-------
                                                                 PB82-188699
   Sulfate and Particulate Emissions  from In-Use
   Catalyst Vehicles: Regulated/Unregulated
   Emissions and Fuel Economy
  -New York State Dept. of Environmental
  Conservation, Albany
   Prepared for

   Environmental Protection Agency
   Research Triangle Park, NC
ttOlor Vehicle Emission Lab
        LIBRARY
   Dec 79
U.&. Department of Commerce
National Technical Information Service

-------
                  RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional  grouping  was consciously
planned to foster technology transfer and a maximum interface in related fields
The nine series are*

    1. Environmental Health Effects Research

    2. Environmental Protection Technology

    3. Ecological Research

    4. Environmental Monitoring

    5. Socioeconomic Environmental Studies

    6. Scientific and Technical Assessment Reports (STAR)

    7. Interagency Energy-Environment Research and Development

    8. "Special" Reports

    9. Miscellaneous Reports


This report has been assigned to the MISCELLANEOUS REPORTS series. This
series is reserved for reports whose content does not fit into one of the other specific
series Conference proceedings, annual reports, and bibliographies are examples
of miscellaneous reports.
                        EPA REVIEW NOTICE
This report has been reviewed by the JJ S. Environmental Protection Agency, and
approved for publication  Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.

This document is available to the public through the National Technical Information
Service. Springfield. Virginia 22161.

-------
                                    EPA-600/9-79-047

                                        December 1979
Sulfate and  Participate Emissions
  From  In-Use Catalyst Vehicles:
 Regulated/Unregulated Emissions
           and  Fuel  Economy
                        by

          R.E Gibbs. G P. Wotzak. S M. Byer, and N P. Kolak

                 Division of Air Resources
               Automotive Emissions Evaluation
       New York State Department of Environmental Conservation
                    50 Wolf Road
                 Albany. New York 12233


                  Grant No. R803520-01


               Project Officer Frances Duffield

           Environmental Criteria and Assessment Office
               Research Triangle Park, NC 27711
                     Preoared for

           U.S. ENVIRONMENTAL PROTECTION AGENCY
              Office of Research and Development
           Office of Health and Environmental Assessment
           Environmental Criteria and Assessment Office
              Research Triangle Park. NC 27711

-------
                                DISCLAIMER
     This report has been reviewed by the Environmental Criteria and
Assessment Office, U.S. Environmental Protection Agency, and approved for
publication.  Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial produces constitute
endorsement or recommendation for use.
                                     11

-------
                                   FOREWORD                  •     ;  .


       To .issess tlie effects of pollution on thr environment and the public

  health, a broad range of scientific and technical  information is needed.

  This means that the Environmental  Protection Agency must carry out

.  activities simultaneously on several fronts, including the measurement,

  analysis, and precise characterization of the pollutants invading the

 •--environment,  as well as the evaluation of the varied and oilen complex

  biological effects of these pollutants.  By critically .reviewing ar.d

  interpreting  such information, the Environmental Criteria and Assessment

  Office of EPA provides a scientific basis for decisions on the regulation

  of pollutants that may affect the environment or the public health.

       this report presents- the results of a study on the pollutant emissions

  and fuel economy of selected cars over a two and one-half year period.  In

  focusing on catalyst-equipped vehicles operated under "real world" conditions,

.  this study attempts to provide information needed to accurately assess a

1' number of pollution problems associated with the use of automobiles.
        '"i                        •               '                 \

 V  '• :   \   • "•                                  •                \
••  '.  '     \                                      Lester D. Grant   \
  \       \        '                           -  Director.
  \       \                                     Environmental Criteria and
          \                                      Assessment Office-
                                      Jin

-------
                                   ABSTRACT
     An emissions and fuel economy study of 56 catalyst cars in consumer use
and maintenance has been performed by repeated testing of the cars over a two
and one-half year period.  This report summarizes analyses of the data base,
and includes results on i^.le CO levels, mass emissions of HC, CO, NOX, sulfate.
S02 and total particulate; total particulate elemental analyses, catalyst
activity, and fuel economy.  Test cycles used were the 1975 FTP, one-hour 50 mph
cruise, Congested Freeway Driving Schedule, Highway -Fuel Economy Test, and idle,
30 and 50 mph cruise for catalyst activity tests.  Fuel economy data for over-
the-road driving are also presented from on-board totalizing fuel and engine
hour meters on each car.

     Idle CO indicative of naladjuct«?d carburetors (> 1%) was found to cor-
relate with FTP CO emissions, purge of stored sulfur in the form of S02 from
catalysts, and decreases in catalyst activity at idle in comparison to 30 and
50 mph activity results.  Particulate sulfate emissions accounted for only 3.7%.
of fuel sulfur for the 256 CFDS tests in the data base.  Over-the-road fuel
economy was most closely represented by the FTP (city) value.
                                              i                    •       •
                                              i
                                        iv

-------
                              CONTENTS
Disclaimer	    ii
Abstract	   ill
Figures  	 ........ 	  ......     v
Tables	viii
Abbreviations and Conversions  .................     x
Acknowledgements ........................    xi

     1.  Introduction   .....................     1
     2.  Conclusions ......................     6
     3.  Regulated and  Sulfate remissions	     8
     4.  Fuel Economy	    24
     5.  Characterization of Particulate  Emissions  ...» ,.  .  .    40
     6.  Catalyst Activity Tests  ..*  	  ........    57
     7.  Sulfur Dioxide Emissions   ..i.  ...........    64
     8.  Experimental Procedures  and F  Jipment  .........    72

References ...........  	  .......   100
Appendix A	   1Q4

-------
                                   FIGURES

Number                                                                   Page

  1   Mileage Test Point Roster. ............... 	   4

  2   Mileage Accumulation Trends for HC Emissions ...........  12

  3   Mileage Accumulation Trends for CO Emissions and
        Mileage Accumulation Trends for Idle CO. ............  13

  4   Comparison of Idle CO and FTP CO Trends. .............  15

  TJ   Mileage Accumulation Trends for NOX Emissions	  17

  6   Mileage Accumulation Trends for SO^ Emissions. ..........  18

  7   FTP, CFDS, HFET Driving Schedules	26

  8   Fuel Economy by Test Mode. ....................  28

  9   Fuel Economy by Test Mode:  Chrysler 225 CID 1-6	29

 10   Fuel Economy by Test Mode: • Chrysler 313 CID V-8	  30

 11   Fuel Economy by Test Mode:  fiuick 350 < ID V-8	31

 12   Fuel Economy vs. Mileage Accumulation, Car #2. ..........  32
                                                                   i
 13   Fuel Economy vs. Mileage Accumulation, Car #19 	 .....  32

 14   Fuel Economy vs. Mileage Accumulation, Car #25 ..........  32

 15   Mileage Accumulation Trends for Carbon Balance Fuel Economy. ...  33

 16   Seasonal OTR Fuel Economy. .'...................  34

 17   Seasonal OTR Vehicle Speed	'.	35

 18   Cumulative Frequency Distribution OTR Vehicle Speed	37

 19   Seasonal OTR Fuel Economy  for Control Vehicle	38

 M   Seasonal OTR Vehicle Speed for Control Vehicle 	 	39


                                     vi

-------
                                   FIGURES

tlumber                                                                   Page

 21   Sulfatc Emissions for Successive CFDS Cycles:
        Monolith,  no air pump. .....................  41
 22   Sulfatc Emissions for Successive CF^,- . /c-les:
        Monolith, air pump .........
 23   Sulfate Emissions for Sur-o^sivo iJFDS Cycles:  Beaded,
        no air pump. ...............•«««••«««•«  41

 24   Fuel Analyses, Three Month Running Averages. ...........  44

 25   Frequency Distribution of Particulate Bromine Emissions. .....  49

 26   Frequency Distribution of Particulate Lead Emissions .......  49

 27   Frequency Distribution of Particulate Zinc Emissions ...... .  SO

 28   Frequency Distribution of Particulate Copper Emissions ......  50

 29   Frequency Distribution of Particulate Iron Emissions .......  51

 30   Frequency Distribution of Particu'ate Sulfur Emissions ......  51

 31   Frequency Distribution of Particulate Calcium Emissions. .....  52

 32   Frequency Distribution of Particulate Phosphorous Emissions. ...  52

 33   Frequency Distribution of Particulate Aluminum Emissions .....  53

 34   Frequency Distribution of Particulate Manganese Emissions. ....  53

 35   Frequency Distribution of Percent Particulate Sulfur Recovery. . .  54

 36   Frequency Distribution of Percent Particulate Lead Recovery. ...  54

 37   Frequency Distribution of Percent Particulate Manganese Recovery .  55

 38   Purge of S02 from Catalyst ......... ...........  66

 39   SO 2 Purge Fractions by Idle CO Level:  50 mph cruise .......  67

 40   SO 2 Purge Fractions by Idle CO Level:  CFDS. ...........  68

 41   OTR Fuel Meter Installation ............. . ......  75

 42   Collection of Tank Fuel Samp-le ........... .......  75

 43   Vehicle Check-In ... ......................  77


                                    vi i

-------
                                    FIGURES
                                                                                        I i
Number                                                                    Page          j 1
 44   Vehicle Check-In Log Sheet 	   78            j
 4?   Car Mover Operation	   79           ;,
                                                                                        h
 46   Before/After Catalyst Sample Ports 	   79           • j
 47   Emissions Test Bay 	 ................   80
 48   Dynamometer, Cooling Fans	   81
 49   Exhaust Sampling Equipment ....................   81
 50   Schematic of Exhaust Handling and Particulate Sampling System. . .   83
 51   Particulate Sample Probes. ... 	 ...........   84
 52   Oxygen in Raw Exhaust Sample System. ........ 	   86
 53   SO2 Measurement System 	  ........   87
 54   S02 Electronic Integration Switching System. ...........   88
 55   Microbalance for Particulate Mass. ................   91
 56   BCA Apparatus Set-Up .......................   93
 57   Schematic for Automated BCA Analysis of Sulfate. .........   94
 58   XRF System for Particulate Analysis. ...............   95
 59   Comparison of Total Particulate Emissions for Two Probes  .....   97
 60   Comparison of 1C and BCA Sulfate Analysis	...«   98
 61   Comparison of 1C and XRF Sulfur Analysis	   99
                                     viii

-------
                                    TABLES


Numbc r                                                                    Page


  1   Test Croup Roster. 	    3


  2   Classification of Cars and Tests	    5


  3   Average Emission Results by Car. .................    9


  4   Average Emission Results by Mileage Intervals. ..........   10


  5   CO Trends by Mileage Accumulation. ................   16


  6   Average Emission Results, All Tests, All Manufacturers 	   19


  7   Average Emission Results, General Motors Vehicle Tests 	   20


  8   Average Emission Results, Ford Vehicle Tests ...........   21


  9   Average Emission Results, Chrysler Vehicle Tests .........   22


 10   Tests Grouped by Emission Cut Points	   23


 11   Average Fuel Economy from Test G^oup Vehicles. ..........   25


 12   Test Mode Characteristics	   24


 13   Sulfate Emissions as Percent of Fuel Sulfur Recovery 	 ..   43


 14   Total Particulate Emissions by Car ................   45


 15   XRF Detection Limits	* * *'i	   ^7
                                                       i
 16   Average XRF Elemental Emissions by Car	'.........   48


 17   Total Particulate Subclassification. .... 	   56


 18   Catalyst Activity Measurements at Steady State:  Idle	   58


 19   Catalyst Activity Measurements at ?-.cady State:  30 mph.  .....   59


 20   Catalyst Activity Measurements at Steady State:  50 mph	   60
                                       IX

-------
                                    TABLES




Number                                                                    Page




 21   Before/After Catalyst Measurement Comparison. ...........  61




 22   Fuel Sulfur Recovery	69




 23   Data List For Each Emissions Test	73




 24   Typical Test Day	74




 25   Exhaust Gas Measurement Instrumentation ..............  85




 26   Computer Output for Typical Emissions Test. ............ 105




 27   Computer Output Parameter List. .................. 106-7

-------
                            LIST OF ABBREVIATIONS
FTP        -- (1975) Federal Test Procedure
CFDS       — Congested Freeway Driving Schedule, also known as S-7, SET-7,
                CUE
HFET       -- Highway Fuel Economy Test:
OTR        — Over.the-road
CVS        — Constant volume sampler
XRF        — x-ray fluorescence
EGA        — Barium chloranilace
k          -- thousand (as in 5k miles = 5,000 miles)
1C         — Ion Chromatograph
AEL        — Automotive Emissions Laboratory, NYS Dept. of Environmental
                Conservation, Latham, NY
CID        — Cubic inch displacement
S          — sulfur
mi         -- mile(s)
hr         — hour(s)
km         — kilometer
g          — gram
mg         — milligram
uS         — micro gram
mpg        » miles per gallon
1          — liter
mm         ~ millimeter
nm         — nanometer
                                 CONVERSIONS
    to convert from           to            multiply first column unit by

          mi                  km                        1.6
         mi/hr               km/hr                      1.6
          g/mi                g/km                      0.625
         rag/mi             .  mg/km                      0.625
          mpg                km/1                       0.421
         gm/gal              gm/1                       0.264
                                    xi

-------
                                ACKNOWLEDGMENTS

     Project Officer Vandy DuffieId's dedicated assistance contributed to this
study from its inception to conclusion,  and is gratefully acknowledged.
Analysis of fuel samples was performed by Bob Jungers and the staff of the
Source, Fuels, and Molecular Chemistry Section at RTF.  Vehicle owners, who
with their cars, became collectively the important feature of this "real-world"
experimental study arc each acknowledged for their generosity of involvement.
The cooperation of many individuals from organizations with participating fleet
vehicles was also instrumental in carrying out the study.
                                     xn

-------
                                 SECTION 1

                               INTRODUCTION
BACKGROUND

     In 1974 and 1975 several engine stand ?nd prototype vehicle studies'1'8)
demonstrated the potential of catalyst equipped cars to emit suIfuric acid
fsulfate) aerosol at sufficient levels to be of identifiable concern.  As the
tnpnufacturing commitments to oxidaiive catalyst emission control technology
were made well in advance of these findings, the need for a sulfate emissions
data base from assembly-line produced, consumer-driven and consumer-maintained
vehicles was evident.  Sulfate emissions drta for this puipose were part of a
more comprehensive investigation of in-use catalyst cars summarized in this
project report,  \fliile this work was in progress much of the concern for
vehicular sulfate emissions lessened, mostly in response to the low emission
rates found, especially from non-air pump cataiyst cars(9-12).  In the
present study, a group of vehicles were repeatedly tested over a period of
two and a half years to characterize suifate emissions, HC/CO/NOX emissions
under different test modes, idle HC/CO levels, fuel economy in laboratory
and over-the-road (OTR) driving, catalyst activity, purge of stored sulfur
from catalysts, particulate emissions, state of engine tune, and tank fuel
characteristics.

     The collection of field-service vehicular data is usually more time-
consuming, cumbersome and expensive than permitted or warranted by the demands
of -time and the many questions for which data are needed.  However, emission
and fuel economy characteristics of consumer-driven and maintained vehicles
relate directly to air pollution and energy consumption in general, and pro-
jections for the vehicle popul  .ion at large are not always accurate if based
on results from prototype vehicles.  Within limitations, this project's data
base should be useful for a variety of emission and fuel economy evaluations
for first generation catalyst cars.

VEHICLE TESTING METHODOLOGY

     A vehicle test protocol WPS adopted in response to specific data elements
considered essential to the study.  Vehicles were tested in "as-received"
condition upon delivery to the New York State Department of Environmental
Conservation Automotive Emissions Laboratory (AEL).  Numerous engine param-
eters and idle HC/CO exhaust levels were logged, and a tank fuel sample was
collected in preparation for dynrmomstcr testing.  HC/CO/NOX emissions were
measured by the 1975 federal Test Procedure (FTP)(13) applicable to these cars.

-------
A one hour 50 mph steady cruise test was included to: 1) collect particulate
for 10 elemental analyses by x-ray fluorescence (XRF)i 2) pre-condition the
vehicle's catalyst for subsequent sulfate measurements during the Congested
Freeway Driving Schedule (CFDS)(14); and 3) provide a comparison'of sulfate
emissions between 50 mph cruise and the CFDS.  Five successive CFDS test
cycles were adopted to insure stabilized sulfate emission rates, since sulfur
storage/release from catalysts had been identified as causing observations of
erratic values of tailpipe sulfate emissions for successive test cycles (2,15-17).
At the last vehicle test catalyst activity for HC and CO conversion was
measured by sampling raw exhaust before and after the catalyst at idle, 30 mph
and 50 mph.

     Fuel economy was measured in all dynamometer test modes by carbon balance
procedure.  In addition, each vehicle was equipped with an engine hour meter
and totalizing fuel meter throughout the project to provide over-the-road
average speed and fuel economy between tests.  Necr the end of the project, a
Highway Fuel Economy Test (HFET) was added to further characterize dynamometer
fuel economy.

     Test protocol and laboratory analyses procedures are covered in Section 8
in further detail.

VEHICLE TEST GROUP

     Fifty-six 1975/76 model year catalyst-equipped cars made up the test
group sample.  Table 1 is a roster of these vehicles listing vehicle informa-
tion and a "car number" identifier used throughout this report.  Figure 1 is
a mileage test point roster.  While a total of 266 tests were performed, 10
tests were deleted as technically defective; therefore, 256 vehicle tests
serve as the data base for this report.

     Car #1 was stationed at AEL as a control vehicle and served as an over-
night loan car in order to gain access to other test-group vehicles.  It was
fueled exclusively at AEL and maintained in accordance with manufacturer's
specifications.  The remainder of the test group vehicles were drawn from
four institutional fleets in the Albany, N.Y. area and private vehicles
accessed by letter solicitation to owners of all 1975/76 cars in the New York
State Department of Environmental Conservation parking lot, 50 Wolf Road,
Albany, N.Y.  No screening criteria were used in establishing the test group.
Private vehicle owners were provided a fill-up of gasoline and two car wash
tickets as the only 'incentive for participation.  Vehicle test and check-in
results were provided to these owners only upon their request to minimize the
influence of the testing program oh these vehicles.

