROBABILITY     46 8O43
                                  X 2 LOG CYCLES   »DE IN u.i... .

                                    KEUFFEL & ESSER CO.
       99.99
                                                                                                         0.2 0.1 0.05    0.01
 O
 J-
 u
O
0)
4J
(V
E

-------
                         -133-
The data for Converter D, a reduction catalyst  (Table 29),
was not plotted or included in the discussions about the  other
converters, since the conditions under which this converter
could be run were so limited.  Several runs were aborted  because
the air/fuel ratios were not in a range which would allow any
reduction in NO .  The runs reported show only a minor reduction
               X
in NO , but a noticeable increase in particulate mass.  This
     X
increase was attributed in part to the rich air/fuel ratio
necessary for operation of the converter.  This device was not
run in conjunction with an oxidation catalyst.

A significant decrease in the MMED of the particulate mass col-
   ted WTS noted in the r:ase of all t' '-f-o ox:i Lit don  • ••• ta 1 y-7t •:•
and EGR.  The mass size distributions for various runs are
plotted in Figure 31-39.  Table 32 is a comparison of the dis-
tribution to the baseline runs made in Task II  (Figures 22-27).
As is shown, the percent of the particulate less than 0.55
microns and 0.97 microns increased substantially with the addition
of a catalytic device.  There was also a significant increase with
the addition of 0.5 cc lead.  It is interesting to note that Con-
verter A plus leaded fuel was higher than 0.5 lead fuel alone.

The decrease in the particulate size noted when comparing the
Converter E baseline to the original baseline is partially
explained by the fact that the intake system and carburetor
of the engine was modified to take the EGR  (Converter E).
Thus, the two baselines are not directly comparable.  The
addition of EGR to the system further decreased the overall
particulate size.

-------
                                         TABLE 32

                               MASS MEDIUM EQUIVALENT DIAMETER
                            FOR BASELINE AND CONVERTERS A, B, C,  E
Conditions:  60 mph

             Standard Spark

             Standard Air/Fuel Ratio
                     Baseline
                                          Converter
% Particle
<0055 Micron
% Particle
<0.97 Micron
No



Lead 0.5 cc Lead

45 73

A A w/0 . 5 cc Lead

88 89

B

94

C

80

E

85

E Baseline

73


i
i— '
U)
i
60
87
89
92
97   88   88
82

-------
                            -135-
D.  TASK IV

    1.  Introduction
    The objective in Task IV was to evaluate the particulate
    emission levels of various vehicles equipped with various
    control devices.  Table 33 is a description of the vehicles
    tested and the number of runs on each one.

    2.  Conclusions
        a.  The vehicles on which mileage accumulation tests
            were made exhibited a large degree of fluctuation
            with respect to grams/mile of particulate mass as
            a function of mileage.  No clear trends have been
            established.

        b.  The precision of measuring particulate mass from
            a vehicle exhaust was substantially lower than
            that of measuring an engine stand run, due to the
            variations in driving conditions prior to testing.

        c.  In general, the particulate matter which exhibited
            higher percentages of carbon also exhibited higher
            parts per million of benzo-a-pyrene.

        d.  The mass medium equivalent diameter became larger
            with mileage for two of the three mileage
            accumulation cars, while decreasing for the other.

        e.  The mass medium equivalent diameter for the device
            equipped vehicles in general correlates well with
            the numbers obtained during the engine stand runs
            even though the overall mass of the particulate
            changed.

    3.  Discussion
    The raw data for the vehicles described in Table 33 are presented
    in Tables 34-43.  The mass distribution plots corresponding to

-------
                                        TABLE 33

                            VEHICLES TESTED AND NUMBER OF RUNS
Vehicle
Series
of Runs
1970 Chevrolet 350 CID     1

1971 Chevrolet 350 CID     3

1971 Chevrolet 350 CID     3


1972 Pontiac 400 CID       4

1972 Mercedes Benz Diesel  2

1971 Oldsmobile 350 CID    1

1972 Chevrolet 400 CID     2

Mail Jeep,  Ford            1

1971 Pontiac               1

1970 Chevrolet             1
Control Device
Vehicle ID
         Base metal,  beaded    ES 60311

         Noble metal, monolith 61314
         Base metal, beaded,
           EGR

         Base metal, beaded

         None

         Not known

         Particulate trap

         Stratified charge

         Questor converter
                    61329

                    2477

                    EPA supplied

                    EPA supplied

                    PPG

                    EPA 801692

                    EPA supplied
         Thermal reactor, EGR, Dupont
           cyclone collector
Controlled Emissions

HC, CO

HC, CO

HC, CO, N0x


HC, CO
                    Particulate

                    HC, CO,  N0x

                    HC, CO,  NC)
                                        HC,  CO,  NO ,  Particulate
                                                  X

-------
                        -137-
the 60 mph steady-state runs in Tables 34-43 are presented in
Figures 40-57, and follow the appropriate table.  Data for the
vehicles as a function of mileage is plotted in Figures 58-62.

Many possible conclusions can be drawn from the large volume
of data generated on the various vehicles tested.  Several
which are thought to be significant will be discussed.

First, it does not appear that any of the mileage accumulation
vehicles showed any marked trend toward higher particulate mass
levels with time.  Car number 61329, a 1972 Chevrolet, increased
particulate mass somewhat as measured during a federal cycle hot
start, but showed sporadic mass collection rates at the 60 mph
steady-state run.  Two other cars, the 400 CID Pontiac #2477
and another 1972 Chevrolet #61314, actually decreased slightly
with time.  This data is plotted in Figures 58-62.

The Pontiac #2477 showed an actual decrease in particulate mass
collected when the control device was installed  (Figures 60 and
61).  This observation was in contrast to the reported increase
in particulate mass when oxidation catalysts were installed on
an engine stand.  An explanation of part of the effect might be
that the exhaust system of the vehicle acts as a particle trap
in the early stages.  However, the 60 mph steady-state results
for the Pontiac #2477 showed a general reduction in particulate
mass with mileage, out to about 12,000 miles, and the particulate
mass collected on the 4 cfm filter stayed essentially constant
after installation of the catalyst.

The effect of mileage accumulation on the mass medium equivalent
diameter was somewhat inconclusive, since two of the vehicles
(Car 61314 and the Pontiac) exhibited increased particulate size
with mileage, while the other (Car 61329) showed a particulate
size decrease.

-------
                                             TABLE 34
                       CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES
Car Number:
Vehicle Type:
Converter Type:
ES 60311
1970 Chevrolet 350 CID
Non-noble Metal - Pelleted
                                                                 Grams/Mile Particulate
Run
No.
68A
68B
68C
Car
Miles
80,000
80,000
80,000
Converter
Miles
50,000
50,000
50,000
Test Mode
FC CS
FC HS
60 mph
Andersen
Sampler
-
-
Millipore
Filter
-
-
-
Andersen +
Millipore
.
-
-
Glass 'Filter
1 cfm 4 cfm
.0242
.0016
.0174
                                                                                                                  u>
                                                                                                                  00
                                                                                                                   I

-------
Continuation of Table 34
                                            EXHAUST GAS ANALYSIS
                   % by Volume
Parts per Million
Run
No.
68A
68 B
68C

CO

-
12.6

°2

-
3.9

N,

-
82.4

CO
-
-
.17
Total
H.C.
-
'-
45

N02
-
-
32

NO
-
-
1450

NO

-
_
                                                                                 Exhaust Condensate  (ppm)
                                                                                     HCHO  *        NH,
                                                                                                                   VD
                                                                                                                   I

-------
                                    PROBABILITY     46 8O43
                                    X 2 LOG CYCLES   HADE IN U.S.A. .

                                      KEUFFEL a ESSER CO.
       99.99
                99.9 99.8
                             99
                                                                                                                0.2  0.1 0.05    0.01
 10
 C
 o
 s_
 o
i.

-------
                                             TABLE 35
                       CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES
Car Number:
Vehicle Type:
Converter Type;
61314
1971 Chevrolet 350 CID
Noble Metal - Monolithic
                                                                 Grams/Mile Particulate
Run
No.
69A
69B
69C
94A
9
-------
Continuation of Table 35
                                            EXHAUST GAS ANALYSIS
Run
No.
69A
69B
69C
94A
94B
189A
189B
18 9C
18 9D
* by Volume Parts per Million
Total
COj 0, N0 CO B.C. N02 NO NO^
____ ____
•____ ____
11.2 5.0 82.3 .03 4 50 1200
____ ____
____ __-_
____ ____
13.5 3.4 82.2 .03 10 8 1070
_.___ _ - __
____ - - - -
to
1
ppm in
Exhaust Condensate (ppm) Exhaust Gas
HCHO NH3 HCHO NHj
-
-
-
-
-
100 6.6
51 3.6 2.77 0.34
-
-

-------
Continuation of Table 35
                                        ANALYSIS  OF EXHAUST PARTICULATE
                                                                                             Measured in Particulate
Run
No.
69A
69B
69C
94A
94B
189A
189B
189C
189D

Fe Ni
-
-
.011 .008
—
-
6.3 <1.0
2.9 <.34
-
- -
Trace Metals on Millipore Filter (%)
Cu Al Ca Mg Mn Cr Sn Zn
_-_
_________
.006 .002 .040 .008 <.00.1 <.001 <.001. .003
_"_
_
8.8 2.3 41.0 8.5 <1.0 <1.0 <1.0 4.4
2.1 0.6 16.0 3.7 <.34 40 .34 1.6
-._
--------
% Pb
Ti Absorp
-
-
<.001
-
-
<1.0
<.34
-
- '-
% C on
Glass
Filter
-
-
-
-
-
61.4
13.2
-
—
ppm
BaP
-
-
<19
-
-
100
<15
- - 1
- it*
U)
1

-------
       99.99
 CO
 £=
 o
 s_
 (J
o»
E
(O
•r—
Q


0)
s_
(O
o.
                                    PROBABILITY     46 8O43

                                    X 2 LOG CYCLES   -ADE l« U.I... .