     Table 2 provides a breakdown for 256 vehicle tests by vehicle manufacture,
model year and ownership.
                '.
     The test group is not statistically representative of the vehicle popula-
tion at large.  No particular attempt was made to accurately represent all
makes, engine family types, inertia weight classes, etc.  However, the test

-------
                                             Table  1




                                           TFST GROUP ROSTF.R
Make
            Model
                                Trana  Carp Vent.
                                                          Faml ly
                                                                                                            Air Cond








10
11
12
11
14
IS
It
17
IS
19
20
21
22
2)
Ik
25
26
27
28
29
30
11
)2
I)
3'.
31
to
37
38
3»
40
it
42
4)
64
45
4h
47
48
49
50
it
52
5)
V.
55
56
. 	
1975
1 ClJt
i»/O
1975
1'7}
1
-------
                                    Figure
                         MILEAGE TEST POINT ROSTER
                          • -DENOTES EMISSION TEST ON VEHICLE

















to



21
oo
o-»


Z5
2t>
Z7
29
29
3O

32
33
^c
Vi
•«7







4 '








*\4













































































•















































*

*












*















.



















1



















.

























































*





































































*.








r M
























































.

* -~





























































































.












































































































































• r















































































































t ₯




1
5
     0    5    10    15    20   25    30    35   40    45   50    55    60   65

                              MILEAGE IN THOUSANDS

                                      4

-------
group encountered "refl-world" factors in nuch the same manner as the general
vehicle population.  This hypothesis is supported by the similarity of idle
CO patterns in the test group to those from P larger sample of catalyst cars
throughout New York Stfte. tested ?s prrt of s 25,000 car, 5-year idle
emissions inventory '11, 18).
                TABLE 2.	CLASSIFICATION OF CARS AND TESTS

56 Cars
29 Fleet Cars
26 Personal Cars
1 Control Car
1975 Model Cars
1976 Model Cars
1977 Model Cars

256 Emissions Tests
143 Fleet Tests
102 Private Tests
I
t
11 Control Tests
General Motors
21
6
14
1
8
11
2

95
29
55
11
Ford
10
2
8
0
4
6
0

38
7
ji
0
Chr.-sler
24
20
4
0
17
6
1 i
1
1
120
104
16
0
AMC
1
1
0
0
0
1
0

3
3
0
0

-------
                                 SECTION 2

                                CONCLUSIONS
SULFATE EMISSIONS

     For 256 vehicle tests, CFDS sulfate emissions averaged 3.1 rag/mi, and
only 147. of these tests gave sulfate emissions in excess of 10 mg/mi.  These
emission rates are significantly less than prototype results  (I, 15, 16, 17)
and are attributed to oxygen starvation of non-air pump catalyst systems with
maladjusted carburetors.  Another factor influencing these results was the
low sultur content of commercial unleaded gasoline used Cor testing (project
average 0.020 wt % S).

FTP CARBON MONOXIDE EMISSIONS

     CO was the most common pollutant outside the design standard for these
vehicles, being greatly affected by maladjusted carburetors.  Only 93 of 256
tests gave FTP CO at or below the 15 gin/mi standard.  Idle CO level corre-
sponded to FTP CO emissions.  For the 116 tests characterized by idle CO less
than 1% FTP CO emissions averaged 12.9 gin/mi, in contrast to the 140 tests on
vehicles with idle CO greater than 1% which averaged 42.5 gtn/rai FTP CO.

FUEL ECONOMY

     Laboratory carbon balance fuel economy measurements showed close corre-
spondence to EPA certification values applicable to test group vehicles. Fuel
economy based on 1.5 million miles of over-the-road driving averaged about
10% higher than the measured FTP (city) values.  Over-the-road vehicle speed
pveraged 33 mi/hr in contrast to 21 mi/hr for the FTP.
PURGE OF S02 FROM CATALYSTS

     Catalysts stored sulfur in some operational modes, and released S0£ upon
deceleration to idle.  This phenomenon was pronounced for vehicles with
carburetors characterized by idle CO > 1%.                                /

CATALYST CONVERSION ACTIVITY

     Exhaust sampling before/after catalysts near the conclusion of the
project showed 70% of the vehicles (30 out of 43) to be capable of 90% CO

-------
ppd 75" HC conversions.  Therefore, most  LesLs  in  this  project  are considered
to 'i.-»v»' iH-fii performed on vehicles with active  cptalysts.

     Hvon active catalysts showed large- decreases  in  CO conversion at  idle
if the crrburetor was adjusted to give high engine-out  CO  0  17,).   This
phenomenon results in dormant catalysts at times of high emissions, and also
accounts Cor the observed decrease in CO  emissions for  cars  restored to
proper carburetor adjustmc-nt.

EMISSION TRENTJS WITH MILEAGE ACdWULATION

     Emission rates of the measured pollutrnts  were not found  to be a
consistent function of vehicle mileage.

-------
                                 SECTION 3

                      REGULATED AND SULFATE EMISSIONS
INTRODUCTION

     No single method for organizing the data from these in-use vehicles has
been -found to be completely satisfactory.  Instead, several different
a  roaches have been included in this report in order to provide a composite
picture of how various emissions related factors interrelate.  In this
section the data base has been analy7td by the following: 1) individual
vehicle emissions averages; 2) mileage accumulation trends of the overall
fleet; 3) individual vehicle mileage accumulation trends; and 4) tests grouped
by various parameter subclassifications.

EMISSION RESULTS AVERAGED BY CAR
                                                                      i
     Emissions of each car, averaged over all tests on that car, are shown by
car number in Table 3.  The number of tests per vehicle and the mileage
interval spanned from the first to last test are indicated for each vehicle.
HC/CO/NOX results are reported for the FTP. CFDS, and 50 mph cruise tests.
CFDS values in Tnble 3 are taken from the second CFDS cycle, as discussed in
Section 5.

EMISSION TRENDS WITH MILEAGE ACCUMUTATION:  OVERALL TEST GROUP

     Changes" in emissions with mileage accumulation for the test group were
investigated by averaging all tp«=ts in the data base in 5,000 mile intervals
(i.e. 0-5k, 5-10k miles, etc.).  These results are shown in Table 4.

     Individual columns in Table 4 show average emission rates for successive
5,000 mile intervals.  Idle CO averaged 1.3% in the first interval, rose to
2.47. in the 5k to 10k mile interval and was relatively unchanged thereafter.
The increase in FTP CO in the second 5,000 mile interval parallels the in-
crease in idle CO.  FTP HC emissions show an overall increasing trend with
mileage accumulation.  N'0X levels showed no significant change with mileage.
Particulate sulfate emissions in both the 50 mph cruise and the CFDS show a
significant falloff with increasing mileage.

-------
                                                                3.  Avriagc tnlnslnn Ki'Bulll by Car

CAR MMC'i
i rrsii TEWrt
1 11 2'.'J76.(i
2 I, 3i-.'«.7.7
1 7 41nb<>.l
4 '. 3 1 6 3 1 . 6
1 4 l.t.9.7
6 1 JJJI9.4
1 5, J14b4.9
e 5 11)114. 9
9 i i727e.5
10 5 10509. *'
11 5 17666.3
1? 0 36715.1
13 1C 14719.')
14 2 7H2B. 1
IS 4 28799.9
16 j 37876.2
17 S 36202.9
IB 5 12412.6
19 37367.]
20 404A4.9
21 V9012.6
22 11961.1
2} 2943B.2
24 1286.4
35 28704.0
26 ::i7i.O
27 26067.9
2B 19104.7
29 21752. J
30 1794-1.)
31 1P091.4
32 37030.7
33 26S60.4
34 24631.7
Jl 11)861.1
36 31692.2
37 10944.2
38 30299.9
39 14162. J
40 4222.8
41 2)181.9
42 27107.7
4J 29JJ6.8
44 13B09.7
45 12J84.1
46 2713S.4
47 26144.9
48 2J5V0.5
49 6I«.0
jO . 6084.0
11 J3771.6
52 15487.9
51 76846.7
54 31842.9
11 " 17011.6
56 4V19D.6

IMF
CO *
O.dl
l.-ir
J.7J
4.16
1 .80
O.U4
2.74
1. 14
3. .4
1.08
2.00
0.04
5.39
0.70
3.95
1.57
0.00
3.18
1.90
1.46
5.06
2.00
5.17
1.75
0.00
0.28
3.10
2.92
1.98
0.30
0.38
5.32
0.97
5.24
0.66
1.90
4.B7
0.07
0.63
4.45
2. 65
2.98
1.98
0.03
2.40
7.18
1.55
4.28
3.80
0.60
U.OO
1.23
0.4U
0.08
3.b3
2.37
FTP MJ-I CFDS
HOT
HC CO CO(l) NT* HC CO TJOX Sfto -.MID HC CO HOZ SC4 SC4I?)
U. II >1.28 1.36 l.'lj U.O,' li.UI I.JI1 ').7', 14.44 U.Of 1.10 1.-4 9.CI 14. ',0
l.JM Ji.80 2li.'.l J."7 II.IM '..l; .'.n O.JO O.J7 0.1" 13.75 2.«0 0.22 0.4|
2. .7 56.79 4..-.V3 J.t.1 0.01 (..ii7 ..7'J j.31 4.39 I'.il 15.71 J.16 1.3V 2.bb
1.16 66.06 47.71 1.J3 a.i.t |.l; .01 1 . ?4 2.04 J.H. 17.02 1.72 1.20 2.14
i.i't 41.45 .(J.07 2-iH U.l.u '..'.I .-it I..J4 0.56 U.67 /. Id 2.19 U.."j 0.41
11.16 7.68 4.13 2.-J1 u. Ill U.,/4 .1.1 1.U2 2.31 U.ll 1.52 3.2P 0.72 1.7?
2.47 30.14 20.74 3.1" O.U9 O.UO .1J >-.|9 6.17 0.93 6.42 2 95 0.29 0.'J4
O.U9 5.82 11.71 1.12 0.13 O.U9 .""I 1U.34 22.23 0.13 0.46 2.51 8.04 21.00
2.17 4:. 54 1C." 2.J7 0.13 U 05 .71 1.54 9.72 0.47 4.50 2.15 1.28 4.81
1.24 21.02 '.->•<• 2.22 0.06 U..., .91 4.60 5.33 0.15 1.12 1.75 O.U5 0.93
1.52 25.56 9.1J 3.J2 0.06 0.00 .32 4.42 5.04 0.19 2.16 1.00 1.01 1.31
2.49 29.78 B.73 1.80 U.22 0.17 .71 6.15 7.86 0.38 1.60 2.09 9.78 14.12
1.74 75.00 51.41 3.12 0.03 O.t'4 .67 1.98 3.66 0.64 17.39 4.45 0.15 1.02
0.93 39.13 31.60 1.10 0.11 12.38 .63 3.07 6.04 0.23 16.65 1.09 0.67 1.45
2.01 56.38 24.84 2.71 O.C8 0.03 .42 1.43 12.20 0.16 7.88 1.90 1.1!) 2.41
1.69 44.10 11.49 1.79 0.11 0.03 .76 4.20 7.14 0.17 2.90 2.09 4.97 9.81
1.71 8.22 4.33 2.17 0.21 0.24 .16 1.26 6.P2 0.32 2.00 2.79 3.84 4.97
1.40 28.36 11.18 1.68 0.10 0.01 .11 1U.48 13.31 0.30 4.76 1.S6 1.7h s.BIl
2.09 46.75 17.61 2.33 0.11 0.10 .72 13. 5fl 18 80 0.16 4.18 2.38 6.S2 10.79
1.55 26.58 8.20 2.96 D.Ob 0.07 .56 4.29 5.1V 0.27 2.78 2.J3 2.52 3.02
2.72 49.22 30.70 2.16 0.12 U.U9 .45 2.17 2.66 0.63 9.06 1.26 0.11 0.71
1.17 20.28 16.34 1.89 0.05 .1.40 .1H U.ll 0.27 0.25 6.21 .'.26 0.07 O.It
2.32 41.02 28.40 2.91 0.07 0.00 .54 3.91 6.03 0.16 9.47 2.37 0.36 0.54
1.25 24.90 24.27 2.03 0.13 2.77 .34 9. OR 13.98 0.40 8.95 2.31 2.34 4.22
0.87 3.41 2.33 2.91 0.14 0.17 .14 7.19 8.11 0.27 0.7S 1.72 8.P6 10.23
1.17 13.91 10.35 3.84 0.72 4.17 .J3 6.76 8.85 0.92 4.91 1.51 7.0J 9.73
4.23 52.2? 44.34 2. '2 U.ll 7.46 .19 0.4U 0.74 1.41 24.40 2.56 0.42 0.67
1.44 20.92 16. b9 2.6i 0.04 U.UU .}'. 0.44 0.61 0.36 4.78 2.11 0.37 0.61
1.34 15.18 11.87 2.40 0.04 (1.00 .13 0.16 0.70 0.30 4.05 2.61 0.11 0.71
0.71 6.55 2.82 6.06 0.1)6 0.01 .49 0.17 0.87 0.15 1.7J 5.73 0.11 O.M
1.28 28.80 21.21 2.64 0.115 1.24 .11 2.78 2.98 0.42 14.51 1.16 0.82 0.87
2.42 34.76 25.61 2.65 0.05 0.00 .08 0.18 0.44 0.",2 v.10 2.83 0.58 1.62
1.64 26.21 20.48 2.61 0.11 l.HO .92 1.11 0.97 U.68 12.07 2.00 0.5) O.M
2.14 67.60 6J.H7 2.49 0.04 O.UJ .11 11.57 16.91 0.61 21.56 1.13 0.54 O.bl
1.51 11.72 C..08 2.46 0.04 0.02 .34 17.25 20.99 0.21 2.42 2.96 1.79 5.91
1.10 17.02 1.77 3.40 0.09 0.04 .48 6.31 9.54 0.19 1.44 2.65 0.97 1.45
1.27 29.11 22.04 1.91 O.Q4 fl.Ol .12 0.46 0.61 0.18 10.17 1.73 0.57 0.74
0.74 6.68 1.67 1.34 0.09 0.01 .57 2.48 1.74 0.17 0.97 1.19 1.41 2.26
1.01 9.81 7.71 1.86 0.07 1.02 .18 0.55 1.19 0.17 1.47 1.64 0.69 1.10
2.20 34.80 10.31 7.09 C.06 0.01 .27 1.49 1.20 0.61 8.00 2.23 0.44 0.19
O.C9 20.08 11.09 4.7* 0.19 3.00 .IS 0.20 0.42 0.35 9.05 1.94 0.68 1.34
1.U1 36.68 24.75 .'.23 n. 10 0.01 .21 1.38 11.11 0.41 8.40 2.71 1.30 2.PO
1.64 j4.91 11.04 2*81 0.11 O.in .19 2.77 4.41 0.17 5.25 2.01 0.50 0.84
0.49 2.21 0.51 4.71 0.12 0.01 .74 18.49 18.16 0.19 0.40 5.08 16.25 16.11
1.18 28.71 23. Ill 2.17 0.31 !.?7 .16 4.19 5.92 0.46 7.61 2.44 3.10 4.14
1.50 "18. 98 15.11 1.61 0.24 0.78 .11 7.17 10.68 0.52 7.00 1.8] 8.18 12.22
1.41 14.41 9.96 1.70 0.69 1.11 .49 4.44 6.49 O.U9 1.45 1.55 1.66 6.81
1.17 27.45 21. lit 2.91- O.UJ 0. 1U .76 0.11 0.97 C . 24 6.00 1.68 0.14 0.18
1.00 21.11 20.12 1.72 0.08 O.OU .03 1.72 8.87 0.57 7.4] 3.84 0.91 1.17
1.21 12.30 1.18 2.12 U.07 0.03 .06 1.U1 8.44 0.21 2.10 2.21 Lit 1.66
0.18 H.04 4.8V 2.11 O.Ub 0.01 .32 2.1} 1.22 0.18 4.10 2.20 0.9* 1.67
0.8A 2.9) 0.12 1.04 0.11 0.02 .1) 30.17 54.12 0.21 0.10 2.03 33.18 61.57
1.17 11.46 6.96 2.77 O.UJ 0.01 .'11 5.41 7.21 0.24 1.01 1.60 1.87 1 67
u.85 11.01 7.92 l.HO O.OH 0.47 .211 U.41 0.76 0.20 5.1) 2.28 0.45 0.82
5. OB 110.91 97.34 1 . -Ji 1.77 41.77 .98 0.16 0.97 2.77 61.01 2.44 0.64 1.11
1.17 11.77 47.12 1.16 4.50 211.12 .09 11.99 12.81 2.30 16.70 2.86 11.79 10.90
 H*«n-   4.6   27117.0    2.16   1.72   2b.»0   19.JO    2.6)   0.2S    2.25


NOTK.  HC. CO. NOX all  (|a/nl).  S04 (ng/crt)
      (I) Hot FTP CO with Big 111 for Bag I
      (2) S04 v«lue> (djuitid to 0.010 ut. X fuel (uUur
                                                                                 2.24
                                                                                        1.14   7.77    0.14    8.2i   2.73    1.20    5.29

-------
                         Table 4
          AVERAGE RESULTS BY MILEAGE INTERVALS
MILEAGE
INTERVAL
0-5
5MO
10-13
IS -2O
20-29
25-30
30-35
35-40
40-45
45-5O
>50
•«ft
TESTS
27
29
37
28
37
25
26
13
16
7
9
IDLE
C0(%)
1.3
2.4
2.2
2.3
2.9
2.2
1.5
'2.3
2.0
2.0
2.5
FTP
HC CO NOx
.0 17.5 2.6
.4 25.8 2.6
.6 27.5 2.6
.8 29.7 2.5
.6 31.2 2.5
.7 31.6 2.7
.9 29.2 2.7
.9 31.3 32
2.3 329 2.9
3.3 46.8 2.4
2.4 38.0 2.9
50 mph CRUISE
HC CO NOx S04
O.I 06 2.3 11.8
0.1 0.4 2.1 6.7
C.2 1.4 2.2 7.3
0.1 2.5 20 7.2
0.2 1.7 2.1 5.7
0.2 2.2 2.5 8.1
0.3 2.2 2.4 8.3
O.I O.I 2.7 4.9
0.2 1.0 2.6 52
«.7 10.7 2.8 6.5
0.1 O.I 2.7 4.5
CFDS
HC CO NOx S04
0.2 3.8 2.7 100
O.4 7.6 2.6 7.7
0.7 7.1 2.7 3.7
0.5 9.5 2.5 4.5
0.9 7.8 2.6 2.7
0.5 9.2 2.9 6.8
0.5 6.9 2.9 4.1
0.5 7.2 3.3 1.8
0.8 8.9 3.3 3.0
1.3 19.1 3.0 6.7
0.5 7.2 3.2 2.4
NOTE:  MILEAGE INTERVALS IN THOUSANDS OF MILES
      HC, CO, N0», ALL (grit/mi)
      S04 MEASUREMENTS NORMALIZED TO 0.030 WT.% FUEL SULFUR, IN (mg/mi)

-------
EMISSION TRENDS WITH MILEAGE ACCUMULATION:  INDIVIDUAL VEHICLES

     Loast-squares-regressions of emissions results for tests on individual
vehicles have been used to compute mileage accumulation trends.  The compu-
tation?! procedure is simil?r to that used to determine "deterioration
fr-ctors" ?s defined in federal certification procedures (10).  In new car
certification, the change of an emissions parameter with accumulated mileage
is computed as the ratio of the emissions at 50,000 miles to emis.sions at
4,000 miles, as determined by the straight line regression of test data.  This
definition of deterioration could not be applied here since all cars did not
accumulate the same number of miles, and the emission data sets frequently
exhibited sufficient scatter so es to preclude extrapolation to a common
50,000 :nile basis as required by the "deterioration factor" definition.

     A common 10,000 mile basis for comparison of emissions trends among test
group cars was adopted to avoid extrapolation difficulties.  For each vehicle,
a straight line regression was used to compute a change in emissions for this
common 10,000 mile basis.  Dividing this emission change per 10,000 miles by
the mean of the emission data set used for the regression yields a normalized
"percent change in 10,000 miles".  These values are not a comparison of the
absolute emission rates among the test group vehicles, and only indicate how
an individual vehicle's emissions changed as a percentage of its own average.
The "percent change in 10,000 miles" values for the 56 test group cars thus
serve as a basis for additional comparisons; histograms of these values for
the test group give a picture of the variability in trends with accumulated
miles for various emission parameters and test cycles.

Hydrocarbon Trends                           ,

     Figure 2 contains histograms of the mileage accumulation trends in HC
emissions for the test group for FTP. CFDS and 50 mph cruise.  The "percent
change in 10,000 mile" abscissa ranges from -100% to +1007., the ordinate,
"test group cars", is expressed as a percentage of the vehicle sample.  In a
few instances the least squares regression lines resulted in trends in excess
of + 100% change in 10,000 mites, and these have been arbitrarily excluded in
the preparation of histograms (the number of vehicles used being noted on
each histogram).  The mean HC trend for the FTP is a 14% increase in emissions
per 10,000 miles.  CFDS and 50 mph cruise are similar to the FTP, although
the absolute emissions levels in these test modes are lower (Table 4).

Carbon Monoxide Trends                                   V

     Figure 3 shows mileage accumulation trend results for CO emissions in
the same format as Figure 2.  Idle CO trends are also presented in this figure.
For each test mode in Figure 3 the mean change is only a few percent, con-
sistent wit'. ..he relatively unchanged emissions in the 5,000 mile intervals
of Table 4.

     The range of "percent change in 10,000 miles" of FTP CO appears to bo
less than either the CFDS or 50 mph cruise.  This must be viewed in light of
                                    11

-------
Tig  2 MILEAGE  ACCUMULATION  TRENDS FOR  HC EMISSION'S
JC
28
24
§
u
§16
6
I"
8
4
rt









nil
N=54







-


























                 4O   80

28
24
20
16
12
8
4'
n
Men



pp


i nrrrf











•





i
52
i=16.4






ft
•?•£
28-
24
20
16 •
12
8
4'
n







nnf
M^nt(B7






II







™








"

—




n
                                -80  -4O
                                                  4O   80
                                                                  -80  -40
   % Change m 10,000 Mi
           FTP
% Change m C.OOOMi
       CFOS
% Change in 10,OOOMi
    SOmph Cruise
                                          12

-------
Fig. 3  MILEAGE ACCUMULATION TRENDS FOR  CO EMISSIONS
C.O

24-
g20-
2
o
ex
6 12-
Tn
8
4-
0
28

24-
§20-
e
o
o 16-
~ 12-
M
8-
4-
n























I







n








N = 52
Mean= 4 7
— .























i r
-80 ' -40 ' 0 40 8O
% Change in 10,000 Mi
FTP









"



















IF






















N=43










"


~








Mean= -34






_ _

e.o

24-
g20
a is-
^12-
8-
4-
28

24-
g20-
C
O
I16
»12.
^i
8-
4-
n







Ifflff
N=50
Meon=-14






—





"i ^n
-
-80 -40 0 ' 40 80
% Chgnge in 10,000 Mi
CFDS








n r
^l
N = 49
'Mean = 53




















!•











- •

-i i-j
nn
 -80   -40    o    *0    80
     % Change m iO.OOOMi
          SOmph Cruise
-160  -80    o     80
     %  Change in lO.OOOMi
             IDLE
                                13

-------
the absolute CO mass emissions in each segment, FTP, CFDS and 50 mph cruise
averaging 29.1, 7.8, 1.6 g/rni respectively.  Small changes in emissions from
test to test for an individual vehicle often have a greater relative effect
on the CFDS and 50 mph cruise.  In Figure 4 "percent change in 10,000 miles"
values for idle CO and FTP CO are plotted against each other.  Car number
identifiers ?re indicated beside each point.  The results of test data
presented graphically in Figure 4 are summarized in Table 5.  Trends in idle
CO and FTP CO values correspond except for values for 6 vehicles with increas-
ing idle CO and decreasing FTP CO.  Four of these six vehicles are Fords
(air pump vehicles).

     Two institutional flsets began to use HC/CO analyzers to maintain their
vehicles near the conclusion of this study.  This change was unknown to us at
the time, but corresponds to observations of decreasing idle CO values
observed for several high mileage vehicles.  T.-»n of the 21 vehicles with
decreasing idle CO values were from these two fleets.

NOy Trends

     Figure 5 shows histograms of NOX trends for the FTP, CFDS end 50 mph
cruise test modes.  The range of mileage accumulation trend values for NOX
are less than for HC and CO, and are also more consistent among test modes.

Particulate Sulfate                  t

     Figure 6 shows the effect of mileage accumulation on particulate sulfate
emission rates for the CFDS and 50 mph cruise, with emission rates normalized
to a common 0.030 wt % sulfur fuel.  The substantial percentage changes are
again in part a reflection of sensitivity due to low emission rates.

EMISSIONS RESULTS CATEGORI7ED BY INDIVIDUAL TESTS

     Above, the data for each test group car were treated as an independent,
mileage-related data set.  Analysis of test results for mileage accumulation
trends from individual cars implicitly assumes a relationship among the test
data for any given car.  The fact that tests were all performed on the same
vehicle does not totally define this relationship for the test data since
events between test points Xparticularly vehicle maintenance) can abruptly
influence emissions.  The range of positive and negative trends in the above
histograms, especially idle CO, demonstrates this point.  The predominant
such event observed in this study was a major change in idle CO between tests.
                                                          <•
     As an alternative to treating the data on each car as a mileage dependent
data set, each test was considered as being independent of other tests.  In
Table 6 the results of all tests have been tabulated for various subclassi-
ficstions without regard to the cars on which they were performed.  The number
of tests and cars in each classification is indicated.  Tables 7, 8, and 9 are
similar to Table 6 with only the cars of the indicated manufacturer included.
Sulfate results in Tables 6, 7, 8, and 9 are as measured, and not normalized
to 0.030 wt 7, for sulfur fuel.
                                    14

-------
      Fig. 4  Comparison  of Idle CO and FTP  CO  Trends
  100-
   50-
o
o
o

o"
  "•
2
o
  -50-
 -100-
 -150-
       50   51
                                        ts
                                               V  ««.  .»
                                                 »6
                                              r.s32-«'
                                                —1» II
                                                         •19
                                                          40
                                               |»
                                               IT
                                                       ..  V4
                                                            2 Tests
      -350 -300  -250 -200  -150  -100  -50    0    50   100   150   200

                                     % Change in 10,000 Mi

                                             IDLE
                             15

-------
              Table 5
CO Trends  by  Mileage Accumulation
 Comparison of Idle CO and FTP CO
56 CARS
IDLE
C0(%)
increasing t
decreasing |
unchanged -
FTP C0(gm/mi)
increasing t
19
4
4
decreasing 1
6
19
2
unchanged -
2
0
0
                 16

-------
Fig  5  MILEAGE ACCUMULATION  TRENDS FOR NO,  EMISSIONS

-------
      Fig. 6  MILEAGE ACCUMULATION TRENDS  FOR SULFATE  EMISSIONS
o
o
It

12-
ID-
S'
6-
4-
2
o
N= 51
Mean= 0.2
•




r


••







MB





••












-



-








-






-i
11
-80   -40
80
            % Change in 10,000 Mi
    Particulate Sulfate, SOmph Cruise, .03Owt %
    Fuel Sulfur
it

12-
10-
o
o
& 6-
o
I4'
2-
o
N = 47
























—























Mean =0.1












                                                  -80    -40
                       40    80
       % Change in 10,000 Mi
Particulate Sulfate, CFDS, .030 wt %
Fuel Sulfur
                                        18

-------
                                                             TABLE  6

                                                    Average Emission  Results
                                                  All Tests, All Manufacturers
vO
Classification _. No.
of Tests . - Tests
All
FTP CO < 15 gm/rai
FTP CO < 15 em/mi. HC < 1.5 ^m/mi
FTP CO < 15 gm/mi, HC < 1.5 gm/mi
NOv < 3. 1 gm/mi
Idle CO ^ 1%
Idle CO » 1%
FTP CO *• 45 gm/mi
Stall in Beg I of FTP
Fleet Vehicles
Private Vehicles
0 - 15,000 miles
15,000 - 30,000 miles
30,000 - 45,000 miles
AS. OOP miles
256
93
87
66
116
140
51
58
143
102
93
90
57
16
No.
Cars
56
31
28
26
39
47
18
31
29
26
45
51
37
13
Idle
COX
2.2
0.4
0.4
0.5
0.2
3.8
4.9
1.8
2.4
2.1
2.0
2.5
1.9
2.3
FTP
gm/mi
HC
1.7
0.9
0.8
0.8
1.0
2.3
3.4
1.5
1.9
1.6
1.4
1.8
2.0
2.8
CO
29.1
8.0
7.8
8.0
12.9
42.5
70.3
24.6
35.1
22.6
24.1
30.9
30.8
41.9
N0,:
2.7
2.8
2.8
2.3
2.7
2.6
2.6
2.4
2.5
2.9
2.6
2.6
2.9
2.7
1 Hr

HC
0.2
0.1
0.1
0.1
0.1
0.3
0.5
0.1
0.2
0.2
0.2
0.2
0.2
0.3
50 m.ph
gm/mi
CO
1.6
0.2
0.1
0.1
0.6
2.5
5.0
0.9
1.3
2.3
0.9
2.1
1.4
4.7
Cruise

NOx
2.3
2.4
2.4
1.9
2.3
2.2
2.7
2.1
2.2
2.5
2.2
2.2
2.6
2.6
mg/mi
504
5.0
7.3
7.9
7.8
6.9
3.5
4.7
7.8
5.1
4.5
6.1
4.5
4.3
4.5

HC
0.5
0.2
0.2
0.2
0.2
0.8
1.2
0.4
0.5
0.5
0.5
0.5
0.6
0.9
CFDS
gm/mi
CO
7.8
1.8
1.7
1.9
2.4
12.3
21.4
6.5
8.3
7.9
6.3
8.7
7.6
12.4


NOX
2.8
3.0
2.9
2.5
2.9
2.7
3.1
2.6
2.7
3.0
2.7
2.6
3.1
3.1

mg/mi
S04
t
3.1
i
6.0
6,1
6.4
5.5
1.2
0.7
5.2
2.3
I
3.5 !
4.0
2.7
2.3
3.0

-------
           TABLE 7

  Average Emission Results
General Motors Vehicle Tests
Classification
of Tests
All Oncr.il Motors Vehicles
FTP CO < 15 gm/mi
FTP CO < 15 gm/mi, HC < 1.5
FTP CO < 15 gm/mi, HC < 1.5
N'Ox < 3.1 gm/mi
Idle CO < 17.
Idle CO ^ 17.
FTP CO •> 45 gm/mi
CFDS S04 > 10 mg/mi
Fleet Vehicles
Private Vehicles
0 - 15,000 miles
15.000 - 30.000 miles
30.000 - 45.000 miles
45,000 miles
No.
Tests
95
46
gm/mi 45
gm/mi ,
36
53 '
42
7
6
29
55
•" '33
40
19
3
No.
Cars
21
13
13
12
15
14
3
2
6
14
16
19
11
3
Idle
C07.
1.6
0.2
0.2
0.2
0.1
3.6
3.8
0.0
0.7
2.4
1.6
2.1
0.9
1.3

HC
1.4
0.8
0.7
0.7
0.9
2.1
4.3
0.7
1.1
1.8
1.1
1.7
1.2
2.7
FTP
gm/mi
CO
21.8
8.2
8.1
8.4
9.9
36.8
84.3
9.2
14.5
27.8
18.8
26.0
17.7
25.8

NOX
2.7
2.8
2.8
2.3
2.7
2.7
2.6
1.9
2.4
3.0
2.4
2.7
3.2
2.2
1 Hr

HC
0.1
0.1
0.0
0.0
0.1
0.2
0.9
0
0.1
0.2
0.1
0.2
0.1
0.2
50 mph Cruise
gm/mi
CO
2.4
0.1
0.1
0.1
0.3
5.1
20.7
0
1.3
3.5
1.5
3.6
1.2
4.0

NOx
2.2
2.2
2.2
1.7
2.2
2.3
2.3
1.4
1.9
2.6
1.9
2.3
2.8
2.4
mg/mi
S04
2.3
3.3
3.3
3.8
3.8
0.5
0.4
13.4
1.6
1.2
2.4
1.8
2.9
5.8
HC
0.4
0.2
0.1
0.1
0.2
0.7
1.9
0.1
0.3
0.6
0.3
0.5
0.4
0.8
CFDS
gn/mi
CO
8.1
2.3
2.3
2.5
2.8
14.8
44.5
1.0
5.8
10.7
6.5
10.2
6.0
9.9


NOX
2.7
2.8
2.8
2.4
2.8
2.6
2.6
2.1
2.7
2.9
2.4
2.8
3.2
2.7

mg/mi
S0£
1.8
2.8
2.9
3.4
3.0
0.4
0.4
14.9
1.1
0.7
1.8
1.6
2.1
4.4

-------
         TABLE 8

Average Emission Results
   Ford Vehicle Tests
Classification
of Tests
All Ford Vehicles
FTP CO < 15 em/mi
FTP CO < 15 sm/mi, HC < 1.5 gin/mi
FT? CO < 15 gm/mi, HC < 1.5 gm/mi,
KOX < 3.1 gm/mi
Idle CO < IT.
Idle CO >> 17.
FTP CO -• 45 gm/ml
CFDS S04 •» 10 mg/mi
Fleet Vehicles
Private Vehicles
0 - 15.000 miles
15,000 - 30,000 miles
30.000 - 45,000 miles
45,000 miles
No.
Tests
38
.24
:
21
12
23
15
0
12
7
31
18
15
5
0
No.
Cars
10
7
7
5
P
6
0
6
2
8
8
9
5
0
Idle
C07,
1.3
0.8
0.9
1.4
0.2
3.0
.
0.8
1.2
1.3
0.9
1.8
1.2