                                      KEUFFEL ft ESSER CO.
                                                                                                                          0.01
                   Figure  42

               MASS  DISTRIBUTION

                   Car  61314

                    Run  No. 189B
                                                                    11 ;: i   MI HI  ii! i
                                                                    H' TiTT "i TtTTiitr it I'ltn
                                                         Particles  of Diameter  
-------
Car Number:
Vehicle Type:
Converter Type:
                            TABLE 36

      CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES

61329
1971 Chevrolet 350 CID
Base Metal Beaded + EGR
                                                                 Grams/Mile Particulate
Run
No.
138A
138B
138C
139A
139B
139C
204A
204B
204C
204D
204E
205A
205B
205C
205D
205E
205F
205G
205H
231A
231B
231C
231D
231E
231D
Car
Miles
6,000
II
II
6,700
It
II
11,300
II
II
It
II
II
It
II
11
II
II
"
II
16,659
II
II
"
n
n
Converter
Miles
2,500
n
it
3,200
n
n
7,800
II
II
II
II
II
II
II
II
II
II
II
II
13,159
"
n
"
ii
n
Test Mode
FC HS
FC HS
FC HS
FC Mod.
60 mph
FC CS
FC Mod.
60 mph
FC HS
FC HS
FC HS
FC Mod.
60 mph.
FC HS
FC HS
FC HS
FC HS
FC HS
60 mph
FC Mod.
60 mph
FC Mod.
FC HS
FC HS
FC HS
Andersen
Sampler
-
-
.1434
.0108
.1533
.0826
.0067
-
-
.1130
.0073
-
-
-
-
-
.0139
.0826
.0068
.0435
-
-
—
Millipore
Filter
-
-
-
.0130
.0165
.0133
.0087
.0202
-
-
.0174
.0368
-
'
-
-
-
.0032
.1130
.0547
.0522
-
-
-
Andersen +
Millipore
-
-
.1564
.0273
.1666
..0913
.0269
-
-
.1304 .
.0441
-
-
-
-
-
.0171
.1956
.0615
.0957
-
-
-
Glass
1 cfm
.0233
.0080
.0149
.0060
.0519
.0166
.0065
.0291
.0200
.0266
.0233
.0239
.0510
.0167
.0100
.0133
.0800
.0733
.0143
.0348
.0620
.0391
.0300
.0300
.0300
Filter
4 cfm
.0070
.0080
.0130
.0087
-.0528
.0183
.0054
.0291
.0133
.0147
.0125 ,
.0097 £
.0487 <*
.0067
.0091
.0108
.0358
.0358
.0073
.0152
.0629
.0163
.0125
.0142
.0117

-------
Continuation of Table 36
                   % by Volume
EXHAUST GAS ANALYSIS
      Parts per Million
Run
No.
138A
138B
138C
139A
139B
139C
204A
204B
204C
204D
204E
205A
205B
205C
205D
205E
205F
205G
205H
231A
231B
231C
231D
231E
231F
C02 Oj

-
-
-
11.5 5.8
-
-
11.3 5.8
-
-
-
-
11.8 5.9
-
-
-
-
-
11.6 6.37

12.0 5.4
-
-
-
-
Total
N2 CO H.C. N02 NO NO^
_ _ _ _
• ._ _ _
_ _
_ _
81.8 .03 10 8 270
_ _
_
81.5 .03 5 5 150
_ _
- _
. _ _ _ _
- _
81.3 .03 3 60 1050
- _
- _
_ _
- _
_ •
81.2 .03 28 40 200

81.6 .03 5 10 240
_ _
_ _
_ _
_ _
                                                                                Exhaust Condensate (ppm)
                                                                                    HCHO         NH,
                                                                                    27.3
                                                                                    30.8
                                                                                    58.5
                                                                                    33.6
                                                                                   143.0
                                                                                    50.12
                                                                                     1.24
                                                                                    98.9
                                                                                                16.4
                                                                                                 2.8
                                                     13.9
                                                      9.73
                                                      2.4
                                                      3.26
    ppra in
  Exhaust Gas
HCHO       NTT
                                                                                                 .U
                                                                                                 -J
                                                                                                 I
                                                                   0.92
                                                                             0.87
                                                                   2.0
          0.29
7.8       1.3

0.07      0.25

-------
Continuation of Table 36
                                       ANALYSIS OF EXHAUST PARTICULATE
                                                                                             Measured in Particulate
"Run
No.
"138A
138B
138C
139A
139B
139C
204A
204B
204C
204D
204E
205A
205B
205C
205D
205E
205F
205G
205H
231A
231B
231C
231D
231E
231F
Trace Metals on Millipore Filter (%)
Fe Ni Cu Al Ca Mg Mn Cr Sn Zn
-.-
_^_
__________
2.3 <.6 2.66 1.0 24 4.0 <.3 . <.6 <.6 2.0
0.2 <.04 .2 .06 1.6 .26 <.2 <.04 <.01 <.01
3.0 <1.0 6.0 1.5 37 6.0 <.3 <.2 <.6 <.3
1.9 <.5 4.7 <.50 16 1.5 <.5 <.5 <.5 1.6
.056 <.016 .20 <.016 .46 .64 <.01 <.01 .027 .12
_•_
__________
__________
__________
__________
_._ _ __
_._
---------
__________
---------
1.2 .20 1.6 .62 9.0 1.8 <.2 .24 <.2 1.2
8 <2 10 3 64 14 <2 <2 <2 6
8 <2 8 3 94 14 <2 <2 <2 10
8 <2 11 4 64 12 <2 <2 <2 8
__________
__________
_______ — — —
% Pb % C on
Atomic Glass ppm
Ti Absorp Filter BaP
- - - -
- - - -
_ _ _ _
<.6 7.5 63.8 320
<.04 5.0 1.4 <4
<.6 <.l 80.7 <93
<.5 Nil 100 670
<.01 - <5 <5
- - - -
_

(

_
_
_
_
_
<.2 <1.3 35.8 <27
4.8 - - <120
.2 - - 57
11.1 - - <100
_
_ _ _ -
_ - - -

-------
                                                 46 8O43
                                                 HIDE m u.l.i.

                                      KEUFFEL A ESSER CO.
PROBABILITY
X 2 LOG CYCLES
       99.99
                99.9  99.8
                                                                                                             0.2  0.1  0.05
                                                                                                                         0.01
 o
 S-
 o
 a>
 E
 
-------
                                               46 8043
                                               MADE IN U.S.A. «
                                    KEUFFEL & ESSER CO.
PROBABILITY
X 2 LOG CYCLES
       99.99
               99.9 99.8
                                                                                                                    0.01
 O
 J_
 O
01
£
S-
(O
0.

                  Figure  44

              MASS DISTRIBUTION
                  Car 61329
                   Run  No.  204B

                                                                                  ji | ; I  •  ;•
                                           Total in  Particles  of  Diameter  98   99.
                                                                                                        99.8 99.9
                                                                                                                   99.99

-------
                                    PROBABILITY
                                    X 2 LOG CYCLES
            46 8043
            MADE IN U.S.A. •

KEUFFEL a ESSEB CO.
        99.99
                 99.9 99.8
                                                                                                               0.2  0.1 0.05   0.01
 to
 C
 o
 i.
 u
 s_
 a;
to

o



(J
•r—
4->
S-

Q.
                    Figure  45

               MASS  DISTRIBUTION

                    Car  61329

                     Run  No. 205B

                                              Total  in  Particles of  Diameter  
-------
                          PROBABILITY     46 8O43
                          X 2 LOG CYCLES    «.OE IK U.S.A. .