HC
1.1
0.9
0.8
0.8
0.9
1.4
.
0.8
0.9
1.2
1.0
1.2
1.4

FTP
gm/mi
CO
13.6
5.4
4.5
3.4
8.7
21.1
'
3.9
15.4
13.2
8.3
18.7
17.6


1 Hr
50 mph Cruise
gin/mi
NOX
2.8
3.1
3.1
2.2
3.1
2.3
.
3.2
2.3
2.9
3.4
2.2
2.1

HC
0.3
0.3
0.2
0.2
0.3
0.3
.
0.2
O.I
0.3
0.3
0.2
0.3

CO
1.8
0.5
0.2
0.1
1.9
1.5
.
0.3
3.6
1.3
1.3
1.9
3.1

NOX
2.5
3.0
3.0
2.1
3.0
1.8
.
2.9
1.5
2.7
3.0
2.1
2.0

mg/mi
S04
9.6
13.0
13.8
16.1
12.2
5.7
.
18.0
8.3
9.9
11.2
8.9
6.0

CFDS
gm/mi
HC
0.5
0.4
0.3
0.3
0.4
0.6
.
0.3
0.3
0.5
0.4
0.4
0.6

CO
4.2
1.1
0.8
0.5
2.7
6.4
.
0.6
5.1
4.0
2.2
6.2
5.4

NOX
2.9
3.3
3.3
2.5
3.2
2.4
.
3.4
2.1
3.1
3.5
2.5
2.3

mg/mi
S04
9.3
13.5
14.2
16.5
12.8
3.9
.
20.8
6.0
10.0
11.5
7.7
5.8
,

-------
TABU 9
Average Emission Kesuics
Chrysler Vehicle Tests
Classification
of Tests
All Chrysler Vehicles
FTP CO < 15 gm/mi
FTP CO < 15 Rm/ml. HC < l.S cm/mi.
FTP CO < 15 gm/mi, HC < 1.5 gra/mi,
NOX < 3.1 gm/mi
Idle CO < 17.
.Idle CO ^> 1%
FTP CO •> AS gtn/ni
CFDS S04 > 10 mg/mi
Fleet Vehicles
Private Vehicles
Police Cruisers
Fleet -- No Police Cars,
Fleet and Private Vehicles --
No Police Cars
0 - 15,000 miles
15,000 - 30,000 miles
30,000 - 45.000 miles
45,000 -liles
No.
Tests
120
22
20
17
38
82
44
19
104
16
28
76
92
40
34
33
13
No
Cars
24
10
8
8
15
24
14
11
20
4
4
16
20
20
22
22
10
Idle
C07.
2.9
0.6
0.6
0.6
0.3
4.1
5.1
1.9
3.0
2.5
3.2
2.9
2.8
2.9
3.4
2.5
2.5
FTP
gm/mi
HC
2.2
1.0
0.9
0.9
1.2
2.6
3.2
1.4
2.3
1.6
2.6
2.1
2.0
1.7
2.1
2.6
2.S
CO
39.8
10.5
10.5
10.2
19.3
49.3
68.1
30.3
42.2
22.9
50.8
39.3
36.4
35.9
41.5
40.4
45.5
NOX
2.6
2.5
2.4
2.2
2.6
2.6
2.6
2.4
2.5
3.0
2.8
2.4
2.5
2.4
2.6
2.8
2.8
I Hr
50 mph Cruise
gm/mi
HC
0.2
0.1
0.1
0.1
0.1
0.3
0.5
0.1
0.3
0.1
0.5
0.2
0.3
0.1
0.1
0.2
1.0
CO
1.0
0.0
0.0
0.0
0.0
1.4
2.5
0.0
l.l
0.0
3.1
0.4
0.2
O.I
0.3
1.2
4.9
NOx
2.3
2.3
2.2
2.1
2.2
2.3
2.7
2.4
2.3
1.9
3.2
2.0
2.0
2.1
2.1
2.5
2.7
mg/mi
S04
5.8
9.8
10.3
11.1
8.3
4.6
5.3
18.5
5.9
5.1
4.6
6.4
6.2
7.0
5.9
4.9
4.2
CFDS
gm/mi
HC
0.6
0.2
0.2
0.2
0.2
0.8
1.1
0.3
0.6
0.5
0.8
0.6
0.6
0.6
0.5
1.0
0.9
CO
8.7
1.4
1.3
1.3
1.3
12.1
17.7
5.9
9.1
5.9
14.9
7.0
6.8
7.7
8.0
8.9
13.0
NOX
2.8
2.8
2.7
2.5
2.8
2.8
3.2
2.7
2.6
2.7
3.7
2.5
2.5
2.5
2.6
3,2
3.2
mg/mi
SO*
2.2
*.7
5.1
5.9 ,
4.8 >
i
i.o !
0.8
6.9
2.4
0.9
2.3
2.4
2.2
2.7
1.8
1.9
2.6


-------
     Tables 6, 7, 8,  and 9 were used  to evaluate the  cars and tests  against
various  emission criteria.  Applicable emission standards for these  vehicles
ere 1.5/15/3.1 (gm/rai)  for HC/CO/NOX  respectively.  Table 10 is extracted
from Tables 6-9 and indicates the number of cars and  tests meeting various
combination v-of these emission standards.  The idle CO < 17. criteria shows
a general correspondence to the FTP CO < 15 gin/mi criteria.
                                Toblt 1O
          TESTS  GROUPED  BY  EMISSION  CUT POINTS
     ALL TESTS

     FTP:CO< 15

     FTP-CO<15,HC<1.5

     FTP-CO 1%

     CFDS  S04>10mg/mi
                                   ALL
                                  TESTS
37
                                      19
        GM
FORD
Chrysler
                    22
                                  NOTE- 3 tests on 4 AMC vehicle not included
                                       HC.CO. NO, oil (gm/mi)
                                 23

-------
                                   SECTION 4

                                  FUEL ECONOMY

LABORATORY AND OVER-THE-ROAD DATA

     Laboratory fuel economy was measured by the carbon balance technique for
FTP, CFDS and 50 mph cruise segments of each vehicle test.  HFET fuel economy
was added in the final few months of testing.  Average over-the-road (OTR)
fuel economy and vehicle speed were obtained between vehicle test points by
use of fuel and hour meters installed on each car at the beginning of che
project.  Further experimental details are presented in Section 8 of this
report.

     Table 11 lists the average fuel economy results obtained for each of the
test group cars throughout the two year.' of testing.  The HFET was included
as a part of the test sequence at test #118 in August 1972; by that time 12
vehicles had left the project.  Except for three vehicles with more than one
test after this date, HFET and Combined fuel economy reported are for the
final test on each vehicle.  Table 11 also gives EPA fr.el economy results for
certification vehicles corresponding to test group vehicles by e.igine family
and inertia weight specification(20-22).  Figure 7 shows speed versus time
traces for the three EPA driving schedules used in this study; Table 12 gives
some characteristics of the various laboratory test cycles.
                     TABLE 12.  TEST MODE CHARACTERISTICS

FTP
HFET
Combined
CFDS
50 Cruise
length
(miles)
11.1
10.2
10.7
13.5
50.0
average speed max speed
(mph) (mph)
21.3
48.2
28.4
34.8
50.0
56.7
59.9
59.9
57.0
50.0
time stops/mile
(sec.)
1877
765
1135
1398
3600
2.1
0.1
0.2
0.2
0.0
time at idle
(W
19.2
1.0
2.1
2.3
0.0
     Average fuel econotiy from carbon balance and OTR measurements are shown
graphically in Figurt S as a function of average vehicle speed  for the various
test segments.  The C.~R data covers 1.5 million vehicle miles and averaged
32.8 mph and 15.1 mpc.
                                     24

-------
                   TABLE 11
AVERAGE FUEL ECONOMY FUCK TEST CRCXT VEHICLES
AEL Carbon Balance KPC Hc»«ur«neni»
                       At.L  Over  Tnt  Ro«d Meat jreaent i
                                                             FPA UPC
Car «
1
2
3
6
5
6
7
B
9
10
11
12
13
16
1}
U
1?
IB
19
20
21
22
23
24
25
26
27
28
29
30
?l
31
33
31
35
56
37
3e
39
60
41
42
43
6i
45
66
47
48
49
SO
51
52
S3
54
55
56
Means
STD. DEV
FT?
9.9
12.1
9.1
10.3
16.9
11.9
16.6
13.6
11.3
16.9
16.9
10.2
9.4
8.5
10.6
10.7
11.2
10.9
11.0
16.7
16.1
IS 3
16 0
9.S
19.3
11.6
14.2
16.7
17.9
U.I
12.0
20.2
15.0
9.6
10.1
18.0
IS. 9
1S.S
11. S
12.6
1°.B
11.9
17.6
16.9
10.7
18.0
12.1
23.6
17.3
10.2
12.4
16.6
9.7
13.3
11.6
8.1
13.7
3.S
H"tT
1S.S
..
..
17.6
2S.9
..
28.1
16.0
22.2
2S.1
23.8
13.4
..
..
17.8
17.6
-.
16.7
IS. 8
2S.2
23.1
-.
22.8
..
29 2
17.4
23.4
23.6
33. 5
-.
IS. 9
3S.O
21.5
16.9
16.6
23.6
..
21.3
..
..
27.9
19.7
2S.6
20.5
16. S
27.0
19.7
36.3
2S.O
16.2
17.3
1<».5
17.8
18.1
17.3
13.2
21.4
S.S
CoiMne>!
12.1
..
..
13.4
20.0
..
22.3
17.2
13.8
21.0
19.0
11.3
••
..
13.6
13.4
..
13.2
12.4
19.6
18.3
--
18.3
..
22.7
13.9
19.9
19.6
23.3
..
13.6
26.3
17.5
12.5
12.6
20.3
..
17.5
..
.-
22.3
14.7
20.9
17.7
13.1
21.2
IS. 2
27.6
20.
11.
16.
16.
13.
13.
13.?
10.0
17.0
6.2
CFD5
13.3
15.8
13.0
16.0
23.0
16.0
22.6
16.8
16.7
22.8
23.2
13.3
13.6
11.7
16.6
16.6
IS. 2
16 4
14 7
22.8
22.2
20.5
21.6
13.2
25.8
15.3
19 7
21.9
26.3
21.1
15.6
28.1
18.5
13.8
14.1
22.7
20.6
19.9
15.7
16.6
26.6
16.5
22.9
19.9
16.7
26.3
16.6
31.7
22.6
13.7
16.3
17.8
13.6
16.8
15.2
11.6
16.3
6.6
50 Cruise
15.6
17.9
16.9
18.6
25.4
18.0
25.9
18.3
18.6
26.3
26.3
17.1
15.6
13.0
18.6
16 6
17.5
18 3
17.7
26.3
26.1
26 1
25.6
16.9
31.7
18.1
23.9
26.7
36 1
26.3
17.6
34.3
21.6
17.7
17.9
25.6
23.1
22.8
17.7
19 3
30.0
20.8
25.9
21.6
17.3
26.1
19.9
36.9
25.9
15. S
19.0
20.3
16.2
19.9
17.7
13.8
21.5
5.6
                                                      FTP   HFET    COB* i-
30.5
30.5
27.6
33.0
26 8
35.1
33.6
36.2
38.6
SO. 6
36.2
39.2
37.0
37.6
28.2
33.6
31.6
37.3
38.7
38.6
3. .3
:s.o
36.2
37.1
36 1
27.5
28.5
21.6
60. 3
36.1
19 2
35.2
40.2
36.8
36.9
36.6
26.6
36.1
36.2
23.9
35. 2
26.8
31.1 '
22.6
33.0
32.5
35.7
25.7
19.6
26.1
31.9
27.6
36.3
32.2
26 8
65.4
32.8
6.0
10.6
11 7
7.1
11.9
16.3
13.2
16.9
11.6
13.1
21.7
18.2
1!.3
6.2
6.3
13. S
12.4
11.0
13.2
13.7
17 8
16.6
15.2
16.6
12.6
23.8
12.2
16.1
16.9
25. 8
26 5
9.7
23.7
19.2
12.8
12.5
17.6
16.7
17.6
13.6
10.7
20.3
13.1
21.8
15.7
15.6
20.6
16.6
22.8
..
..
13.5
16.6
8.7
13.1
12.0
..
1S.1
6.6
10
16
10
12
17
16
17
16
12
17
17
12
10
10
12
12
16
12
12
18
18
17
17
10
26
13
IS
18
22
IS
13
19
17
13
13
18
16
16
IS
13
19
13
16
16
11
22
13
30
18
12
16
16
11
16
13
9
1S.O
3.9
16
18
IS
17
23
18
23
18
17
23
23
17
IS
16
17
17
16
. 17
17
23
23
25
23
16
36
19
23
23
35
19
16
78
23
17
17
23
21
23
21
18
28
17
23
21
16
31
19
39
23
16
19
21
15
19
18
17
20.6
5.2
11
IS
12
16
19
IS
19
16
16
19
19
16
12
11
16
16
IS
16
16
20
20
20
19
11
27
15
16
20
26
17
15
22
19
16
16
20
16
19
17
IS
22
15
20
ie
13
26
IS
33
20
13
16
16
13
16
16
11
17.0
4.3
                      25

-------
        TRANSIENT
          PHASE
         BAGSI83
  too
  80
 = 60
 i«o
  20
   O
20
                                               STABILIZED
                                                 PHASE
                                                 BAG 2
          200      400      600      600
                              TiME, sec
                         FTP (or LA-4.UODS)
                                             10 oo
                                                      1200
                                                              1J7I
  100
  80

.1 *°
  20
   0
6O
40
          200      40O      600      800
                              TIME, sec
                        CFDS(orSET-7,(CUE)
                                             IOOO
                                                      <200
                                                              use
                                    765
                         Figure 7
         FTP.CFDS AND HFET  DRIVING SCHEDULE
                     (SPEED vt TIME)
                            26

-------
     Vehicle test group averages are presented for measured carbon balance
FTP, HFET, CFDS and 50 mph cruise fuel economy at the bottom of Table 11.
The EPA certification FTP fuel economy value of 15.0 mpg was in very close
agreement to the measured OTR value of 15.1 mpg.  Measured FTP fuel economy
averaged 9% less than the OTR economy while the HFET and 50 mph cruise values
overestimated the actual OTR economy by 41 and 427. respectively.  Figures 9, 10
and 11 show the same results as Figure 7 for three engine family groups:
Chrysler 225 CID 1-6 cylinder, Chrysler 318 CID V-8, and Buick 350 CID V-8,
respectively.  Laboratory fuel economy results within these engine family
groupings are quite uniform as seen by the + Lr bounds indicated.

Fuel Economy Trends With Mileage Accumulation

     Plots of fuel economy vs. mileage accumulation were prepared for each test
group vehicle.  From these, data trends of fuel economy with increasing vehicle
age can be evaluated.  Figures 12, 13 and 14 are typical of the variety of
fuel economy results obtained on three test group vehicles.

     For most vehicles the fuel economy is relatively unchanged with mileage.
Some long-term drift, both increasing and decreasing fuel economy, is observed
as in Figures 12 and 13.  Large jumps in fuel economy between two test points,
such as in Figure 14, are not uncommon however.  It has proved impossible to
systematically determine the reasons for such changes in every case.  Change
in vehicle driver, rapid deterioration of drive-train, major and minor main-
tenance, etc., are not part of the data base, making correlation of fuel
economy with all pertinent vehicle parameters impossible.  Increases i'n  fuel
economy have been noted for several (but not all) vehicles when idle CO  level
dropped significantly.

     Fuel economy and mileage accumulation data were fitted with straight
lines from which slopes, normalized to a 10,000 mile basis, were computed in
the same manner as for emissions  trend analysis as  in Section 3.  The slopes
from all vehicles were then used  to prepare histograms showing percentage
change in ftfel economy per 10,000 miles for the test group.  Figure 15 contains
the histograms for the FTP, CFDS  and 50 mph cruise.  In all three cases, an
increase of approximately  27.  tuel economy per  10,000 miles was found.

Analysis of OTR Fuel Economy Results

     The average fuel economy and vehicle speed data between laboratory  test
points has been analyzed for  seasonal variation and effect of vehicle inertia
weight.   Fuel economy  from all  intervals was  first  averaged for each car, and
the ratio of  fuel economy  in each interval to  the overall  average for that
vehicle computed.  Data  from  all  cars and all  intervals were then plotted
against the month in the year,  computed as the midpoint between  test dates.
Figure  16 shows these  fuel economy  results, and Figure 17  shows  average  vehicle
speed plotted in the same manner.  From these  figures, no  seasonal  shifts in
vehicle economy or speed are  ap'parent.  Seasonal changes may be  obscured by the
method of using the calendar midpoint to represent  the interval  between  tests.
The range of  fuel economy  and speed variations  shown  in  Figures  16  and  17 give
an indication of the OTR variability for these parameters. Average vehicle
                                     27

-------
IS}
OB
          E
27
26
25
24
23

21
20

18
17
16
13
14
13

11
10
20
                  FTP
                                   FUEL
         Figure 8
    ECONOMY BY TEST MODE
        mpg  vs. mph
56 Vehicles, 256 Emissions Testa,
1,530,873.7 Over The Road Miles
                                                    i
                                 t> AEL Carbon Balance mpg
                                 1  (±10~ Bounds Identified)
                                 6 EPA Carbon Balance mpg
                                 * Average Over The Road mpg 8 mph
                                     Measurements For  1,530,873.7 Miles
                             25
      30
COMB.
                                              35
                                            CFDS
                                             mph
40
45
50
                      HFET
                                                                                                   CRUISE

-------
NJ
vO
         a
         E
31
30
29
28
27
26
25
£4
23
22
22
21 •
20-
19
18
17
16-j
            15
20  )
   FTP
                                             Figure 9
                                        225-16 CHRYSLER
                                 FUEL  ECONOMY  BY TEST MODE
                                           mpg vs. mph
                                    10 Vehicles,  35 Emissions Tests,
                                    213,667 Over The Road Miles
                                                                          A EL Carbon Balance mpg
                                                                           (1 
-------
w
o
22
21
20
19
18
17
16
15
14
13
12
11
10
 9
 8
 7
 6
 5
20
                                           .  Figure 10
                                      318- V8   CHRYSLER
                                 FUEL  ECONOMY  BY TEST MODE
                                           mpg vs. mph
                                   8 Vehicles,  35 Emissions Tests,
                                    264,229  Over The Road Miles
	£	
                                                                     AEL Carbon Balance mpg
                                                                       (tier Bounds Identified)
                                                                     EPA Carbon Balance mpg
                                                                     Average Over The Road mpg & mph
                                                                       Measurements For 264,229 Miles
   FTP
                           25        |   30
                                   COMB.
                                         45
            CFDS
             mph
HFET
                                                                                     50
                                                                                      T
                                                                                                50
                                                                                              CRUISE

-------
  22
  21
  20
  19
  18
  17
  16
o15
a
6 14
  13
  12

  10
   9
   8
   7
   6
   5
                 Figure 11
             350-V8  BUICK
      FUEL ECONOMY BY TEST MODE
               mpg vs. mph
        5 Vehicles,  25 Emissions Tests,
         167,509  Over The Road Miles
                                           AEL Carbon Balance mpg
                                            (tlor Bounds Identified)
                                           EPA Carbon Balance mpg
                                           Average Over The Road mpg ft mph
                                            Measurements For 167,509 Miles
20
25
                                30
       FTP
        COMB.
 35
Cf^DS
 mph
40
45
1
      5?
HFET   5*0
    CRUISE

-------
  FUEL ECONOMY vs MILEAGE ACCUMULATION
           Figure 12 CAR NO. 2
  20-1
    :
  10
                  ••— f
                                 -•FTP
                             — Ftood
  20
    0  5  10  15  20 25  30  35 4O  45  50
          Figure 13 CAR NO. 19
s   \
115J
1
  10
         Road
                                       FTP
  36

"5
1
    0  5  10  15  20 25  30  35 4O  45  50

           Figure 14. CAR NO. 25

                          50 Cruise
  16
    0  5  10  15  20 25  30  35 40  45  50
                 ODOMETER (thousands)
                 32

-------
                                                     Figure 15
                                          MILEAGE ACCUMULATION TRENDS FOR
                                          CARBON BALANCE FUEL ECONOMY
                                           TOTAL VEHICLE SAMPLE  GROUP
CJ
  20
Q
UJ

V>
£15

OT
UJ

U
             fe
             ^o  5
• . .
J


1

Li

£

MEAN INCREASE" 2 OZ%
(Par 10 ,000 Miles)

-

in
i r



W

1_

y


-------
2.0
1.9
i.e
1.7
1.6
1.5
1.4
I.I
1.2
1.1
1.0
0.9
0.8
0.7
0.6
O.S
0.4
0.3
0.2
0.1
0.0
              M =  (interval DTK rapg)/(Average Car OTR mpg)
•    *
                        *    *
                      *    +
                                 Figure  16.   Seasonal OTR Fuel Economy*

-------
w    -
m    5
2.0
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1.0
0.4
0.8
0.7
0.6
O.S
0.4
0.3
0.2
0.1
0.0
                                                                 S ••-• (Interval OTR mph)/(Average Car OTR wph)
                                                       J      J       A
                                                           Month
                                        .   Figure 17.  Seasonal  OTR Vehicle Speed

-------
speed from all intervals is also shown in Figure 18 as a cumulative frequency
plot.