                             KEUFFEL & ESSER CO.
99.99
        99.9 99.8
                    99   98
                                                                                                            0.01
          Figure 46

       MASS DISTRIBUTION

          Car  61329

            Run  No. 231B




                                    Total  in  Particles  of Diameter  
-------
Car "Rumber:
Vehicle "Type:
Converter Type:
                                     TABLE 37

               CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES

         2477
         1972 Pontiac 400 CID
         Base Metal Beaded "C"
                                                                 Grams/Mile Particulate
Run
No.
162A
162B
162C
162D
177A
177B
177C
2 0*5 A
206B
206C
206D
205E
205F
206G
206H
226A
226B
226C
226D
226E
Car
Miles
4,325
It
"
II
6,000
n
n
10,841
n
n
it
ii
ii
it
it
15,851
II
tt
»
ii
Converter
Miles
455
n
it
n
2,130
n
n
6,971
n
n
ii
n
it
n
n
11,981
"
n
n
n
Test Mode
FC Mod.
60 mph
FC CS
FC HS
FC Mod.
60 mph
FC CS
FC Mod.
60 mph
FC HS
FC HS
FC HS
FC CS
FC HS
FC HS
FC Mod.
60 mph
FC Mod.
FC HS
FC HS
Andersen
Sampler
.1087
.0197
.1267
-
.0478
.0053
.0866
.0869
.0071
-
-
-
.1333
-
-
.0826
.0062
.0478
-
—
Millipore
Filter
.0826
.0636
.1800
-
.0652
.0373
.1266
.0869
.0515
-
-
-
.0133
-
-
.0651
.0329
.0130
-
-
Andersen +
Millipore
.1913
.0833
.3067
-
.1130
.0426
.2132
.1738
.0586
-
-
-
.1466
• -
-
.1477
.0391
.0608
-
-
Glass
1 cfm
.0196
.0504
.0200
.0040
.2282
.0360
.0200
.0239
.0385
.0233
.0266
.0333
.0500
.0333
.0300
.0413
.0257
.0456
.0499
.0466
Filter
4 cfm
.0163
.0440
'.0067
.0040
.0163
.0337
.0100
.0163
.0473 ^
.0133 £
.0133 '
.0166
.0200
.0142
.0117
.0174
.0229
.0163
.0566
.0599
121A
2,000
Car before converter or 1975
     FC Mod.         .1391
hardware was installed
     .1087        .2478
                                                                                         .0652
                                                                                          .0402

-------
Continuation of Table 37
                                            EXHAUST GAS  ANALYSIS
Run
No.
162A
162B
162C
1620
177A
177B
177C
206A
206B
206C
206D
206E
206F
206G
206H
226A
226B
226C
226D
226E
% by Volume
C02 0^ N2 CO
_
11.6 6.5 81.0 .03
_
_
-
11.9 5.4 81.8 .03
_
-
13.0 4.27 81.8 .03
'
_
_
_
_
_
'
11.3 6.4 81.4 .03
_
_
_ _ _

Total
H.C.
-
2
-
-
-
5
-
-
15
-
-
-
-
-
-
-
15
-
-
_
Parts per Million
N0_ KO NO,,
f.' — "•" A
100 1150
. -
_
_
40 1100
-
_
8 850
_
_
_
- _
- -
_
_
100 1600
_
_
_ - _
Exhaust Condensate (ppm)
HCHO NH,

-
-
-
7.0 19
3.2 8
20 3
177.8
11.5 4.41
-
-
-
26.14
-
-
36.38
115.4
77.4
-
_ _
ppm in
Exhaust Gas
HCHO NH3
-
-
-
-
-
-
-
-
0.72 0.49
-
-
-
-
-
-
-
5.8
-
-
- _
                             Car before converter or 1975 hardware was installed
121A

-------
Continuation of Table 37
                                        ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate
Run
No.
162A
162B
162C
162D
177A
177B
177C
206A
206B
206C
206D
206E
206F
206G
206H
226A
226B
226t:
226D
Trace Metals on Millipore Filter (%)
Fe
.28
.041
.22

.54
.087
.41
.28
.063
-
_
-
-
-
10
-
8
_
Ni
<.05
<.006
<.037

.073
.016
<.05
<.05
<.006
-
_
-
-
-
<2
-
<2
_
Cu
.43
.042
.24

.43
.046
.37
.23
.069
-
_
-
-
- ' '
10
-
6
_
Al
.28
.020
.28

.17
.013
.084
.085
.020
-
_
-
-
-
4
-
4
_
Ca
4.3
.44
2.9

3.1
.35
2.0
1.5
.22
-
_
-
-
-
78
-
66
_
Mg
.48
.05
.35

.71
.08
.48
.30
.05
-
_
-
-
-
15
-
14
_
Mn
<.02
<.003
<.019

<.067
<.009
<.053
<.05
<.006
-
_
-
-
-
<2.
-
<2
_
Cr
<.05
.024
.05

<-.067
.022
<.053
<.05
.016
-
_
-
-
-
<2
-
<2
_
<
<


<
<
<
<
<





<2

<2

Sn
.05
.006
.041

.067
.009
.053
.05
.006
-
_
-
-
-

-

_
Zn
<.16
<.016
.19

<.2
<.03
<.16
<.15
<.95
-
_
-
-
-
<6
-
<6
_
% Pb % C on
Atomic Glass
Ti Absorp Filter
<.05 2.5 23.2
<.006 12.5 1.2
<.031 10.0 .5

<.06 <2.5
<.004 5.0
<.053 2.5
<.05 Nil 13.6
<.006 <.2 1.4
_ _ -
_ _ _
_ _
- ' - . ~
_
<2 - -
- - -
<2
_ _ —
ppra
BaP
100
<4
<93

<83
<5
<93
180
6
-
_
-
-
—
130
11
<43
_










1
cn
Ul
1






121A
.32
<.08
.24
Car before converter or 1975 hardware was installed
.08     2.76    .40      .04    .04     .08     .08
.24
.56   61.2

-------
                                       46 8O43
                                       M*0r IN U.3.A. •
                            KEUFFEL & ESSER CO.
PROBABILITY
X 2 LOG CYCLES
99.99
        99.9 99.8
                   99
                                                                                                          0.01
           Figure 47
       MASS  DISTRIBUTION
           Car  2477
            Run  No.   162B
                                   Total  in  Particles  of Diameter  
-------
                                  PROBABILITY
                                  X 2 LOG CYCLES
           46 8043
           MADE IN U. S. A. •
KEUFFEL ft tSSER CO.
       99.99
                                                                                                        0.2  0.1  0.05
                                                                                                                   0.01
 to
 £
 O
 J_
 U
O
i-
(U
O)
a

O)
S-
rd
a.
                 Figure  48
              MASS DISTRIBUTION
                 Car  2477
                   Run  No.  177B
                                           Total in  Particles  of Diameter  
-------
                                   i-r BO43
                                   X 2 LOG CYCLES    «AOE rn U.S.A. .
                                      KEUFFEL A ESSER CO.
       99.99
                99.9 99.8
                            99
                                                                                                      1    0.5   0.2  0.1  0.05    0.01
 O
 S_
 
o>
E
Q

0)

u
                  Figure  49
               MASS DISTRIBUTION
                  Car 2477
                    Run  No.   206B
                                                                                                       irir.i-t
                                              Total  in  Particles  of  Diameter  
-------
                                    PROBABILITY      46 SO43
                                    X 2 LOG CYCLES    MADE IN U.S.A. .

                                      KEUFFEL ft ESSER CO.
       99.99
                99.9 99.8
                                                                                                                          0.01
 C
 o
 i.
 u
 
 O)
 E
O



S-


a.
                   Figure  50

               MASS  DISTRIBUTION
                   Car  2477

                    Run No. 226B
                                           %  Total in Particles  of Diameter  
-------
                                             TABLE 38
                       CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES
Car Number:
Vehicle Type:
Converter Type:
Environmental Protection Agency
1972 Mercedes Benz Diesel (220)
None
                                                                . Grams/Mile Particulate
Run Car
No. Miles
K53A 3,171
2.17A 6,250
217B
217C
21 7D "
Converter
Miles Test Mode
FC
FC
FC
FC
60
Mod.
Mod.
IIS
HS
mph
Andersen
Sampler
.1735
.2739
.2333
.2333
.0390
Millipore
Filter
.4657
2.7696
2.3333
2.3066
.4784
Andersen +
Millipore
p
3.
2.
2.
0
6392
0435
5666
539
5174
Glass Filter
1 cfm
.7715
.6261
.5833
.5633
.2536
4 cfm
.6642
.5371
.4849 '
.4599
.20217
                                                                                                                   a\
                                                                                                                   o
                                                                                                                   I

-------
Continuation of Table 38






                                            EXHAUST GAS ANALYSIS
Run Total
No. CO., 0., Nn CO B.C. NO0 NO NO,,
163A
217A
„. _ No gaseous analyses
^X / a
217C
217D
Exhaust Condensate (ppm)
HCHO
66
71.5
50.9
-
19.9
NH-,

9.2
4.24
-
5.25
Exhaust Gas
HCHO NH3
-
- -
-
-
0.78 0.36

-------
Continuation of Table 38




                                        ANALYSIS OF EXHAUST PARTICIPATE
                                                                                              Measured in Particulate
Run
No.
163A
217A
217B
217C
217D
Trace Metals on Millipore Filter (%)
Fe
.059
.03
.04
.007
_
Ni
.01
-
-
-
_
Cu
.067
.007
.003
.002
_
Al
.038
.05
.03
.005
_
Ca
.74
-
-
-
_
M£
.087
.02
.01
.002
_
Mn
.005
-
-
-
_
Cr
.012
-
-
-
_
Sn Zn
.01 .07
-
-
-
_ _
% Pb
Ti Absorp
.01 .1
.06
.05
.09
_ —
% C on
Glass
Filter
80.0
75.0
80.5
83.3
_
ppm
BaP
<3
24
5
-
4
                                                                                                                   to
                                                                                                                    I

-------
                                    PROBABILITY      46 SO43
                                    X 2 LOG CYCLES   »DE IN U.S.A.

                                      KEUFFEL & ESSER CO.
       99.99
                                                                                                          0.5   0.2  0.1  0.05    0.01
 CO
 C
 o
 s_
 u
 £-
 0)
•p
 (U
 E
 (O
O)

o
•r—
+J
S-
«
Q.
                   Figure  51

               MASS  DISTRIBUTION
               Merc  Benz  Diesel
                    Run No.  217D
                                                                                                                   :.ri'L i "tZTI—
                                              Total  in  Particles  of  Diameter  
-------
                                             TABLE 39
                       CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES
Car Number:
Vehicle Type:
Converter Type:
         Environmental  Protection Agency
         1971 Oldsmobile DRX  401 -  350  CID
         Not known
Run
No.
178A
4,285
Converter
  Miles
  2,200
Test Mode
FC Mod.
Andersen
Sampler
 .0261
                                                                 Grams/Mile Particulate
Millipore
 Filter
  .0087
Andersen +
Millipore
  .0348
                                                                                 Glass Filter
1 cfm
.0087
4 cfm
.0098
!
M
*»
Additional Notes
1)  This car did not start well, looking at the choke it did not appear to be closing completely.   We
    were told by Phillips that this is the way it was designed to work.
2)  The filter papers with the particulate collected on it were very light in color.  Not  at all like
    the 1971 Chevrolet, Federal Cycle cold start runs with choke on.
3)  The dilution tube sweeping  (particulate) did not resemble the usual type of material we  have observed
    in the past.  There was a sparkle to the particulate and the density was apparently very low.
4)  All samples of particulate were given to the E.P.A. for analysis at Ann Arbor.

-------
Continuation of Table 39
                                            EXHAUST GAS ANALYSIS
Run
Mo.
178A
co2
                   % by Volume
°2
Total
H.C.
                                        Parts per Million
NO,      NO      NO
"" 
-------
Continuation of Table 40
                                            EXHAUST GAS ANALYSIS
Run
No.
203A
203B
203C
203D
203E
203F
203G
211A
211B
co2
11.7
-
-
-
-
-
-
12.0
°2
5.2
-
-
-
-
-
-
5.6
^2
81.8
-
-
-
-
-
-
81.4
CO
_
.03
-
-
_
_
-
-
.03
Total
H.C.
_
52
_
_
_
_
-
_
66
NO.,
40
-
_
_
-
-
_
40
NO NOX
-
1650
-
-
-
-
- .
-
1450
Exhaust Condensate (ppm)
HCHO NH3
474.8
266.3 19.6
-
-
328.0
-
-
363 9.26
600 21.24
ppm
Exhaust
HCHO
-
15.7
_
_
-
_
-
-
14.59
in
Gas
NH,

2.0
-
-
-
-
-
-
0.9

-------
                                        '     TABLE 40

                       CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES
Car Number:

Vehicle Type:

Converter Type:
             Environmental  Protection  Agency  Lease 4065

             1972  Chevrolet 400  CID

             PPG Trap Mufflers,  etc0
                                                                 Grams/Mile Particulate
Run
No.
203A
203B
203C
203D •
203E
203F
203G
211A
211B
Car
Miles
14,566
II
II
II
II
II
II
16,000
n
Converter
Miles Test Mode
14,566 FC
60
i. FC
FC
ii FC
n pc
FC
16,000 FC
60
Mod.
mph
HS
HS
Mod.
HS
HS
Mod.
mph
Andersen
Sampler
.0520
.0150
-
-
.0782
.
-
.1043
.0134
Millipore
Filter
.0650
.1880
-
-
.2217
-
-
.0174
.0907
Andersen +
Millipore
.1170
.2030
-
-
.2999
-
-
.1217
.1041
Glass Filter
1 cfm
.0625
.2124
.0666
. .0733
.0978
.0800
.0667
.1054
.0933
4 cfm
.0550
.1791
.0517
.0500
.0586
.0516
.0483
.0619
.0826
I
a\
I







Additional Notes
 1)
Water condensate which dripped out of the tail pipe connection during the test contained an orange-
yellow colored solid material.  An analysis of this material was conducted.
    Phosphorus =  <.8 ppm
    Sulfur     =   .016%
    Zn         =   .02%
                                    Fe = .23%
                                    Pb = .25%
                                    Br = .20%
 2)   Run 211B -  60 mph  steady-state was interrupted by two blown tires during  the  run.
     run was conducted  with a 30-minute time  interruption'to change tires.
                                                                                   A full two-hour

-------
Continuation of Table  40
                                       ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate
Run
No.
203A
203B
203C
203D
203E
203F
203G
211A
211B
Trace Metals on Millipore Filter (%)
Fe Ni
1.2 <.067
.004 <.002
-
- -
o32 <.02
-
-
-
_ _
Cu
.43
.007
-
-
.29
-
-
-
_
Al Ca Mg
.13 2.7 .65
<.002 .016 <.006
_
_
<.02 160 .10
_
_
-
_ _ -,
Mn
<.067
<.002
-
-
<.02
-
-
-
-
Cr
.13
<.002
-
-
<.02
-
-
-
-
Sn
<.067
<.002
-
- '
<.02
-
-
-
-
Zn
.24
.027
-
-
.18
-
-
-
-
Ti
<.067
<.002
-
-
<.02
-
-
-
-
% Pb % C on
Atomic Glass ppm
Absorp Filter BaP
39 33.9 180
20.2 36.6 <1
_ _
_
29.8 20.2 <24
_ _ -
_ _ -
1
I—


-------
                                               46 SO43
                                               MADE IN U.S.A. •
                                    KEUFFEL & ESSER CO.
                                  PROBABILITY
                                  X 2 LOG CYCLES
       99.99
                                                                                                1   0.5   0.2  0.1  0.05   0.01
 c
 o
 i.
 u
t-
O)

O)


-------
                                  PROBABILITY     46 8O43

                                  X 2 LOG CYCLES   NAD[ IN u i.».

                                    KEUFFEL ft ESSER CO.
       99.99
                                                                                                         0.2 0.1 0.05    0.01
o
s_
u
i.

-------
                                             TABLE 41

                       CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES
Car Number:

Vehicle Type:
Converter Type:
Environmental Protection Agency 801692
Mail Jeep Body
Stratified Charge Engine
                                                                 Grams/Mile Particulate
Run
No.
219A
219B
219C
219D
Car
Miles
4,262
II
II
II
Converter
Miles
4,262
n
it
n
Test Mode
FC
FC
FC
60
Mod.
HS
HS
mph
Andersen
Sampler
.1043
.0999
.1066
.0091
Millipore
Filter
.0217
.0199
.0267
.0756
Andersen +
Millipore
.1260
.1198
.1332
.0847
Glass
1 cfm
.0283
.0500
.0666
.1046
Filter
4 cfm
.0358
.0533
.0516
.0942
Additional Notes

1)  There was some question as to whether the engine was running right.  It appeared to have a spark
    plug miss.

2)  Dilution tube sweepings at the end of this series of runs I219A, B, C & D was 45.8 grams which  is
    a gross amount compared to other vehicle tests.  The sweepings were almost all magnetic indicating
    iron from the exhaust system.  We were told this vehicle had not been run for a prolonged period
    which could account for the tube sweepings.

3)  The test vehicle would not obtain 60 mph on the dynamometer so the test was conducted at 50 mph.

4)  At 50 mph steady-state operation on the dynamometer there did not appear to be a miss in the engine.

-------
Continuation of Table 41
EXHAUST GAS ANALYSIS
% by Volume Parts per Million
Run
No.
219A
219B
219C
219D
Total
CO, 0, N, CO H.C.