     Several analyses were performed to establish a relationship between
vehicle inertia weight and Tuel economy.  While inertia weight had a signifi-
cant effect on fuel economy in comparisons among individual cars, the wide
range of results at any one inertia setting and the limited weight range
representation in the test group did not support any conclusions quantifying
a general relationship between fuel economy and vehicle inertia weight.

Control Vehicle Fuel Economy

     OTR fuel economy and vehicle speed are available for the project control
vehicle (# 1) for every tank fill in the course of the scudy, spanning over
30,000 miles.  The control vehicle was fueled exclusively from a 1,000 gallon
tank at AEL using commercial lead free fuel.  These data are for much snorter
time and distance intervals than the 5,000 mile test interval values used for
the calculation of other test vehicle OTR fuel economy.  Figure; 19 and 20
show OTR fuel economy and average speed for this vehicle for each tank fill
by month of the year.

     In Figure 19 a gradual seasonal fuel economy shift is noticeable during
the warmer months.  Each point in Figure 19 represents at most a few hundred
miles and a time period of not more than a week.  This allows the data to be
more sensitive to factors such as type of usage, weather and road conditions,
etc., than for the OTR intervals on other test group cars where eac.h interval
represents about 5,000 miles and several months.
                                    36

-------
  100

S  90-
LJ
vi  BOi

ui  70

V  60-

^  30-
   40*
g  20

58  10
                               Figure 18
                CUMULATIVE FREQUENCY  DISTRIBUTION
                         OTR VEHICLE SPEED
                   56 Vehicles, 178 Intervals,~2 5 Million Miles
     10  12  14  16  18  20 22  24 26  28 30 32 34 36  38 40 42 44  46
                                    SPEED (mph)
                                                                                                  L

-------
u>
 17

 16
 IS
 14

 1)
 12
 11

 10

  9
  8

  7
  6

  5
  4

  3
  2

  1

'0
                                                   **
                          **
                   *  +
                                                                       *      *
                                        AHJJASON
                                                                   Month
                                       Figure 19.   Seasonal OTR Fuel Economy  for Control Vehicle.
                                                                                  mini iMnlffrr	""-

-------
          70
         60
   mph
\o
          40
          30
         20
                                                                             »      «•
'.•       •    .v    .
  •
                                                                     *
                                    AHJJASON



                                                         Month


                                 Figure 20*  Seasonal OTR Vehicle Speed for Control  Vehicle.

-------
                                  SECTION 5

                  CHARACTERI7ATION OF PARTICULATE EMISSIONS
INTRODUCTION

     Particulate samples were analyzed for sulfate content as one of the key
objectives of the project, and these emission retes have been presented in
Section 3.  Addition?! analyses provide a more complete characterization of
the parliculate emissions for these cars and are included in this section.

SULFATE EMISSIONS

Stabilized CFDS Sulfate Emissions

     Previous studies (1-8) of sulfate production from catalyst-equipped
vehicles have shown that the efficiency of conversion of fuel sulfur to
sulfate particulnte is dependent on catalyst type (monolith or beaded) and the
presence or absence of an air pump.  Measurement of sulfate particulate
emissions from catalyst-equipped cars is complicated by storage and release of
sulfur-bearing compounds from the catalyst.  Early studies of prototype cars
(2, 15, 16, 17) frequently showed large variations in observed emission rates
from the same vehicle in series of back-to-back tests.  Therefore, five con-
secutive CFDS cycles were used in order to insure representative CFDS sulfate
values.

     After 155 tests, analysis of the five CFDS cycles yielded fairly consis-
tent patterns of sulfate emissions for three of the four possible catalyst/air
pump configurations.  The five CFDS sulfate emission rates were individually
averaged over all tests representing each configuration to ascertain a com-
posite pattern of sulfate emissions variation for the given system configura-
tion.  These results .are shown in. Figures 21, 22, and 23 for the following
configurations: 1) monolith without air pump, 73 tests; 2) monolith with air
pump, 22 tests; and 3) beaded without air pump, 51 tests.  Since only 9 tests
on two vehicles comprised the last configuration, beaded with air pump, this
group was not analyzed for emission variations.

     Examination of cycle'T sulfate averages for the monolith without air pump
configuration reveals cycle 1 sulfate emission rates which are significantly
higher than the average of cycles 3. 4, and 5.  Indeed, almost half of the
tests on vehicles with this configuration exhibit cycle 1 emissions which are
greater then the above pverage value by more than three times the standard


                                    40

-------
     SULFATE EMISSIONS FOR CFDS CYCLES

        Figure 21.  MONOLITH CATALYST WITHOUT AIR PUMP
   30
   2.0
=!  1.0
to
                                             STD DEVIATION
                                            •*~ BOUNDS
                                             REPRESENTATIVE
                                               AVERAGE
                 234

                    CYCLE NO.
|150-
CO
V)
je
Ul
2 5.0
n









































                                             STD. DEVIATION
                                            •— BOUNDS


                                            REPRESENTATIVE
                                              AVERAGE
o
<
K
LJ
   1.5
   1.0
   05*
  12345

            CYCLE NO.



Figure 23. BEADED CATALYST WITHOUT AIR PUMP
                                     STD DEVIATION
                                    —- BOUNDS,


                                     REPRESENTATIVE
                                       AVERAGE
                 234

                     CYCLE NO.
                            41

-------
deviation.  As seen in Figures 22 and 23, there appears to be little "memory"
of previous test cycles for the monolith with air pump and beaded without air
pump configurations,  -for all three configurations, the second CFDS cycle
gives an average sulfate value within the standard deviation bounds defined
by the lest three CFDS cycles.  Therefore, in order to simplify test protocol
while still maintaining data integrity, only two CFDS cycles were run for
tests #163 and beyond.  On this basis, all individual vehicle sulfate emission
rates presented in Section 3 are the second CFDS value.  Detailed analysis of
sulfate emission rates in Sections 5 and 7 use the second CFDS value fur tests
after #162; for tests where 5 CFDS cycles exist the average of the last 3
cycles were employed.

Sulfate Emissions at Idle

     Two filters were collected during idle periods of the test sequence for
tests up to and including test #162.  One was collected during the 5-minute
idle separating the 50 mph cruise from the first CFDS cycle, the other was a
composite sample from idle periods after CFDS cycles 3, 4, and 5.  BCA analy-
sis of these filters showed low levels of sulfate emissions during idle
operation.  When a driving cycle and its associated idle period were combined,
less than 27, of the sulfate collected and 0.2% of the fuel culfur recovery
could be attributed to the idle period.

Sulfate Emission Rates

     Sulfate emissions as percent of fuel sulfur recovery are presented in
Table 13.  All emission rates have been normalized to 0.030 wt 7. S using
actual fuel sulfur values provided by fuel analysis.  Fuel sulfur content, as
well as fuel lead and manganese, are indicated in Figure 24 as three month
running averages.

TOTAL PARTICULATE MASS

    .Total particulate mass was determined for every filter collected.  Par-
ticulate from the cold-start FTP usually appeared as a black carbon-like
deposit, while the CFDS and 50 mph cruise tests showed a tan or white partic-
ulate.  Sulfete emissions from the FTP were lower than for the CFDS or 50 mph
cruise.  Table 14 gives totnl particulate mass, averaged over all tests on
each car, for the FTP, CFDS, and 50 mph cruise segments.  The percentage of
this particulate found to be sulfate is indicated for each segment.  Also
presented in this table are comparisons of relative emission rates of total
particulate in CFDS and 50 mph cruise relative to FTP results.

ELEMENTAL PARTICULATE ANALYSIS BY XRF

     Perticulate samples from the 1-hour 50 mph cruise were analyzed for 10
elements by x-ray fluorescence (XRF).  Elements analyzed were: bromine, lead,
zinc, copper, iron, sulfur, calcium, phosphorous, aluminum, and manganese.
The 1-hour cruise was adopted in order to collect sufficient particulate for
                                     42

-------
                                               Table 13
                                    Sulfate Emissions as % of Fuel
                                          Sulfur Recovery By
                                    Catalyst/Air Pump Configuration
Configuration
Tests    Fuel Sulfur Recovery as Sulfate(%)
Sulfate Emission Rate (mg/mi)

Monolith '.Jithout Air Pump
Monolith with Air Pump
Beaded without Air Pump
Beaded with Air Pump
All Tests

124
39
80
16
259
FIT
0.82
2.33
0.50
0.60
0.94
50 Cruise
6
14
1
6
6
.31
.26
.58
.32
.04
CFDS
1.98
14.13
0.94
6.00
3.74
HFET
2.79
36.33
2.14
15.74
7.24
FIT
1.72
4.29
0.89
1.34
1.83
50 Cruise
8.08
17.20
2.03
10.16
7.71
cros
3.21
18.70
1.32
10.13
5.39

3
31
?
25
10
IIKET
.53 (24)
.33 (8)
.75 (11)
.49 (5)
.30 (44)
              Note:  All sulfate emission rates normalized to 0.030 weight percent
                     sulfur in fuel.

                     For HFET # of tests are indicated in parentheses.

-------
                                      Figure 24
                                FUEL ANALYSES
                        THREE MONTH RUNNING AVERAGES

                   NUMBER OF SAMPLES USED IN AVERAGES (229 TOTAL)
       8 . B , 6 . 9 t 12 , 15 , 18 , 14 t 7 , 11 , 10, T , 7 , 5 . 1 , 6 , 16, 9 t 9 , 14 g I ,0,9,9.9,9,2
  .020

  .010
1
i
  .000

  .020
    MANGANESE ANALYSIS BEGAN DEC. 1976
o
  .000
   .040-
   D20-
       0
      1975
JFMAMJJASONO
             1976
                                                                     LL
JFMAMJJASONCI   F
             19V7              1978

-------
                     Table  14
        Total Articulate Dritsicns ty car
Total Paniculate ng/n    TP; % of FTP
« T> at S04
CARt t
1
2
3
4
5
6
7
t
9
10
11
12
13
14
IS
16
17
16
19
20
21
22
23
24
25
2fc
27
26
29
30
31
32
33
34
35
36
37
36
39
<0
41
42
43
44
45
46
47
48
45
SO
51
52
53
1<
55
56
AVLFACb

of Tests
11
6
7
5
4
4
5
S
5
5
S
S
10
2
4
3
5
S
4
5
S
4
6
2
6
4
5
5
4
4
4
S
3
S
S
5
3
6
3
2
4
4
4
3
4
5
4
4
3
3
5
3
b
4
3
3


F7P
22.62
10.70
10.90
43. t6
54.28
3.76
15.11
6.34
37.65
2S.41
37.71
36.99
26.95
9.14
52.31
53.16
5.13
.•6.17
34.24
26.77
44.35
4.24
31.68
10.69
11.57
41.46
32.47
3.62
11.51
4.72
11.20
10.09
12.04
22.38
17.96
13.8'.
6.92
7.55
5.78
10.98
8.07
55.35
24.36
35.49
10. 16
15.75
21.33
9.05
7.9d
6.96
4. '6
17 68
14.23
5.74
•16.28
J3.97
21.70

SOC
10. (1
1.C6
S.OS
4.23
4.12
1.92
3.70
11.77
12.70
4. £4
6.25
8.25
4.40
6.46
8.47
6.18
6.10
12.54
13.52
7. 55
5.16
0.79
4.SE
9.69
11. El
13.95
7.34
1.34
1.63
1.41
10.22
O.EO
14.62
16.41
22.19
10.30
1.67
4.93
3.34
4.62
2.12
6.76
7.33
20.64
io.es
13.77
10.60
1.9B
9. 06
0.92
4.70
20.19
10.95
l.f.
11.91
18.47
U.22

CFDS
13.01
l.Et
2.2'i
4.16
4.59
2.49
4.60
14.67
5.75
2.53
3.19
I/. . 57
4.19
11.17
6.35
7.75
4.22
6. El
6.73
4.C4
4.75
1.10
2.76
3.23
13.68
23.74
9.29
1.73
3.16
2.33
9.36
3.75
7.76
4.34
6.79
5.61
5.E5
3.71
4.15
2.04
6.67
9.24
9.08
28.79
9.t5
12.26
14.97
2.<2
3.
-------
detection since emission rates were expected La be very low.  Detection
limits (ug/cm? of filter area) for the :iRK system are shown in Table 15.
Translation of these detection limits to tig/mi for typical l-hour-50 mpb
cruise sampling conditions are also shown in Table 15.  In addition, Table 15
lists the percentage of tests wj.ch samples below the XRF detection limit for
each element.  Table 16 is a tabulation of individual car average particulate
elemental emissions.  No trend with mileage accumulation was observed for
elements analyzed.  Histograms in Figures 25-34 illustrate the distribution
of observed emissions.  Tests with non-detectable emissions have been excluded
from these histograms and the number of exclusions indicated on each figure.

     For lead, sulfur and manganese, the particulate emitted can be compared
to the fuel input for each element during the 50 mph cruise.  Recoveries of
these elements based on fuel usage were low.  Lead and manganese are probably
trapped in the catalyst and engine/exhaust system.  Most fuel sulfur is
emitLed as SC>2 and little is found as particulate sulfur.  Figures 35, 36,
and 37 are histograms of the individual test particulzte recovery percentages
for sulfur, lead, and manganese, respectively.

PARTICULATE ANALYSIS BY 7.0N CHROMATOGRAPHY (1C)

     At the end of the study, ion chromatography (23) was used to analyze the
archived filters previously used for XRF analysis.  Anions determined by 1C
were Cl~, Br~, PO,-, F~, and N0-j~, in water soluble extracts of particulate.
Chromatographs of these filter extracts showed low levels of the ions analyzed.
Section 8 contains a comparison of the results of the BCA, XRF and 1C analyses
for sulfui and sulfate.  In Table 17 the total particulate mass emission rate
during the 50 mph cruise is broken down into a sulfete (based on XRF sulfur),
XRF non-sulfate, 1C non-sulfate and "remainder" contributions.  When sulfate,
XRF non-sulfate, and 1C detected species are combined, they account for
approximately 65% of the total mass of emitted particulate regardless of the
various sub-classifications listed in Table 17.  These findings are in
general agreement with results from similar work at Southwest Research
Institute (14).
                                     46

-------
       Table 15



XRF Detection Limits
                   ELEMENT

Lower limit of detection
by calibration standard
(microgram/cm? of exposed
filter area)
Same as above translated
to typical 1 hr. 50 raph
cruise (micrograms/mi.)
7. of tests lower than
detection limit
Br

0.05
2.2

47
Pb

0.1
4.4

27
Zn

0.2
8.8

74
Cu

0.2
8.8

91
Fe

0.05
2.2

71
S

0.025
1.1

2
Ca

0.008
0.4

33
P

0.09
4.0

24
Al

0.07
3.1

92
Mn

0.011
0.5

67

-------
                                     Table 16*  Average XKF Emissions by Car
w
Miles
Car Tests Tested Br
1 11 49176. b O.UO
2
)
M
5
5
^
8
9
10
11
12
1} 1
14
1 V
If
17
ia
19
;u
21
22
2)
24
25
26
27
28
29
10
)1
12
))
34
Ji
J6
37
18
39
40
41
42
4 J
44
45
46
47
4H
49
50
51
54
51
14
5S
bo
16467.
41869.
llbJl.
12629.
13719.
13904.
JU114.
37270.
3U509.
37606.
48771.
54719.
7B4B.
4H799.
J7b7o.
364U2.
324 12.
17367.
40464.
29U54.
IOJ',2.
29118.
J2B6.
28704.
1217S.
28067.
19504.
21752.
1794}.
I2U93.
17010.
26560.
24611.
JOBbl.
11692.
10914.
30299.
'" 14162.
4222.
414H5.
22107.
29JJ6.
11809.
322B4.
27135.
26544.
21590.
6197.
60S4.
11771.
15487.
0.12
0.04
0.01
0.21
0.01
0.00
0.01
0.01
0.02
0.01
0.00
0.08
0.01
0.01
u.oi
0.00
0.00
0.00
0.01
U.OI
0.14
0.00
0.00
0.00
0.02
0.14
0.02
0.00
0.00
0.25
0.00
O.U5
0.00
0.00
0.00
0.02
0.00
0.13
0.01
U.02
0.04
0.04
0.00
0.00
0.05
.01
.01
.00
.00
.68
.01
76H46.7 0.01
J1B42.9 P. 26
17U51.6 0.17
4V19U.b O.OB
Mean *•» 327UB.il 0.07

Pb
0.01
0.01
0.01
0.01
0.02
0.01
0.02
0.11
0.04
0.01
0.02
0.01
0.01
0.10
0.04
0.01
O.U4
0.01
0.02
0.02
0.01
o.oo
0.01
o.o4
0.01
0.05
0.04
0.02
0.02
0.01
0.12
o.oi
0.08
o.oi
0.01
O.OJ
0.02
0.02
0.04
0.02
O.U2
0.04
O.U2
0.04
O.OS
0.01
0.06
O.UU
0.02
0.01
0.00
0.09
O.OJ
O.Oii
3.0J
O.IJ
0.04

Zn
0.04
0.01
0.01
0.00
o.oo
0.00
o.ui
o.oo
0.04
u.oo
o.ui
0.00
0.04
0.00
n.on
u.iiu
O.OI
U.OI
0.01
0.00
0.01
o.ou
o.ou
0.00
0.00
0.00
0.00
0.00
o.co
o.oi
O.OS
U.HO
0.01
O.UO
O.UI
o.uu
O.UO
O.UO
U.OI
0.00
U.OI
O.UI
o.ui
0.00
u.ul
0.02
u.oo
o.oi
O.UO
0.00
O.UO
0.01
o.ni
o.i-u
0.00
O.M5
0.01

Cu
0.02
0.01
0.01
0.02
n.oo
o.on
0.00
0.00
O.UO
o.ni
0.01
o.ui
u.uo
o.oo
o.oo
U.UU
U.Ul
U.UH
0.04
o.oo
o.uu
O.UO
0.00
0.00
0.01
O.UI
o.oo
o.oo
0.00
o.ou
u.oii
n.oo
o.oo
0.06
o.ui
o.oo
u.uo
U.UU
O.OI
u.oo
u.ou
0.00
o.uu
0.00
11.01
o.uu
0.00
0.00
o.uo
o.uu
o.uu
u.oo
(1.00
U.UO
u.uo
(1.00
0.01

Fe
0.01
0.01
0.01
0.02
0.00
n.oo
o.ou
0.04
n.oi
(i.OO
I). 00
0.01
O.UJ
U.OI
U.UU
U.UU
0.01
u.oo
u.oo
u.oo
0.00
0.01
0.00
0.00
0.00
0.09
11.00
O.OI
o.u.
0.00
0.02
0.00
0.05
U.Ul
0.00 •
U.OI
0.01
11.00
0.00
0.00
u.oi
u.oo
o.uu
0.01
0.01
u.ou
0.01
o.ou
o.ni
o.oo
0.00
0.01
(1. 04
o.ou
u . no
II. (1(1
P. 01

s
2.19
0.05
1.211
0.16
0.00
0.17
0.01
2.6H
1.67
U.96
1.18
1.41
o.co
0.16
1.4B
u.yy
1.70
4.31
3.57
1.19
0.84
U.U2
1.05
2.11
1.79
1.64
0.01
0.11
0.16
0.22
0.75
0.02
0.21
4.59
4.17
2.10
0.15
1.49
0.12
1.01
0.01
1.11
U.B6
l.frB
1.05
1.19
1.1.1
O.U4
1.7V
1.11
O.B1
5.57
1.86
0.07
0.01
1.26
1.45

Ca
0.19
0.00
0.04
0.0}
O.OS
0.02
0.04
0.05
O.OH
0.02
0.01
0.02
0.08
0.00
0.04
.0.0}
0.00
O.OS
0.07
0.04
0.04
0.02
0.01
0.00
0.03
O.OS
0.10
0.02
0.02
0.02
0.07
0.04
0.03
0.04
O.OS
O.OS
0.01
0.04
O.OI
0.00
O.OS
0.16
0.07
0.12
0.03
O.OS
0.08
0.02
0.07
0.06
0.03
0.19
O.OS
O.OS
0.13
0.13
0.06

P
0.17
0.01
0.09
0.01
O.OS
0.01
0.04
O.OS
o.in
0.02
0.04
0.02
0.18
0.02
0.04
O.OS
0.02
O.OS
0.07
0.07
0.07
0.04
0.01
0.01
0.01
0.10
0.12
0.01
0.02
0.01
0.11
0.01
O.OS
O.OS
0.07
O.OS
0.01
0.04
0.01
0.00
O.OS
0.26
0.07
0.11
0.03
0.07
0.07
0.02
0.06
0.08
0.02
0.21
0.01
0.04
0.12
O.lb
0.07

Al
0.00
n.oo
o.no
o.oo
o.oo
o.oo
o.oo
0.00
0.01
O.Ob
o.on
0.00
o.ou
0.00
0.00
0.00
0.01
o.ou
0.00
o.ou
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.01
0.00
O.OI
0.00
0.00
0.00
0.00
0.00
0.00
O.OU
0.00
0.00
0.02
0.00
0.00
0.00
o.ou
o.ou
0.00
0.00
o.ou
o.ou
u.oo
n.oo
o.ns
n.on
o.oc
n.iin
0.00

Mn
0.00
O.UO
0.00
0.00
0.00
0.00
0.00
O.or
0.11
0 •>
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.01
0.00
0.00
0.00
0.00
0.01
0.00
O.OI
0.00
0.00
0.00
0.01
o.ou
0.00
0.02
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.01
0.00
O.UO
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.no
o.no
0.00
            All jjg/mi except S which is mg/mi.

-------
r
c

i
•5
jS
*•*
0
Ul
o
u
£
w
f|
id
cr


24
20

16

12


8

4
n
Figure 25 FREQUENCY DISTRIBUTION
OF
~











• PARTICULATE BROMINE EMISSIONS

134 Emission Tests in Figure









120 Tests Lower Than Detectable
Limit Not Shown



-T

n
1 HfLrrfh fTvTI n-TIr, r™ r^ n
O.OO  OO4  OOB  012   016  O20  O24  O 28  032  O36  040  O44  O48
                 BROM:NE EMISSION  RATE


"yi
£
.5
?
E
•s
5*
>
Z
i±i
3
£5
E
UJ
>
»=
<
UJ
a:



36

32

28




20


16

12


8


4
o
n Figure 26 FREQUENCY DISTRIBUTION






















OF
PARTICULATE LEAD EMISSIONS


186 Emission Tests in Figure
68 Tests Lower Than Detectable
Limit Not Shown


-




















"


>|
1 rrn n n-,-, n -• n r-i r-,
OOO  O04  OO8  O12  O.<8  O2O  O24  O 28  052  036  04O
              BROMINE EMISSION RATE (mg/mO

-------
5 28
£
c
•S 24
j£

•6 20
s?   •
> <6

I  12

I.
§
Ul
                       Figure 27   FREQUENCY DISTRIBUTION
                                            OF
                               PARTICULATE ZINC EMISSIONS
                                    65 Emission Tests in Figure
                                    189 Tests Lower Than Detectable
                                       Limit Not Shown
                                        PI    rn
        OOI  O02  O03  OO4 OO5  O06 0.07  OO8  O.O9  OlO  OH
                ZINC EMISSION RATE (mg/m.)
                      Figure 28   FREQUENCY DISTRIBUTION
S 28
o '
*> 94.
.2
•5 20

> 16
2
Ul
o 12
Ul
ct
«*• 8-
Ul
a ft
wr
PARTICULATE COPPER EMISSIONS











f


































23 Emission Tests in Figure
231 Tests Lower Than Detectable
Limit Not Shown

•









•
in n o
   OOO  004 O08  012  O16 020  024  026
                 COPPER EMISSION RATE (mg/mi)
                             50

-------
36-r
m
I32
•K 28-
•ft
124
0°«
o
5 16
§
£.2
u.
UJ
> 8
S 4-
or
oL
000
Figure 29 FREQUENCY DISTRIBUTION
OF
PARTICULATE IRON EMISSIONS

74 Emission Tests in Figure
180 Tests Lower Than Detectable
Limit Not Shown

-




-
Ih nm n n n
004 008 012 016 O20 O24 028 O32 O,S6
IRON EMISSION RATE (mg/mi)
f

"s e
M
c 7
8
I 6
"5
5s 5
FREQUENCY
c>< *
o
f '
T
nL
: Figure 30 FREQUENCY DISTRIBUTION
OF
PARTICULATE SULFUR EMISSIONS

250 Emission Tests in Figure
-. ,-, 4 Tests Lower Than Detectable





Limit 'Not Shown
I
\



p
m r r r
-T ll" > rrrflfln rfl n
000 040  080
120   160  200  240  280  32O  36O  400  440 480
  SULFATE EMISSION RATE (mg/mi)

              51

-------
 8  .6,

 I  ,«H
I
£  ,0
§
OC
U.
O
UJ
UJ
QL
6
                   Figure 31
                              FREQUENCY DISTRIBUTION
                                         OF
                        PARTICULATE  CALCIUM EMISSIONS
                                 169 Emission Tests in Figure
                                  B5 Tests Lower Than Detectable
                                     Limit Not Shown
UJ
     OO  OO6  012   O18  O24  030  034

               CALCIUM EMISSION RATE  (mg/mi)
    16
VI    '
jt   14

.§
R   12
ti
o   «>
8?

i   8
UJ
3   H
UJ
a:
u.   4
UJ
               f-igure 32       FREQUENCY DISTRIBUTION
                                         OF
                        PARTICULATE PHOSPHORUS EMISSIONS
                                 192 Emission Tests in Figure
                                  62 Tests Lower Than Detectable
                                     Limit Not Shown
                                         r-Tlpn
    00  004  008 Ol?  016  020  024 028 O32  O36  040  044
                 PHOSPHORUS EMISSION RATE tmg/mii
                                  52

-------
« 35
c
Q
1 30-
"B 25-

fc 20-
U
o 15
UJ
DC
u.
uj 10-
i
UJ
K o















™

















1








Figure 33 FREQUENCY DISTRIBUTION
OF

PARTICULATE ALUMINUM EMISS

21 Emission Tests in Figure
233 Tests Lower Than Detectable
Limit Not Shown



-

ip n
    0.0 0.04 008  0.12 0.16  0.20  024 O28  032 036 040
                  ALUMINUM EMISSION RATE (mg/mi)
r
5   7CH
I  **
£  ^
"  40
UJ
3
u
a:
UJ
   30
uj   20

<   10
Figure 34    FREQUENCY  DISTRIBUTION
                       OF
        PARTICULATE MANGANESE EMJSSIONS
             84 Emission Tests in Figure
            170 Tests Lower Than Detectable
               'Limit Not Shown
     00  001 O02 003  004 005 006 O07 O08 009
                 MANGANESE EMISSION RATE (mg/mi)
                                 53

-------
   32-
     «

   28-


   24-


   20-


   16-


   12-


I   8-
                               Figure 35
              FREQUENCY DISTRIBUTION OF PERCENT
              FUEL SULFUR RECOVERY IN PARTICULATE
                                     4.7% Mean Recovery on 250 Tests
—  0
                8    12
                           16    20    24   28
                            Sulfur Recovery (%)
32    36   40
                              Figure 36
              FREQUENCY DISTRIBUTION OF  PERCENT
              FUEL LEAD RECOVERY IN PARTICULATE
                                    1O % Mean Recovery on 176 Tests

                                    Lead values below detection limit
                                    on 68 tests not included
                           16    20    24    28
                            Lead Recovery (%)
                                                  32    36   40
                               54

-------
  8
                Figure 37
FREQUENCY DISTRIBUTION  OF PERCENT
FUEL  MANGANESE RECOVERY IN PARTICULATE
.a
UJ 6
                                   12% Mean Recovery on 69 Tests

                                   Mn values below detection limit
                                   an 85 tests not included
I3'
  2-


  H


  0
                     mi
m
u
               8    12    16   20    24    28
                         Manganese Recovery (%)
                                   32   36    40   44
                              55

-------
             Table 17




Total Particulate Subclassification
Classification # of Tests
All Tests
Ford Tests
CM Tests
Chrysler Tests i
Total Particulate:
< 3 rag /mi
< 10 mg/ml
> 10 mg/mi
Tests in Mileage Interval:
0-10 k mi
10 k - 35 k mi
> 35 k mi
214
29
82 ' :
103

72
163
51

46
127
41
Total
Particulate
(mg/mi)
6.86
11.13
4.15
7.81

1.61
3.87
16.41

7.65
6.76
6.25
Sulfrte
(mg/mi)
4.44
7.99
2.10
5.31

0.67
2.19
11.62

5.92
4.15
3.68
Zxrf
non-sulfur
(mg/mi)
0.25
0.21
0.29
0.23

0\14
0.23
0.31

0.26
0.22
0.33
EIC
non-sulfur
(mg/mi)
0.14
0.08
0.19
0.12

0.11
0.15
0.13

0.17
0.14
0.10
7. of
Total Particulate
(Sulfate+xrf+IC)
64.38
69.30
58.26
67.88

57.48
62.56
70.21
•
73.39
62.30
60.75

-------
                                  SECTION 6

                           CATALYST ACTIVITY TESTS
INTRODUCTION

     Near the completion of the data collection phase of the project the test
protocol was modified to include raw exhaust measurements before and after
the catalyst through sample ports welded into the exhaust system.  Data were
collected at idle, 30 mph and 50 nph cruise.  Parameters measured were HC, CO
CO. concentrations, and exhaust gas temperatures.

     Thirteen of the 56 cars had left the .project prior to the introduction
of catalyst activity testing, leaving 43 cars in the catalyst activity test
data base.  Results of the before/after catalyst tests are summarized in
Tables 18, 19, and 20 for idle, 30 and 50 mph test modes, respectively.

RESULTS AT 30 AND 50 MPH

     Conversions of HC and CO for 30 and 50 mph tests were used to identify
those cars vith active catalysts.  Using an arbitrary criteria of 75% HC and
90% CO conversion, 707. of th'e 43 cars tested were active at the last test in
the project.  A breakdown by catalyst system configuration gave the following
percentage of active catalysts in each group:  1) monolith without air pump,
73%; 2) monolith with air punp, 88%; and 3) beaded without air punp, 54%.
Since this activity test was performed as the last test for each car, we con-
clude that the la-rge majority of tests during the study were performed on
cars with active catalysts.

RESULTS AT IDLE

     Many of the catalyses identified as active for CO oxidation at 30 and
50 inph were inactive at idle.  For example, Table 21 shows a comparison of
results for two cars, similar in their 30 and 50 mph activities, but exhibit-
ing markedly different idle CO conversions.  For car 23, engine-out idle CO
of 1200 ppm is 100% converted, whereas for car 21 no conversion was found with
an engine-out idle CO of 15,000 ppm  (1.5%).  When engine-out CO is high the
intrinsic capacity of the catalyst to oxidize CO is overcome by the CO levels
present in the gas rcream.  This phenomena was not apparent  for HC conversions
at idle.
                                       57

-------
                                         Table 18  Catalyst Activity Measurements at  Steady  Statet  Idle
Ui
00
  Car Number
 1
 6
 s
 7
 8
 9
10
11
12
IS
16
18
19
20
21
23
25
26
27
28
29
31
32
34
35
30
38
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
                      Catalyse
              Inlet Conccntratlons(ppnO
HC
1700
. 2300
600
1400
9000
tSOO
2800
1200
1400
2000
900
2100
3800
2800 .
9100
1600
1500
6500
1800
10000
6600
7000
7800
3800
1700
1600
s:oo
4100
2000
7000
1300
900
3100
1800
3500
4000
3300
5500
5500
3600
8700
6800
9800
CO
1200
15800
700
4100
35600
9000
15800
14800
5300
24400
2700
15000
13600
11200
15000
1200
1400
1700
10500
61200
62000
1400
73500
47000
8000
7600
1300
16JCO
12500
1700
3800
6500
26000
7700
47000
4500
4400
900
14000
2200
2200
26500
35200
Average Converter
 Tegycrature( C)
       347
       296
       244
       196
       216
       214
       136
       218
       375
       25C
       2? 5
       238
       417
       234
       274
       295
       287
       396
       260
       235
       162
       360
       171
       252
       303
       160
       211
       144
       304
       146
       298
       437
       350
       378
       366
       136
       314
       290
       288
       431
       294
       260
       356
Catalytic ConversienQJ
HC
81
22
15
22
13
23
4
0
72
23 .
13 •
33
84
44
86
83
62
89
23
7
34
95
40
27
33
19
43
26
70
11
86
67
20
81
27
23
53
76
15
79
85
24
0
CO
100
0
0
0
15
89
0
2
99
3
0
0
99
17
0
100
100
82
0
1
0
100
23
0
8
0
24
0
85
4
100
65
15
100
0
2
35
88
8
96
100
12
16
Mass Cenversion(g/mln)
HC
0.45
0.15
0.01
0.04
0.25
0.32
0.00
0.00
0.38
0.12
0.03
0.17
1.30
0.24
1.30
0.28
0.14
1.52
0.09
0.09
0.21
1.69
0.27
0.29
0.17
0.07
0.46
0.10
0.29
0.09
0.30
0.24
0.08
0.37
0.12
0.09
0.54
0.82
0.13
0.57
1.22 ;
0.28
0.00
CO
0.80
0.00
0.00
0.00
2.21
5.03
0.00
0.09
3.96
C.32
0.00
0.00
11.27
0.73
0.00
0.51
0.42
0.74
0.00
0.19
0.00
0.71
2.89
0.00
0.40
0.00
0.12
0.00
4.51
0.02
2.05
3.56
1.14
1.39
0.00
0.02
0.96
0.31
0.35
0.85
0.74
1.08
3.23
   Exhaust
How Rate SCm
                                                                 20.2
                                                                 18.6
                                                                  9.2
                                                                  8.3
                                                                 12.7
                                                                 19.1
                                                                  5.0
                                                                  9.0
                                                                 22.9
                                                                 15.8
                                                                 14.2
                                                                 14.7
                                                                 25.0
                                                                 12.0
                                                                 10.2
                                                                 12.8
                                                                  9.0
                                                                 16.2
                                                                 13.7
                                                                  7.7
                                                                  5.7
                                                                 15.5
                                                                  5.3
                                                                 17.3
                                                                 18.5
                                                                  0.7
                                                                 11.7
                                                                  5.8
                                                                 12.9
                                                                  7.4
                                                                 16.3
                                                                 25.6
                                                                  8.8
                                                                 15.6
                                                                  7.7
                                                                  6.6
                                                                 18.7
                                                                 1-2.0
                                                                  9.7
                                                                 12.0
                                                                 10.2
                                                                 10.6
                                                                 17.4