- - - -
_
11.8 5.8 81.5 .02 10
Exhaust Condensate (ppm)
NO, NO NO

-
_
7.0 230
HCHO
33.7
10.0
-
10.3
NH.j
5.4
2.9
_
3.3
-J
to
1
ppm in
Exhaust Gas
HCHO NH,

-
-
0.6 0.35

-------
Continuation of Table 41
                                        ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate


No.
219A
219B
219C
219D
Trace Metals on Millipore Filter (%)

Fe
2
5
4
.03
Tube 40
Sweepings


Ni
.09
.13
.006
.007
802


Cu
.9
.8
.06
.03
.03


Al
.4
1.5
.09
.009
.04


Ca Mg
1 10
16 16
12 .6
= 3 .2
o005 .004


Mn
.2
.3
.03
.006
.2


Cr
.3
.3
.03
.006
.001


Sn Zn
.10
.15
.006
.01
« w


Ti
.02
.10
.009
.003
.005

% Pb % C on
Atomic Glass ppm
Absorp Filter BaP
61.
109.
-
23.
•» _

0 <31
0 <10
<31
2 3.2
_

                                                                                                                   00
                                                                                                                   1

-------
                                              46 8O43
                                              MADF IN U.S.A. •

                                   KEUFFEL ft ESSER CO.
PROBABILITY
X 2 LOG CYCLES
                                                                                                                 0.01
 C
 o
 j-
 o
(V
-IJ
(V
E
to
O)
•4J
S-
rd
a.

                 Figure 54

              MASS  DISTRIBUTION

              Stratified  Charge

                   Run No.  219D
                                          Total  in  Particles of  Diameter  i * i i i i i i i •	LJ—• : i i •  •[•••ii	••	L_J
                                                20   30   40   50  60   70    SO
       oni
                                                                                          98   99
                                                                                                     99.8 99.9
                                                                                                                99.99

-------
                                             TABLE 42

                       CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES
Car Number:

Vehicle Type:

Converter Type;
Environmental Protection Agency

1971 Pontiac

Questor Converter System
                                                                 Grams/Mile Particulate
Run
No.
221A
221B
221C
221D
Car
Miles
8,000
"
"
n
Converter
Miles
8,000
"
"
"
Test Mode
FC
FC
FC
60
Mod
HS
HS
mph
Andersen
Sampler
(Tail pipe
.1399
.1333
.0083
Millipore
Filter
disconnect
.0133
.0266
.0104
Andersen +
Millipore
failure)
.1532
.1599
.0187
Glass
1 cfm

.1600
.1533
.0292
Filter
4 cfm

.0883
.1049
.0175
                                                                                                                    01
Additional Notes
This car was driven on the dynamometer by the driver that delivered the vehicle.  The choke on this
vehicle.  The choke on this vehicle was so adjusted so that it would not close completely and fuel was
introduced at the carburetor to start it.  No cold starts were conducted for this vehicle.  Just  hot
starts and 60 mph steady-state.

-------
Continuation of Table 42
                                            EXHAUST GAS ANALYSIS
Run
No.
          CO..
221A       -

221B       -
221C       -

221D     10.7
                   % by Volume
0_2
7.7
80.6
                                  .03
                        Parts  per Million
                 Total
         CO      H.C.
10
135
                                                             NO
1760
                            Exhaust Condensate  (ppm)
                                HCHO         NH,
                                                                                     2.1
                                                                                       .13
                                                                       97.7
                                                                        4.7
                                                                        ppm in
                                                                      Exhaust Gas
                                                                    HCHO       NH
                                                                                              .007
                                                                                                                            0.4

-------
Continuation of Table 42
                                        ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured  in  Particulate
Run
No.
221A
221B
221C
221D

Fe
8
-
3
.6

Ni
-
.15
.09

Cu
3.3
-
1.4
.52
Trace Metals
Al Ca
1.3 <25
-
1.0 <12
.32 <2
on Millipore Filter
M£ Mn
>3 >.5
-
>12 >.2
>2 >.04
(%)
Cr
-
.3
.2

Sn
.10
-
.08
.06

Zn Ti
.13'
-
.05
.02
% Pb
Atomic
Absorp
-
-
-
% C on
Glass
Filter
-
-
5.1
4.5
ppm
BaP
<5
-
-
<7
Tube     25
Sweepings
15
»09    .2
o07
.02   .5
.5
,09

-------
                                     PROBABILITY     46 8O43
                                     X 2 LOG CYCLES   .HOE in B.I... .

                                       KEUFFEL & ESSER CO.
        99.99
                 99.9 99.8
                             99   98
                                        95     90
                                                     80    70   60   50
    9-

    8-

    7_.


    6..


    5-



    4	
 in
 c.
 o
 i.
 u
i-
0>
+J
(U
e
(O
0>

u
•r—
•4->
S-

-------
                                             TABLE 43
                       CHASSIS DYNAMOMETER TEST OF CONVERTER EQUIPPED VEHICLES
Car Number:
Vehicle Type:
Converter Type:
DuPont
1970 Chevrolet
Thermal Reactor + EGR
Cyclone Collectors
                                                                 Grams/Mile Particulate
Run
No.
222A
222B
222C
222D
222E
222F
222G
222H
2221
Car
Miles
11,376
II
II
II
II
It
II
II
II
Converter
Miles
2,000
it
it
n
it
ii
it
it
»
Test Mode
FC Mod.
FC HS
FC HS
FC Mod.
60 mph
60 mph
FC Mod.
FC HS
FC HS
Andersen
Sampler
.1565
.0733
.0533
.0695
.0147
.0077
.1043
.1666
.1399
Millipore
Filter
.0869
.1200
.1133
.0608
.0178
.0080
.2434
.1599
.1799
Andersen +
Millipore
.2434
.1932
.1666
.1303
.0325
.0157
.3477
.3265
.3198
Glass
1 cfm
.0804
.0466
.0499
• .0826
.0243
.0191
.1674
.0799
.1399
Filter
4 cfm
.0619
.0283
.0333
.0652
.0199
.0155
.1283
.0449
.1183
1
M
•>J
ID
1







Additional Notes:  See attached.

-------
                         -ISO-
Additional Notes

Two different brands of  fuel were used  to make  the  series
of runs.

 (1)  Run  #222 A, B, C, D, E were made on the  fuel the  vehicle
     had  in it when it was delivered.   Supposed to  be  Sunoco #240,

 (2)  Run  #222 F, G, H, I were made on Bay gasoline.
                   GASOLINE ANALYSIS
                                   Bay Gas      Sunoco  #240
RVP
Gravity
I.B.P.
5% distillation
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
E.P.
RON
MON

Pb grams/gallon
Br grams/gallon
10.5
57.4
100.
121.
148.
175.
192.
221.
238.
260.
280.
320.
370.
390.
415.
95.4
84.8
3.30
1.27
7.3
59.1
96.
115.
125.
148.
171.
196.
219.
240.
264.
301.
351.
400.
410.
98.3
87.0
2.34
.91

-------
Continuation of Table 43
                                            EXHAUST GAS ANALYSIS
                   % by Volume
Parts per Million
Run
No.
222A
222B
222C
222D
222E
222F
222G
222H
2221
C02 °2

_
. _
. -
13.1 3.7
13.5 3.1
-
-
_ ' _
Nj CO
-
• -
-
-
82.3 .03
82.5 .03
-
-
_ _
Total
H.C.
-
-
-
-
1
0
-
-
_
NO,
— £
-
-
-
24
7.5
-
-
_
NO
-
-
-
-
545
462
-
-
_
NO
-
-
-
-
-
-
-
-
_

LUSt

Condensate
HCHO NH
9.6
1.8
5.3
.5
1.1
1.2
15.
1.
"
.
,
8.

(ppm)
3
6
85
87
85
87
6
ppm in
Exhaust Gas
HCHO NH,
-
— —
_ —
0.02 0.05
0.07 0.09
- -
1
I-1
CO
i





                                                                                                  4.9

-------
Continuation of Table 43
                                       ANALYSIS OF EXHAUST PARTICULATE
                                                                                              Measured in Particulate
Run
No.
222A
222B
222C
222D
222E
222F
222G

222H
2221
Trace Metals on

Fe
.7
.6
-
-
.5
.6
2

.4
-.

Ni
.03
.03
-
-
.03
.03
.15

.01
-

Cu
.4
.3
-
-
.7
.6
1.8

.1
-

Al
.5
.4
-
-
.3
.4
1.3

.2
-

Ca
3
3
-
-
1
2
9

2
-
Millipore Filter (%)

Mg
3
3
-
-
1
2
5

1
-

Mn
.05
.06
-
-
.02
.04
.2

.04
-

Cr
.1
.1
-
-
.1
.08
.3

.05
-

Sn
.02
.003
-
'
.01
.02
.19

.002
-

Zn Ti
.009
.008
-
-
.01
.008
.02

.004
-
% Pb
Atomic
Absorp
29.0
13
-
-
44
30
37

13
-
% C on
Glass
Filter
20.6
10.6
-
-
1.7
3.1
24.5

18.8
-
.ppm
BaP
53
120
-
-
<8
100
41 .
1
_ I-1
00
to

-------
                                   PROBABILITY      46 8O43

                                   X 2 LOG CYCLES    «»OE 
-------
                                                       46 8O43
                                                       «.ot IN u.j.». .
                                          KEUFFEL & ESSER CO.
PROBABILITY
X 2 LOG CYCLES
        99.99
                  99.9  99.8
                                                                                                                          0.2  0.1  0.05     0.01
 O
 J-
 O
 
 
-------
                           -185-
    ,0800
    0700
    0600
    0500
to
S-
O)
4J
IO
r—
3
O
i.
0}
CL.
0400
    0300
    0200
   ,0100
                                                             Federal:
                                                             Cycle!-;
                                                            Tot
                 2500      5000      7500       10,000     12,500     15,000
                               Mileage, Converter
         Car 61329, Basemetal, EGR - 142 mm  filter,  4  cfm

-------
                            -186-
OJ
to
S-
C3
O)
(O
r—
O
ro
0.
    ;0700
     0600
    ,0500
     0400
,0300
     0200
     0100
          J.

             T'
                _..
                -t
                              _LJ

                 T \
                            x
                  i    i
                  2500
                                         f.


                                              ]
                                      !  !
                                      -f—i-

                                                         i  !
                                                     -jn mxh.
                                                                  r
                                                               F    rr
                        5000       7500.      10,000    12,500   15,000
                              Miles,  Converter
          Car  61329,  Basemetal,  EGR - 142 mm filter, 4 cfm

-------
                           -187-
    0800
   ,0700
   ,0600
CD
.7  .050.0
in
e

-------
                           •-188-
    0700
   ,0600
Ol
•-  .0500
O)
•)-)
tO
3
(J
0400
Q-  .0300
   0200
   0100
                 2500
                        5000      7500      10,000

                             Miles ,  Converter
12,000   15,00(
         Pontiac, Basemetal  -  142  mm filter, 4 cfm

-------
                          -189-
    008
    0700
    0600
Ol
(O
S-
C3
d)
4->
10
S-
(O
CL
    0500
0400
    0300
   ,0200
    0100
       5000     10,000    15,000     20,000     25,000    30,000    35,000
                                Car  Miles
        Car 61314, Noble Metal -  142  mm  filter,  4 cfm

-------
                            -190-
E.  TASK V
    Task V involved a preliminary look at some of the factors
    affecting the particulate mass sampling from a small, one-
    cylinder diesel engine.   Table 44 is a summary of the speci-
    fications of the Labeco  diesel used in the study.  Figure 63
    is a diagram of the dilution tube apparatus used for collecting
    the particulate.

    The tube was designed to give 400 fpm flow rate of air and
    exhaust.  This was roughly equivalent to what was used on
    the gasoline engine studies.

    The first runs were made with the exhaust from the diesel
    entering the dilution tube at an orifice in the tube, hoping
    that the turbulence set  up by the orifice would allow complete
    mixing.   This proved to  be unsatisfactory because of the large
    degree of the exhaust pulsation occurring with the one cylinder
    engine.

    The pulsation effect was greatly reduced by introducing the
    exhaust into the dilution air stream counter to the air flow.
    The pulses were still strong enough, however, to necessitate
    the placement of the exhaust inlet at least 5 feet from the
    filter at the air inlet.

    Only a few runs were made before the lack of time and funds
    forced us to stop.   Several preliminary conclusions can be
    drawn:

        1.  The mass collected on the filter media, both
            millipore and glass fiber, was high enough to
            allow detailed analytical work on the particu-
            late.

        2.  A single cylinder engine such as the one used in
            this work can be a valuable tool for diesel
            studies.

-------
                          -191-
     3.  The size of the particles collected appears  to  be
         quite small, based on the figures  in Table 45 showing
         the amount collected on the Andersen plates  vs.  the
         amount collected on the back-up Millipore filter.

                        TABLE 44
            LABECO DI DIESEL, UNSUPERCHARGED

 Bore:              3.80 in.
 Stroke:            3.75 in.
 Displacement:      42.53 cu. in.
 Weight:            418 Ibs
 Compression Ratio: 16.7:1

 Brake Torque at 1600 rpm                26.7
 Brake Horsepower at 2800 rpm            11.8
 BMEP at 1600 rpm                        94
 FMEP at 2800 rpm                        56
 FMEP at 2000 rpm                        44
 IMEP at 1600 rpm                       136
 ISFC at 1200 rpm                           .365
 BSFC at 1200 rpm                  .         .511
                        TABLE 45
        GRAMS/HOUR COLLECTED FROM A ONE CYLINDER
                   LABECO DIESEL ENGINE
        (1500 rpm, 900 grams/hr fuel consumption)
                            Grams/Hour
                           Millipore   Andersen +   Fiberglass
Run No.
214A
214B
Time
20 min
60 min
Andersen
.0198
.0036
Filter
.0894
.1494
Millipore
,1092
.1530
Filter
.1221
.1378
Dilution tube flow rate was 400 ft/min, or 65 cubic feet
per minuteo

-------
FtOW -
CONTROL
                                 FIGURE 63 - DIESEL DILUTION  TUBE AND SAMPLING
                                                          SET-UP           ' ;

-------
                      -193-
                    APPENDIX A

   AN INVESTIGATION OF SOME VARIABLES OBSERVED
WHEN SAMPLING PARTICULATE MATTER FROM AIR DILUTED
               AUTOMOTIVE EXHAUST
         Otto J.  Manary   0. C. Valenta

                      and

               Michael J. Baldwin
            The Dow Chemical  Company
               Midland, Michigan
                  October 1971

-------
                         -194-
                       SUMMARY
Both the quantity and quality of particulate matter* collected
from air diluted automotive exhaust are affected by such variables
as sampling temperature, dilution ratio, flow rate and by the
presence of gasoline additives.  An investigation of the effect
of these variables is presented in this report.
*Particluate matter is defined to be that nongaseous matter
 collected at filters under the sampling and operating conditions
 specified for each separate run described herein.

-------
                        -195-
                   INTRODUCTION
 In 1969 a study of the participate emissions present in the
 exhaust effluent of automobile engines v/as initiated under a
 government contract at Dow.  The problem at hand was to
 evaluate the effect of gasoline additives on the nature of
 such emissions.  This necessitated the development of a
 reliable particulate sampling procedure.  This procedure,
 described in a previous report1 was found in duplicate tests
 to afford samples of particulate matter repeatable to within
 ±10% on a weight basis.

 During the first year of the above program particulate samples
 were collected from the exhaust system of an internal combustion
 engine operating under controlled conditions on a dynamometer.
 The left bank of cylinders of a V8 engine was discharged via a
 convectional automobile exhaust system into a 27' x 18" poly-
 vinyl chloride dilution tube where the exhaust effluent was
 diluted tenfold with filtered air.  This condition permitted
 isothermal, isokinetic sampling of particulate matter at the
 end of the tube remote from the engine (See reference 1).

 During the second year of the research program the results
 obtained in the above engine studies were related to those
 obtained for vehicles operating on a chassis dynamometer.
 Physical restrictions necessitated that changes be made in
 the particulate sampling procedure.  A six hour sampling
 period was found to be the most practical  as compared to a
 48 hour period in the previous engine dynamometer studies.
 This reduction in sampling time would be expected to yield
 an eightfold reduction in weight of particulate matter collected
 However during the chassis dynamometer studies the total  vehicle
 exhaust was discharged to the dilution tube.  An appropriate
 change in the air dilution ratio was made to afford the same
 overall flow rate within the dilution tube.  Thus during the
 six hour sampling period and under otherwise identical  sampling
 conditions it was expected that one fourth of the weight of
 particulate matter collected in the engine dyno runs would be
 collected during the chassis dynamometer tests.

This smaller weight of particulate matter proved inadequate
 for comprehensive analysis.  It was therefore decided to
 supplement the Andersen sampler and filter combination
operated at 1  cfm and used exclusively to this point of the
 program with an additional  separate 142 mm filter operated
at 4 cfm.   One might expect the 4 cfm filter to collect
four times the quantity of particulate matter collected at
 the 1  cfm Andersen and filter combination.   In fact the
      Government  Report  #  CPA-22-45-145)

-------
                         -196-
4 cfm filter collected from 20 to
matter than the ideal.
       70% less participate
In viev/ of the trend to nonleaded gasolines and the necessity
for sampling participate matter in the relatively short cycling
sequences of the LA-4 and new Federal test procedures it was
felt to be .imperative that this anomaly be resolved and that
the particulate sampling procedure be refined to afford meaning
ful and reproducible results under the above conditions.
                    APPARATUS
1.  Chassis Dynamometer
2.  Engine Dynamometer
3.  Andersen Sampler
4.  Filter Holder
    a.  Glass fiber filter
    b.  Millipore membrane
5.  Analytical  balance
6.  Electrical  heated oven
7.  Particulate collection
     CLAYTON
     DYNAMATIC

     GELMAN
     GELMAN
filter
system (See Figure I
                     PROCEDURE
Details of the operating and sampling procedures are presented
in Reference 1.   All  engines and vehicles were operated at the
equivalent of 60 mph  road load conditions.