-------
                                        Table  19 Catalyst Activity Measurements at Steady State:  30 qph
in
NO
 Car Hunter
 1
 4
 5
 7
 8
 9
10
11
12
IS
16
16
19
20
71
23
25
26
27
28
29
31
32
34
35
36
38
41
42
43
44
4}
46
47
48
49
50
it
52
53
54
Si
56
                      Catalyst
              Inlet Concentrations(ppin)
                                Average Converter
                                 Temperature(  C)
                                                                            Catalytic Converston(I)
 HC


  500
 1200
 1200
 1000
 2300
 1400
 1200
 1100
 1400
 1300
 1500
 1400
 1'.00
 2000
 9100
 1400
 1700
  700
 1300
 2400
 1400
 1400
 1700
 2500
 1700
 1400
 1500
 1300
 2200
 1600
  600
  500
 3100
  500
 2500
 13CO
 1800
 1300
 1600
 1000
 1100
 5300
10000
    CO


    1800
    1900
    1100
     700
    9200
    8000
    1300
     900
    1300
    6500
     800
    1300
     900
    2C.OO
     800
     500
   19HOO
    3800
    3600
    6000
    1700
     400
     900
   15500
     500
     900
     800
     900
    6500
     900
     400
... 4200
   19800
    1800
    6800
     800
    4200
     600
    3600
    1400
    1300
   50000
   11900
425
366
360
330
375
386
352
364
380
370
343
374
392
360
382
357
462
502
465
325
360
442
310
326
362
324
302
354
378
340
422
506
424
458
425
330
450
428
428
464
370
394
554
HC
87
16
90
86
43
82
92
84
88
86
85
91
93
92
98
91
82
76
24
29
90
95
59
19
93
80
76
90
92
82
86
67
16
82
62
89
41
91
86
71
88
23
27
CO
100
15
100
100
34
100
100
100
100
99
100
100
100
100
100
100
96
100
0
0
100
100
61
0
100
96
87
100
100
97
100
72
21
100
36
100
54
100
100
99
93
12
44
                                                                        Mass Conversiendt/mllc)
HC
0.28
0.09
0.34
0.25
0.36
0.41
0.38
0.34
0.62
0.56
0.57
0.56
0.76
0.77
2.98
0.48
0.50
0.30
0.11
0.23
0.32
0.63
0.17
0.20
0.81
0.37
0.46
0.35
0.81
0.49
0.28
0.23
0.15
0.26
0.28
0.41
0.41
0.70
0.70
0.21
0.36
0.54
1.78
CO
2.36
0.28
0.70
0.44
2.33
5.82
0.90
0.67
1.33
6.54
0.72
1.15
1.06
2.19
0.54
0.38
14.21
4.41
0.00
0.00
0.69
0.38
0.77
0.00
0.51
0.58
0.56
0.55
5.25
0.65
0.49
1.98
2.53
2.20
0.90
0.57
2.54
0.72
3.18
0.79
0.90
5.46
7.00
                                                                                   Exhaust
                                                                                Flow Rate SCfM
39.8
29.5
19.4
19.0
22.7
22.1
21.0
J2.7
31.0
30.8
27.3
26.7
35.7
25.6
20.4
23.1
22.0
35.?
22.1
19.9
15.9
?9.0
IliO
25:7
J1.2
20.5
24.4
18.5
24.5
22.6
37.2
40.2
18.6
37.1
11.1
21.6
34.0
36.3
26.8
17.2
22.8
26.7
40.7

-------
                                      Table  20  Catalyst Activity Measurements at Steady States  SO oph
Car Number
     1
     4
     5
     7
     a
     9
    H-
    11
    12
    IS
    16
    IS
    19
    20
    21
    23
    25
    26
    27
    28
    29
    31
    32
    34
    35
    36
    38
    41
    42
    43
    44
    45
    46
    47
    48
    49
    50
    SI
    52
    S3
    54
                          Catalyst
                  Inlet  Concentratlena(ppm)
HC
100
800
1800
700
600
1500
900
sno
800
500
800
1400
900
• 1900
8900
1300
900
900
600
700
1100
600
1200
700
1100
800
1800
1300
1500
1300
500
500
1900
1000
1600
600
600
600
800
200
600
3100
9500
CO
4600
900
4000
700
4400
1300
2:00
1100
1200
300
1500
1100
1200
1700
1100
1000
2400
1900
6000
1000
800
1500
1000
600
1200
1000
200
6600
1300
1200
800
900
800
900
2400
900
1300
1300
1600
1000
1400
23600
29300
Average Converter
 Temperature(°C)
Catalytic Convorslon(Z)
       641
       S09
       514
       460
       527
       534
       518
       526
       530
       480
       518
       S38
       532
       493
       512
       498
       492
       S4P
       518
       494
       454
       S98
       442
       502
       501
       507
       444
       S18
       516
       490
       536
       566
       593
       509
       587
       473
       583
       SS4
       536
       573
       541
       566
       628
HC
94
22
85
94
77
82
92
88
75
87
86
91
92
94
98
94
76
95
16
94
94
97
90
94
94
86
93
94
93
84
79
52
84
84
95
91
94
94
84
87
91
34
28
CO
100
39
84
100
99
98
100
100
90
100
99
100
100
ICO
100
100
96
100
0
100
100
100
100
100
100
98
100
94
100
97
99
64
98
100
99
100
100
100
99
100
100
14
46
Mass Conversion(g/mllc)
HC
0.11
0.1S
0.87
0.48
0.44
l.OS
0.63
0.35
0.74
0.43
0.70
1.21
0.94
1.03
5.78
1.03
0.51
0.96
0.06
0.60
0.49
0.68
0.51
0.61
0.81
0.45
1.36
0.67
l.OS
0.76
0.42
0.26
0.97
0.81
0.66
0.47
0.60
0.64
0.83
0.09
0.44
0.89
3.07
CO
11.23
0.65
3.84
1.02
8.61
2.17
3.42
1.63
2.56
0.56
2.67
2.11
2.73
1.97
1.47
1.69
3.62
4.40
0.00
1.74
0.76
3.54
0.96
1.55
O.S1
1.27
0.33
6.87
1.98
1.63
1.68
1.19
0.96
1.84
2.09
1.21
2.94
2.78
3.76
0.92
2.28
5.67
31.69
   Exhaust
Flow Rate SCFM
                                                                  70.9
                                                                  55.7
                                                                  34.7
                                                                  44.2
                                                                  60.0
                                                                  51.9
                                                                  47.2
                                                                  44.8
                                                                  72.0
                                                                  56.5
                                                                  58.9
                                                                  58.1
                                                                  69.0
                                                                  35.2
                                                                  40.4
                                                                  51.2
                                                                  47.6
                                                                  70.2
                                                                  41.9
                                                                  52.6
                                                                  29.0
                                                                  71.7
                                                                  29.1
                                                                  58.6
                                                                  31.2
                                                                  39.5
                                                                  49.6
                                                                  33.6
                                                                  46.2
                                                                  42.6
                                                                  64.5
                                                                  63.2
                                                                  37.2
                                                                  62.0
                                                                  26.6
                                                                  40.6
                                                                  68.6
                                                                  64.8
                                                                  71.5
                                                                  29.3
                                                                  49.3
                                                                  51.0
                                                                  71.7

-------
                   TABLE 21
BEFORE/AFTER CATALYST MEASUREMENT COMPARISON
                      CAR 2\
                  IDLE 30mph 50mph
    CAR 23
IDLE 30mph 50mph
Engine out CO (ppm)
Average temperature (°C)
Catalyst conversion of C0(%)
Catalyst conversion of HC(%)
15,000
274
0
86
800
382
100
98
1100
512
> 100
98




1200
295
100
83
500
357
100
91
1000
498
100
94

-------
 ANALYSIS OF CATALYST ACTIVITY RESULTS

      Although the steady state test program emphasized a determination of
 catalyst activity for each car, other catalyst behavior information was
 obtained.  This data has been used to provide an insight into the disparity
 between idle and high speed CO oxidation, and to provide a possible explana-
 tion of S02 purge behavior presented in Section 7.  Idle catalyst activity
 corresponds to high-speed activity for cases with low idle CO; however,
 vehicles with high idle CO exhibit lower CO conversions than can be projected
 from 30 and SO mph results, even though sufficient oxygen appears to be
 present in the exhaust stream during idle.  A conservative method was used to
 project idle catalyst conversions from high speed results.  Assuming a first
 order rate law for CO oxidation on automotive catalysts in the low CO con-
 centration regime (24, 25, 26), rate constants at measured idle gas stream
 temperatures were calculated by use of the standard Arrhenius law.  An acti-
 vation energy of 30.0 kcal/gmole - °K was used; this vplue is consistent with
 both reported kinetic data (24-29) and apparent activation energies calculated
 from the present data.  Using the above method and a 30 mph rate constant
 calculated from the data, an -idle rate constant was projected.  Idle conver-
 sions of CO were then calculated from these projected rate constants.  Those
 tests which had measured CO conversions less than the projected conversion
 were classified as being idle-inactive.  Considering only active catalysts
 (based on 30 and 50 mph conversions), 90% were found to be idle-inactive when
 idle CO was greater than 1%, but only 217. were idle-inactive for idle CO less
 than 1%.  High CO appears to inhibit CO conversion over catalysts which are
 active under low CO conditions.

      This inhibition of CO oxidation at high CO concentrations (greater than
 1%) for catalysts in actual field use agrees with laboratory studies on CO
 oxidation over supported noble metal catalysts.  Kinetic studies (24-27)
 indicate that CO oxidation is first order in CO below ~100 ppm CO (at approx-
 imately one atmosphere reactor pressure), negative order in CO above ~1% CO,
 but there is a wid« disagreement in the 100 ppm to 1% CO range for the temper-
 atures at which automotive catalytic converters operate.  Uncertainty in this
 concentration range partially involves the transition from first to negative
-order kinetics, but above kinetic studies of this reaction system explain
 this uncertainty to be a result of the existence of multiple steady states.
 Various researchers (30-32) attribute this multiplicity to intraparticle
 diffusion effects, although recent experimental work (26, 33) points to
 surface-phenomena-based explanations for the multiple steady state (or
 hysteresis) behavior.

      The cited experimental evidence indicates that CO oxidation over noble
 metals is first order in carbon monoxide at low concentrations.  As CO level
 is increased, a critical CO concentration is reached at which a rapid tran-
 sition to negative order CO kinetics occurs, accompanied by a large decrease
 in the oxidation rate.  These laboratory results corroborate our field studies
 where steady-state test segments with high CO concentrations exhibit very
 poor carbon monoxide conversion, even though the oxygen content of the exhaust
                                     62

-------
stream (> 27. 02) favors more complete CO conversions in the catalytic
converter.

     It appears that the high CO levels found at idle in improperly tuned
cars doubly impairs the operation of automotive catalyst systems.  Not only
do these high idle CO levels place a large load on the catalytic converters
in terms of pollutant mass input, but the existence of these high CO levels
forces converter performance into a regime characterized by inefficient
operation relative to original design specifications.
                                    63

-------
                                   SECTION 7

                            SULFUR DIOXIDE EMISSIONS

INTRODUCTION

     Most sulfur present in gasoline is emitted from the engine as S02«  As
exhaust gases pass over the catalyst some of  this SO2 may be oxidized to SO^
which will quickly combine with water vapor in the exhaust to form sulfate
aerosol particulatc upon cooling.  Other sulfur compounds may form in catalysts
(34, 36) (e.g. -h"2s» COS) and though these, if formed, could have important
consequences, they probably do not constitute a significant percentage of the
total fuel sulfur throughput.  SOo in the exhaust can also interact wit i the
catalyst resulting in storage and/or release  of sulfur compounds, again
principally as S02.  Thus, measurement cc S02, though not a complete analysis
of sulfur compounds or the primary focus of the study, can provide insight to
the dynamic catalyst behavior during various  vehicle test modes.

     S02 was monitored continuously in dilute exhaust.  SO2 mass emitted during
any particular test segment was obtained by integration of S02 concentration
and the known CVS flow.  Separate SO2 mass emission values were obtained for
the 5 minute idle periods and the actual test segments.  Details of this
detection system are given in Section 8.

S02 PURGE AT IDLE

     Two distinct S02 emission patterns were  found in the 5 minute Idle periods
separating the various te:..: modes.  The first pattern is characterized by
insignificant S02 emission in idle periods, consistent with low fuel consumption
and correspondingly low sulfur throughput.  S02 emission dropped raonotonically
to these idle values when the vehicle was decelerated from either the 50 mph
cruise or CFDS.

     The second S02 emission pattern is characterized by a significant release
of S02 during the deceleration to the five-minute idle period following com-
pletion of the 50 mph cruise or CFDS.  Based on fuel sulfur throughput during
idle, this quantity of S02 can on.ly represent the release of previously stored
sulfur from the catalyst.  This S02 purge is  characterized by a maximum
emission level up to twcncy-fivs times the stabilized SO2 level attained
during 50 mph cruise.  Representative purges  in the idle following a CFDS
cycle usually exhibit ~.iximuro SO? emission rates of less than one-half those
associated with the 50 mph cruise, and arc found to begin during the final
idle of the CFDS.  Within a given test, there is a reasonable consistency of
purge magnitudes for all CFDS cycles.  A correlation was found between the
magnitude of S02 purge and idle CO levels.  For example, for all three tests

                                      64

-------
through  12,753 miles, Car 3 exhibits S02 emission behavior similar to the S02
trace  from Test 41 in Figure 38.  Very little SC>2 release is observed during
idle periods  from this vehicle, characterized by low  idle CO.  At Test  57 at
20,000 miles  this car showed high idle CO and a dramatic change  in S02
emissions pattern occurred, also shown in Figure 38.   Large~SO2  purges  are
noted  during  idle periods for this vehicle exhibiting high idle  CO.

     One percent idle CO is an approximate cutoff value separating small and
large  idle S02 purges.  In order to quantify purge phenomena,  S02 concentra-
tions  in the  dilute exhaust were integrated during each driving  cycle and idle
period,  yielding corresponding S02 mass values  for each segment. A  ratio of
these  masses  was defined as follows:

                                       idle purge SO9 macs
     SOo purge fraction =              ,—,_ f   g—— f ..        _.
        * r  °            previous cycle  S02 mass + idle purge S02 mass

Vehicles with idle CO values greater than 1% yield larger purge  fractions than
those  with lower CO values, as illustrated by  Figures 29 and 40  for  post-50 mph
cruise and post-CFDS cycles, respectively.

TOTAL  SULFire  RECOVERY

     Total •• ilfur recoveries for a given  cycle  were calculated r.s  the sum of
sulfur output in the form of cycle sulfate and  S02, as compared  to sulfur input
..computed from fuel analysis multiplied by fuel  consumption  for the cycle.   In
general, total sulfur recoveries were  considerably less  tlian  fuel  sulfur input,
averaging 32% for all 50 mph cruise tests.  When  idle purge  S02  was  included,
an average of 457. of fuel sulfur was recovered.  Corresponding values  for the
CFDS were 587. and 77%,  respectively.   Several  factors have  been  considered  in
an attempt to resolve the difference between  fuel  sulfur  input and measured
sulfur species output,  but no single satisfactory explanation  has  been  found.
Although it is unlikely on the basis of  investigation, the most  simple
explanation would be a  systematic error  in the  SO2 detection  system. More
likely are the complexities of long-term sulfur storage  and  release  of
different sulfur compounds in relation to the  specific driving cycles of the
laboratory test, and over-thc-road use.   In either case, purge fraction is
essentially unaffected,  being only a relative  measure of when  S02  emission
occurs in  the test driving cycle.

     The magnitude of the  idle purge in  relation  to  fuel  sulfur  input  is
demonstrated  in  Table  22  where the ratio of  idle  period  purge  S02  to fuel
sulfur input  to  the  catalyst  in  the preceding cycle  is tabulated as  "S02
purge  sulfur  recovery  (7.)".  Marked differences are  apparent in  purge magni-
 tude for tests with  idle  CO  less  than  and greater than 17..   Total  fuel  sulfur
 recoveries  are  also  listed  in  Table  22.   These ''total cycle sulfur recoveries
 (7.)" include  the S02 purge contribution  fron the idle following each cycle.

      A  few vehicles  exhibit  high CO emissions during the 50 mph cruise  (Table
 3).  Compared to similar vehicles  with low CO emissions in the  50 mph cruise,
 these high CO emitters  exhibit  lower  idle S02 purges even though both are

                                     65

-------
--

                                               Figure 38
                                  PURGE OF  S02  FROM  CATALYST
10-


6-
i—
 4
la,
Ul
UJ 0
t—
_J
O
-10-
CL
a. 8-
cvl
O
W g.

4-

2
0

•
1975 PLYMOUTH
440 V8/A3
12,753 miles
IDLE CO = 0.2%
TEST 41


FTP

' rf

50 MPH CRUISE
5 MIN IDLES . •

1975 PLYMOUTH
440 V8 'A3
20,200 miles
IDLE CO = 7.0%
TEST 57
i —"''"-."
•
_. 	



NO PURG
f
fliM

SET-7




E ATIDL

.J»

SET-7




E




IDLE PURSE OF S02
i^**"




i */





^| 	 »





^





J*k
SET-7





















A





,AA
SET-7







^SA^J



















^U

SET-7







l\ 	





















1
f




3
                           30      60      90     120     150     180     210     240
                                              TIME (min.)