1.  Handling and Weighing of Filter Papers

    The normal procedure for handling and weighing of filter
    paper was as fol1ows:

    a.   The paper was  stored in an air conditioned room at
        75°F and weighed prior to use.
        After sample collection the paper was weighed within
        minutes of removal  from the filter holder and
        when the weight had stabilized on the balance
        which was in the same air conditioned room at
                           again
                           pan
                           75°F.
        An experiment was  conducted to evaluate the effect of
        heating on the weight of glass fiber filter pads.   The
        results are presented in Figure §2.   Since no weight
        loss  occurred between the temperatures of 75°F and

-------
                        -197-
        100°F it was felt that the error in handling filter
        papers in the above manner was negligible.

2.  Milli pore ve r s u s Gel man F i1t e r Papers

    In most of the work a glass  fiber filter was used.   However
    in some incidents a membrane type filter was used to obtain
    particulate on a soluble substrate which could  be used in
    various analytical  procedures.  It is important that both
    filter papers be equally efficient in particulate collection
    (Figure #3).

    The data shows only a small  difference in the efficiency of
    the two filters opera-ting at 1 cfm flow rate.  The  difference
    could be a function of the fuel  additive.  The  data presented
    includes no lead fuel and leaded fuel for comparison.

3.  Exhaust Gas Velocity Through Filter Paper - 1 cfm vs.  4 cfm

    If one compares a 1 cfm filter to a 4 cfm filter, the  temperature
    of the exhaust gas  in the 4  cfm filter is higher due to the
    shorter time it had in the sample line between  the  dilution
    tube and the filter.   Consequently in order to  compare the
    direct effect of flow rate on particulate collection the
    sample line leading to the 1 cfm filter had to  be heated to
    maintain the same temperature as the 4 cfm filter.

    As can be seen from Figure #4 there was a considerable loss
    in filter efficiency as the  face velocity of the gas stream
    through the filter  is increased.  The exhaust particulate
    from leaded gasoline were less sensitive to filter  flow rate
    than those from nonleaded fuel.   This is probably due  to a
    much higher level of volatile organics associated with non-
    leaded gasoline exhaust particulate.

4.  Exhaust Gas Temperature at Filter

    It is not surprising  that the temperature of the filter would
    have a pronounced effect on  the amount of particulate  matter
    collected on the filter (See Figure #5).  Again the use of
    nonleaded gasoline  has a greater effect on the  percent of
    particulate retained  as the  filter temperature  is increased.
    As was also expected  the mild cycling conditions show  the
    greatest percent change due  to the lower boiling materials
    one would expect in the exhaust gas.

-------
                       -198-
5.  Leaded Fuel Versus Nonleaded Fuel

    The percent of lead in the gasoline had a definite effect
    on the difference in the participate pick-up on the 1  cfm
    filter plus Andersen sampler versus the 4 cfrn filter
    only (See Figure #6).

    A tabulation of the runs that were made at 60 mph road
    load steady state operation shov/ that the particulate
    matter collected from  leaded gasoline exhaust is the
    least sensitive to changes in sampling procedure.

    It is felt that the increasing differences observed with
    the reduction of lead  in the fuel are due to the increased
    level of volatile organics associated with the particulate
    matter resulting from  the combustion of nonleaded fuel.
    The face velocity on the filter and the higher operating
    temperature of the 4 cfm filter would have a greater
    tendency to remove the more volatile compounds.

6.  1  cfm Filter Plus Andersen Sampler Versus 1  cfm Filter
    Without Andersen Sampler

    A comparison was also  made between the efficiency of the
    1  cfm filter alone and the 1  cfm filter used in conjunction
    with an Andersen sampler.  With leaded gasoline the difference
    in efficiency varies from 2.8 to 13.9% (See  Figure £7).  Using
    nonleaded gasoline the efficiency of the two systems varies
    from 39.5 to 82.4%.   Of particular significance is the fact
    that the Andersen sampler collects 70 to 80% of the particulate
    matter compared to the 1  cfm filter when using ncnleaded fuel.
    However when leaded fuel  is used the Andersen sampler  accounts
    for only 35 to 40% of  the particulate matter collected.   It
    is felt that the difference in collection efficiency between
    nonleaded fuel and leaded fuel  is again due  to the high  ratio
    of volatile organics present in the particulate matter from
    the nonleaded gasoline.   The magnitude of the thermal  drop
    across an Andersen sampler is similar to that of a filter so
    one would expect to collect more particulate on the combined
    .1  cfm filter/Andersen  system.

7.  Thermal  Profile of Sampling System

    The data tabulated in  Figure #8 shows the average thermal
    drop across a 1 cfm filter to be 36.4°F and  that across  a
    4  cfm filter to be 12.7°F.   The temperature  drop across
    the Andersen sampler was  found  to be 17.4°F  and  that across
    the combined Andersen  and 1 cfm filter to be 53.8°F.

-------
                       -199-
8.  Unbound Mater In Two Types of Filter Media Before and
    After Partlculate Col 1ection

    In order to assess the possible effect of unbound v/ater
    on the weights of particulate matter collected a glass
    fiber and millipore filters, both types of filter pads
    were desiccated both prior to and after sample collection
    The data is tabulated in Figure #9.

    It was found that the glass fiber filter has a very low
    water retention this was the main filter used for the
    particulate collection studies to date.  The membrane
    filter was very susceptible to water pick-up and must be
    used with caution.

                    CONCLUSIONS
1.  The temperature of the diluted exhaust gas has a significant
    effect on the quantity of particulate matter collected in
    the sampling system described in this report.

2.  The flow rate of the exhaust gas being sampled through a
    filter .paper was found to have a definite effect on the
    amount of particulate collected on the filter  paper.

3.  Fuel additives such as TEL have an effect on the efficiency
    of particulate collection system as a result of changes in
    particulate composition.

4.  The major filter media used for particulate collection was
    glass fiber filter with no binders.  This type of filter
    media presented no gross  problem if proper handling and
    weighing procedures were  followed.


                  RECOMMENDATIONS
1.  The effects of exhaust gas dilution ratio,  dilution air
    moisture content, dilution air temperature, and residence
    time in the dilution tube are other factors that should
    be studied as to their effect on the collection of
    particulate emissions.

2.  Any definition of particulate matter must be referred to a
    very well  defined set of sampling  parameters.

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                                    Flow Diogrom for Engine Exhoust
                                        Particulote Collection
                                                                                  Air
                                                                                  out
                                                                                   n
        Filter
           I
               Instrument
_   .   „     v7-   and
^Engine Roo.n  Rj Control  Room _

         Mix-ing           -*-—""
       *.   I fel    _
Air
  in.
    Part iculate
Gravimetric Fallout
 Flow —
Control
        Eng ine
      Dynamometer
Eng ine
                                               Sampling  Slits
              Tail Pipe
                            is
                              Standard  Muffler
                      Scott  Reseorch \r\s,
                         NO  and N02
                          Analysis
                      Fisher Gas Part i'c i oner
                         CO, C02, M2, 02
                                     Total Hydrocarbon
                                     Analyzer
             Exnaust  Pipe
                                                                         Anderson
                                                                         Separator
                                                                         Millipore
                                                                          Filter
                                                                         Flow Meter —
                                                                         Vacuum
                                                                          Pump
                                                                                                  *
                                                                                                  /
                                                                                Air
                                                                                Pump
                                                         I
                                                         ro
                                                         o
                                                         I
                                                                                                Manome
                                                                                             Figures  ]

-------
                                   -201-
                               FIGURE-#2
                TYPE "A" GLASS FIBER FILTER #61698 142 mm
                 All temperatures were held for one hour
                 before weighing.  Six papers were used
                        to check reproducibility
                                            Filter Paper No
Temperature °
Wt. grams at
l-.'t. grams at
Total grams 1
Wt. grams at
Total grams 1
Wt. grams at
Total grams 1
Wt. grams at
Total grams 1

Start wt. gra
48 hrs. wt. g
F
75°
100°
OSS
150°
OSS
200°
OSS
250°
OSS
The
ms at .
rams at
#1
.9341
.9341
.0000
.9338
.0003
.9335
.0006
.9333
.0008
six filter pa
room over
75° .9341
75° .9340
#2
.9572
.9572
.0000
.9567
.0005
.9563
.0009
.9563
.0009
pers were
weekend a
.9572
.9570
#3
.9404
.9404
.0000
.9400
.0004
.9398
.0006
.9396
.0008
returned
nd reweigh
.9404
.9403
//4
.9565
.9565
.0000
.9564
.0001
.9557
.0008
.9557
.0008
to storage
ed
.9565
.9564
#5
.9471
.9471
.0000
.9467
.0004
.9464
.0007
.9464
.0007

.9471
.9471
#6
.9453
.9453
.0000
.9450
.0003
.9444
.0009
.9444
.0009

.9453
.9449
Permanent wt.  loss grams   .0001
.0002
,0001
.0001
.0000
0004

-------
                               -202-
                           FIGURE  #3
                           SAMPLING
              Same Exhaust for Same Time Period
               Flow Rates on All Filters 1 cfm
                      Mil 1i pore •

                     0AAWP  14200
                  AA 0.8 p  pore size
                  White Plain 142 mm
                   Membrane Type	
                         Gel man

                   Glass Fiber Filter
                     Type A - 142 mm
                  99.7% Efficient for
                 Removal of .3 u particles^
                   Change
Run #44
Nonleaded Fuel
.0402 grams
.0377 grams
-6.2
Run #75
Leaded Fuel
.0652  grams
.0701  grams
+ 7.0

-------
«*- o
O -J

r— t_
  GJ
O +•>
•!-> i —
o o
<_) C
  a
E S_
<+- O
O 4-
  4-
      +20


      + 10


        0


      -10


      -20
                                                    FIGURE #4

                                    DILUTED EXHAUST PARTICULATE FILTRATION
                                                                                      -— Nonleaded Fuel
                                                                                      	 Leaded Fuel

•• » '     !     i ™ ™* •"••, ^» •« «K ^^ ^^ ^^
                                        •- «
  110°F -  79
                                             -152°F  -  79
                                             133°F  -  78



                                             101°F  -'77

                                               93°F  -  78
                                            !' ""temp". '"'F'of"'
                                            i   Filters,  Run #
                                                    -  77
                                   !
                                    	!	J.	t ....
                              8   10   12    14    16   18   20   22    24


                             FOOT PER MINUTE GAS  VELOCITY PAST  FILTER
                                 26    28
30
                                                                                                               ro
                                                                                                               O
                                                                                                               CO
                                                                                                               i
                                                     X =
              1  cfm
            = 4  cfm

-------
O — J

•— S_
o +->
-(-> r—
  Lt.
CJ
i-
£ O
o o
o c:
  o
E s-
4- CU
O >4-
                                                   FIGURE #5

                                     DILUTED EXHAUST PARTICULATE  FILTRATION
      +20—	
      + 10	
                                                                                           — Nonleaded Fuel
                                                                                            - Leaded  Fuel
                                            \ Rn  #79


                                          cefm        ;
                                               i

                                         #77  -  60 mph ss


                                     ;• 4"  cfm  60 moh ss
                                                      \\   #78  Mild  Cycling
                                                                                rv>
                                                                                o
                 100
110
120       130       140        150

  EXHAUST GAS TEMPERATURE  °F AT  FILTER
160
170
180
                                                                                              X  =
                                                                       1  cfm
                                                                     =  4  cfm

-------
                         -205-
                    FIGURE f/6
The effect of leaded gasoline on the difference in
participate pick-up on the 1  cfm filter and Andersen
versus 4 cfm filter only.
             Number       Percent Less Particulate Collected
 TEL in      of Runs      on 4 cfm Filter Compared to 1  cfm
Gasol ine	Averaged	Filter and Andersen
None            6                    -72.23%

.5 cc/gal.       4                    -40.60%

3. cc/gal.       9 .                   -19.29%

-------
                               FIGURE  #7
Leaded Gasoline
  Participate
Grams Per Mile '
% Change
1 cfni Filter
Run # 1
80



81



No n leaded


82
Mil 1 i pore
Glass


cfm Filter
.0117
(60.6%)
.0121 ' \
(65.0%) v-
.01228
(64,0%)
.01253
(66.5%)
Gasol ine


.0010
(14.4%)

.0019
(30.10%)
Andersen
.0075
(38.8%)
.0065
(39.6%)
.0069
(35.9%)
.0063
(33.4%)

\
\
.0057
(82.6%)

.0044
(69.8%)
Total
.0193

.0186

.01918

.01883




.0069


.0063

1 cfm
Only
.0166

.0164

.01826

.01883




.0012


.0038

Compared to
1 cfm & Andersen
-13.9%

-11 .82%

-4.7%

-2.8%




-82.4


— d y . b /<>

                                                                                              I
                                                                                              l\5
                                                                                              O
                                                                                              0>
                                                                                              I

-------


THERMAL
-207-
FIGURE #8
PROFILE OF SAMPLING SYSTEM
Chassis dynamometer 60 mph steady
s t a t.e w i t h air to exhaust dilution
ratio between 4:1 and 6:1
Tempera
CC of TEL
3.0
0.0
0.5
3.0
0.5
0.0
3.0
0.0
0.0
3.0
3.0
3.0
0.0
i
Of Sample 1 cfm
167.2
144.2
147.0
147.2
141.4
139.0
156.6 108.
116.7 101.0
92.7
125.2 105.1
131.8 103
105
129.8 108
106
128.4 98.6
104.0



ture °F
Andersen
Plus 1 cfm
Filter
81 .5
92.0
90.0
87.5
84.3
82.4
86.0


86
86
88
86
82
82.4




i
4 cfm
Filter
143.5
142.0
137,0
136.1
132.0
126.0
139.
102.2
93.6
117.0



Run //

 50
 58
 61
 67
 70
 72
 75
 77
 78
 79
   4
 80

 81

 82

Avg.  Temp, °F =           139.5       103.1          87.5         126.8

-------
           FIGURE #9
DESICCATOR STUDY OF FILTER PAPER
           New Tare
Tare
Mi
Fi
Gl
Fi
Mi
Fi
Gl
Fi
After 48 hrs. Moisture
in Desiccator Loss
IHpore t #1 3.2961 gm 3.2883 gm .0078 gm
Hers V. #2 3.2945 gm 3.2868 gm .0077 gm
ass •/ #3 1.1226 gm 1.1223 gm .0003 gm
ber x #4 1.1321 gm 1.1318 gm .0003 gm
Immediately After
Particulate Collection New Tare Particulate
11 ipore / #1
Her x #2
ass /
ber ^
#3
#4
3
3
1
1
.3019
.2984
.1295
.1394
gm
gm
gm
gm
After 48 hrs.
in Desiccator
Mi
Fi
Gl
Fi
11 ipo're / #1
Hers ^ #2
ass r
bers ^
#3
#4
3
3
1
1
.2934
.2919
.1293
.1390
gm
gm
gm
gm
3.2883
3.2868
1.1223
1 .1318
gm .0136 gm
gm . 01 1 6 gm
gm .0073 gm
gm .0076 gm
After 24 hrs. Moisture
in Desiccator Loss
3.2959 gm .0060 gm
3.2925 gm .0059 gm
1 . 1 294 gm .0002 gm - g
1 .1392 gm .0002 gm '
Moisture
Loss
.0085
.0065
.0003
.0004
gm
gm
gm
gm



-------
                                          -209-
                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
1. REPORT NO.

 APTD-1567
                             2.
             3. RECIPIENT'S ACCESSION'NO.

               PB-224243/AS
4. TITLE AND SUBTITLE
 Characterization  of Particulates and Other Non-Regulatec
 Emissions from Mobile  Sources and the Effects of Exhaustje
 Emissions Control Devices on These Emissions
             5. REPORT DATE

               March 1973
             i. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

 J. E. Gentel, 0. J. Manary,  Joseph C. Valenta
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
                                                           10. PROGRAM ELEMENT NO.
 The Dow Chemical  Company
 Midland, Michigan  48640
             11. CONTRACT/GRANT NO.


               EHS 70-101
 12. SPONSORING AGENCY NAME AND ADDRESS
 U.S. Environmental  Protection Agency
 Mobile Source Air Pollution Control
 Emission Control Technology Division
 Ann Arbor, Michigan  48105 .	
             13. TYPE OF REPORT AND PERIOD COVERED
             14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
 fhe effect of emission control devices on the particulate emissions of an automotive
 power plant was  investigated.   The work was divided  into five tasks as follows:
 TASK I was the characterization of a particulate trapping system, and the determina-
 tion of what effects,  if any,  were noted as conditions  within the system were control-
 lably varied; TASK  II  was the  definition of a particulate baseline for a 1972 400 CID
 engine, using non-leaded and low lead fuel - no emission control devices were used for
 the baseline runs;  TASK III was the evaluation of  the particulate emissions from a
 1972 400 CID engine equipped with the following control devices - three different
 oxidation catalysts, one NOx catalyst, and one exhaust  gas recirculation system; TASK
 IV involved testing automobiles equipped with control devices for particulate emis-
 sions - these vehicles were supplied by both the contractor and the Government; and
 TASK V was to define a preliminary collection system for diesel engine particulate
 sampling.  In all tasks, r>articulate mass emission rates were measured, as well as
 particle mass size  distribution, carbon and hydrogen, trace matal? and benzo-a-pyrene
 content of the particulate. Ammonia and aldehydes were measured in the exhaust gas
 condensate, and  gaseous emissions were determined  as a  routine check on engine
 operating conditions.
17.
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                             b.IDENTIFIERS/OPEN ENDED TERMS
 Air pollution
 Particles
 Exhaust emissions
 Air pollution control  equipment
 Gas sampling
 Catalytic converters
 Spark ignition engines
 Diesel engines
                          c.  COSATI Field/Group
                            13B
13. DISTRIBUTION STATEMENT
                                              19. SECURITY CLASS (ThisReport/
                                               Unclassified
                           21. NO. OF PAGES
                            216
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20. SECURITY CLASS (Thispage)
  Unclassified
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                                                                -210-

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-------