-------
Figure 39



0.60
^
§
fc
^
^
«S °-40
0.20
0.00
S02 PURGE FRACTIONS
BY IDLE CO LEVEL'
SOmph CRUISE
.
IDLE K

	 ' '0
IDLE T
CO>1%L
•
w/////m.

-




^


jg
NJ
^^M
~|
_J


1


























MONOLITH MONOLITH PELLETED
W.O AIR PUMP W AIR PUMP W.O. AIR PUMP


-------
                        Figure 40
0.60
0.40
0.20
o.oo
               SOz PURGE FRACTIONS
             BY IDLE COT LEVEL • CFDS
                    C0<1%  fcSI


                    C0>1%  I	I

         MONOLITH
        W 0 AIR FUMP
 MONOLITH
W. AIR PUMP
 PELLETED
W.O. AIR PUMP

-------
                                                   Table 22

                                             Fuel Sulfur Recovery
Category
   S0; Purge Fraction      SO., Purge Sulfur -RecoveryQO   Total  Cycle  Sulfur RecoveryC/.)

SOmph Cruise  CFDS Cycle     SOmph Cruise  CFPS Cycle         SOmph  Cruise  CFDS Cycle
A)  Monolith Without
       Air Pump
      (111 tests)
       All Tests           0.39
        CO < 1%            0.24
        CO > 1%            0.44

B)  Monolith With
       Air Pump
      (37 tests)
       All Tests           0.11
        CO < 17.            0.07
        CO > 17.            0.17

C) • Beaded Without
       Air Pump
      (72 tests)

       All Tests           0.39
        CO < 1%           ' 0.12
        CO > U            0.62
                 0.22
                 0.16
                 0.25
                 0.13
                 0.06
                 0.24
                 0.29
                 0.09
                 0.49
15.3
 8.0
17.8
 5.3
 2.0
10.1
13.6
 2.4
24.8
16.5
11.8
18.2
 9.2
 3.6
17.3
20.6
 5.7
35.5
45.2
41.8
46.5
57.2
49.7
68.2
33.8
22..
44.7
77.2
76.1
77.6
76.8
76.7
77.0
67.1
64.2
70.1

-------
characterized by idle CO in excess of 1%.  Finally, a comparison of tests
performed at low mileage (< 15,000 miles) and high mileage indicates no
statistically significant effect of mileage accumulation on SC>2 purge behavior.

DISCUSSION OF S02 PURGE PHENOMENA

     Comparison of occurrences of S02 purges during idle periods characterized
by high CO levels provides a basis for relating SC>2 purges and catalyst opera-
tion.  With this connection taken into consideration, analysis of catalyst
operation under high CO level conditions points to two plausible hypotheses
for the existence of SC>2 purges.

     Parametric temperature sensitivity of the reactor system to relatively
small changes in converter inlet conditions (i.e. CO concentration) may
explain these S02 purge patterns.  However, temperature data obtained since
our earlier analysis(ll) of this S02 release mode indicate that catalyst
temperature excursions do not appear to be sufficient in most cases to accou.it
for release of significant S(>2 during idle periods.  Even though CO loads on
the catalyst systems are sufficiently high, the very low conversions character-
istic of the negative order CO kinetic regime do not result in heat production
rates large enough to yield significant temperature increases within in
catalyst substrate.

     An alternative explanation of the occurrence of S02 purges focuses upon
surface phenomena characteristic of supported noble metal catalysts operating
•fn the presence of high lex-els of carbon monoxide.  CO oxidation at these
conditions appears to be negative or.ler in CO because of the strong adsorption
of CO on platinum relative to other species present in the engine exhaust
stream(24, 25, 26).  As gas phase CO concentrations increase, surface coverage
by adsorbed CO (on Pt) increases to the point where adsorbed Oo (necessary
for the oxidation reaction) is displaced by adsorbed CO, thereby reducing the
CO oxidation rate.  Our evaluation of the pertinent Langmuir-Hinshelwood type
rate equations for CO oxidation indicates that the surface coverage of
adsorbed oxygen in the catalyst falls off faster than the corresponding rise
in CO surface coverage with increased gas phase CO levels.  Therefore, bince
the CO oxidation rate is proportional to a product of 02 and CO surface
coverages, the overall CO oxidation rate falls off with increasing CO gas phase
concentration at high CO levels.  If high CO levels strip the catalytic surface
of adsorbed 02, the same phenomena can occur with adsorbed S02 and other sulfur-
bearing species.

     The following scenario is proposed  to explain the purge of S02 after
deceleration to idle in the presence of  high idle CO levels.  The  large
increase in gas phase CO concentration coincides with deceleration  to idle
results in a much greater concentration  of CO on the catalyst surface than
characteristic of non idle operation during the previous  test cycle.  Catalyst
surface coverage by CO  becomes  so  large  that significant  amounts of adsorbed
02(  M>2 and possibly other sulfur-bearing species  are quickly stripped off
the  catalytic surface and dumped  into the converter gas stream, creating an
S02  purge.  This surface phenomena model of S02 purges  is  supported by the
 finding  that purge magnitude  correlates  with idle  CO concentration.

                                      70

-------
     Also in agreement with the above proposed hypothesis is the observation
that no significant S02 purges were found for vehicles exhibiting high CO
emissions during the 50 mph cruise despite the high idle CO exhibited by these
same vehicles.  If the exhaust during the 50 mph cruise has high CO levels,
then the corresponding large CO surface coverages limit the amount of S02
adsorbed during the 50 mph cruise.  The advent of high idle CO during the
subsequent idle period does not result in a S02 purge because very little
adsorbed sulfur is available for stripping off into the gas stream during
idle.
                                    71

-------
                                  SECTION 8

                    EXPERIMENTAL PROCEDURES AND EQUIPMENT

EMISSIONS TESTING

Background

     This study was initiated in response to the need for data on sulfate
emissions from catalyst cars during extended periods of mileage accumulation
in consumer use.  Regulated emissions, fuel consumption, non-sulfate particu-
late, and tune-up parameters were also of interest for cars in the study since
1975 marked the public introduction of oxidaLive catalyst emission control
technology.  The testing sequence adopted to obtain these data at each vehicle
test point is shown in Table 23.  In the course of two and one half years of
data collection, modifications were incorporated to this initial test protocol.
These changes are listed at the bottom of Table 23 with the vehicle test
number at which the change was instituted.  Table 24 shows the typical time-of-
day schedule for the various test segments.

Vehicle Check-In and Soak                                    i
                                                             i
Fuel and Hour Meters —

     Upon introduction to the test group, each vehicle was outfitted with an
engine hour meter (Engler Instrument Co., Model J12N6) and a totalizing fuel
meter (Service Recorder CO., Service Oil Meter).  These meters remained on
the vehicle throughout th». project.  A typical fuel meter installation is
shown in Figure 41.  The fuel meter is a positive displacement type (no
minimum flow requirement) with an accuracy of + 17..  Fuel meters and a pro-
tecting fuel filter were installed between the fjel pump and carburetor.  The
hour meter was connected to the ignition switch and was in operation whenever
that switch was in the "start" or "run" position.

Tank Fuel Sample —

     Vehicles were tested in "as received" condition such that owner's tank
fuel was used whenever possible.  Since the length of each tesc was approxi-
mately 120 miles, the vehicle- tank, had to be at least 1/2 full prior to
testing.  When vehicles were delivered to AEL with insufficient fuel for the
entire test sequence, enough additional conuiercial lead-free gasoline was
added (and recorded) from the AEL fuel facility to perform the test.  When
sufficient fuel was in the tank, a one gallon sample was pumped, as shoxm in
Figure 42.  These fuel samples were shipped in lots of 10 to the EPA Sourer.
Fuels and Molecular Chemistry Section in Research Triangle Park for analysis


                                   72

-------
                             TABLE 23
                Data List for Each Emissions Test
         Test Segment
               Measurements
Vehicle Check-In before 12-20 | Idle HC, CO; Engine Analyzer Check-in
Hour Soak
(ignition, timing, power balance, EGR,
etc.) Visual emission system integrity.
Tank fuel sample:  Sulfur, Lead, Phos-
phorous, Manganese, Reid Vapor Pressure,
API Gravity, Density, Distillation
(Mote 1)
Odometer, Engine hour meter, totalizing
fuel meter.
 1975  FTP
Gaseous emissions: HC, CO, NOX, C02, S02
One 47mm fluoropore filter for entire
FTP:  Total particulate mass, Soluble
sulfate by Barium Chloranilate (EGA)
SC>2 trace in dilute exhaust and mass by
continuous integration.
02 continuous  trace in raw exhaust.
 1-Hour -  50 MPH Cruise
Same as for  FiT? with  1 additional 47ram
fluoropore filter  for Particulate
Elemental Analysis by X-ray Fluorescence:
Aluminum, Phosphorous, Sulfur,  Calcium,
Iron,  Copper,  Bromine, Zinc,  Platinum,  Lead
and Manganese. Anions:   Cl~,  Br~
Fl", NOo" by 1C.
 5-Minute Idle Periods
 SO2  trace, mass  by continuous integra-
 tion.   Soluble sulfate  mass by BCA from
 47mm filters  collected;  A) one filter
 for  first  idle after 50 cruise and B)
 last 3  idle periods averaged on single
 filter   (Note 2)
 Five CFDS cycles  followed by
 5-minute idle periods
 (Note 3)
 Sane as  for FTP.
 HFET  (Note)
 Same as for FTP,
 Three,  15-minute steady state i  HC,  CO,  C02,  02 and temperature before
 (Idle,  30mph,  50mph) raw      |  and  after catalyst during last 10 minutes
 exhaust tests   (Note 5)       j  of each segment.
 NOTES:  1)  Added nanganeso analysis from tank fuel after test #149, 12/76.
         2)  Dropped idle filters af^er test #162, 3/77.
         3)  Dropped last thre= CFDS segments after test #162, 3/77.
         4)  HFET segment added at test #218, 8/77.
         5)  Added steady state converter performance segments at
             test #218, 8/77.
                                    73

-------
                                  Table 24



                                 Test Day








TVpical Time	Test Segment	




 2:00-4:00              Deliver loan vehicle and pick-up test vehicle.



 3:00-5:00              Check-in test vehicle, collect fuel sample,




                        initiate cold soak,  weld pores for raw exhaust




                        test,  swap tires.



 7:00-9:00              Begin  FTP testing.




 9:00-10:00             Begin  one hour 50 mph cruise.




10:00-11:00             Begin  CFDS cycles.



11:00-1:30              Begin  HFET and before/after  catalyst tests.




12:30-2:00              Prepare test vehicle for owner return.




 1:00-3:00              Return test vehicle, pick up loan vehicle.

-------
   Figure 41.  OTR Fuel Meter Installation.
.    ....   ^ _ t^j^r-
 Figure 42.  Collection of Tank Fuel Sample.
                                     Photography by Robert Johnson
                      75

-------
Analyses performed were:  Sulfur,  Lead, Phosphorous,  Reid Vapor pressure, API
gravity, density, and distillation.  Analysis for manganese was added in
December 1977.

Engine Analyzer ~

     Figure 43 shows a typical engine check-in progress.  Engine and idle
emission parameters were recorded  on a check-in sheet shown in Figure 44.  The
engine analyzer was a Sun Model EET940.  A Sun "EPA-75M" HC/CO analyzer was
used through most of the project,  but was replaced by a Horiba Mexa-300
analyzer for the last six months of testing.  Both instruments were ini-ially
calibrated against NBS traceable gases and checked with working gases period-
ically thereafter.  EGR valve operation was checked by manual application of
vacuum to the EGR valve with observation of drops in manifold vacuum and
engine idle speed confirming its operation.

Cold Soak Preparation ~

     After check-in, the vehicle was prepared for cold soak.  During winter
months front and rear wheels were  swapped to avoid testing with snow tires,
many of which were studded.  The dynamometer tire pressure was set at 35 psi
for all tests.  The checked-in vehicle was normally placed in cold soak about
4:30 p.m. for testing the next morning.  The FTP portion of the test sequence
normally began about 9:00 a.m., resulting in 14-16 hours of soak.  Vehicles
were moved to the test bay from the cold soak bay by a car mover shown in
operation in Figure 45.  Vehicles were soaked in a climate controlled room
with a maximum/minimum temperature thermometer adjacent to the car.  Soak
temperature control set point was 72°F, with an extreme minimum of 6b°F and
extreme maximum of 75°F throughout the two and one-half years of testing.

     For the final test on all but 13 vehicles, raw exhaust sampling and
temperature measurements before and after the catalyst were added.  Sample
ports were welded into the exhaust system to obtain these data as shown in
Figure 46.

Emissions Testing Equipment

Test Bay —                                                \
                                                           I
     The AEL test bay is shown in Figures 47-49.  Two air conditioner/electric
heater/humidity control units circulate 15,000 cfra of room air through over-
head ducts parallel to the vehicle as positioned on the dynamometer.  Tempera-
ture control was maintained at 22 + 2°C regardless of test mode or seasonal
variation; humidity control was less responsive to load changes, and was set
at 507. relative humidity with a range of 30-60% RH bracketing all test condi-
tions.  The dynamometer used for testing was a Clayton CTE-50-full lift,
equipped with automatic road load and direct-drive variable inertia simulation.
A Hartzel Model N24-'JW fan (525t) cfm) was directed at the front of the
vehicle.  A 20-inch squirrel cage blower (7000 cfm), Dayton Model 3C011, was
directed diagonally from the drivers side of the vehicle toward the rear
wheels.  This blower is located behind the converter to provide rear-tire

                                     76

-------
                                       I
                                                •
Figure 43.  Vehicle Check-In.
             77
                                      ,  \

-------
Figure 44.  Vehicle Check-In Log Sheet
AUTOMOTIVE EMISSIONS LABORATORY ($18) 1*57-3200
New York Slate Department of Environmental Conservation
SO Wolf Road. Albany. New York 12233
ENEIhc ANALYSIS CHECK IN SHEET
TEST NUMBER TEST BATE. , DATE VEHICLE
MAKE
START
IDLE
CRUISE
ACCEL-
ERATION
HIGH
SPEED
COHM
^
^B
m
^
w

MODEL TEAS

TEST PROCEDURE
Cranking Voltage
Cranking Coil Output
Cranking Vacuum

Idle Spaed
Dwell
Initial Timing
Hydrocarbon* PPM.
Carbon Monoxide
PCV Tail
Manifold Vacuum

Dwell Variation
Con Polaniy
Spark Plug Firing Voltage
Mr. 'Tium Coil Output
Secondary Circuit Insulation
Secondary Circuit Condition
Coil and Condenser Condition
Breaker Point Condition
Cam Lob* Accuracy
Hydrocarbon* P. P M.
Carbon Mor-oxide Percent
Cylinder Power Balance
Record R P.M.

Bpa'k Mugs Under Load
kccrlerator Pump Action

Timing Advance
Charging Voltage
NydrocaiBons PPM
Carbon Monoxide P -re- •«
Exhaust Restrictiori
READ
Voltmeter
Scope (Display)
Vacuum Gauge

Tachometer
Dwell- Meter
Timing Advance Unit
Hydrocarbons Meter
Carbon Monoxide Meter
Carbon Monoxide Meier
Vccuum Gauge

Dweil Meter
Scone (D-splav)
Scope (Duplex)
Scope pispisv)
Sccoe ;Dispiav)
Scope (Raster)
Scope (Rare')
Scope (R«:er)
Scope (Superimposed)
Hydrocarbons Meter
Caibon Monoxide Meier
Tachometer
1 12 |3
SPECS.























'Illllllli
RESULTS























'•/////////

GOOD

























BAD
























4 IS 16 |7 |8

Scope (Display)
Caibon Monoxide Meter



Timing Advance Unit
Volirneu-r
Hydrocarbons Meier
C-TOon Monoxide Meier
Vacuum Gauge





1 |

1
















LNIS :

                    78

-------
        Figure 45.   Car Mover  Operation.
Figure 4t.  Bcfore/Afl-:r Catalyst Sample Ports,

               i
                    79
                \

                \
                          \
                                                                  •     M
i

-------
J
                       Figure 47.   Emissions Test Bay.
                                    80
                                          '    '•  •
                                                                \
                                                                 >


                                                                                      •
                                                                                 .w. .'•*.-.

-------
                            -**   .-.   - ; .^.*  «_

                              ,.   •      m
                             -i •    -**-Ti^-»/-- j
Figure 48.  Dynamometer, Cooling  Fans*
  Figure 49.   Exhaust Sampling  Equipment,
               .  81

-------
cooling in order Co prevent tire failure.  These fans are shown in operating
position in Figure 48.

Particulate Collection and Exhaust Handling —

     Exhaust particulate was collected in a standard dilution tunnel(37, 38)
connected between the ir.let of the Scott model 302 positive-displacement-pump
constant-volurae-sampler (CVS) and the vehicle exhaust inlet.  CVS flow was a
nominal 400 cftn.  The dilution tunnel and particulate collection probes are
shown schematically in Figure 50.  Dilution air inlet to the standard filter
box was ducted from the exit of one of the test bay air conditioners.  Parti-
culate was collected through two probes (1 in I D x 6 In lengths) into 47 ram
Millipore filter holders.  These probes and filter holders were rigidly
mounted by a quick disconnect clamp to a 6 in diameter probe access port on
the dilution tunnel.  The probes are shown in Figure 51.  Flow control through
the probes was regulated by 10-turn Parker-Hannifin (N-800-B11) valves.  Flow
rate was monitored by Brooks model R-8M-25-2 flow meters.  A vacuum gauge
between the filter and the control valve was used to make pressure corrections
to compute total volume filtered.

     The CVS was outfitted with 9 sets of exhaust/background bags to accom-
modate the test sequence without delays for bag evacuation.  Background
sample was collected from the dilution air filter box.  CVS blower differential
and absolute pressures were measured on Merian 10AA25WM-36 and 2QAA25WM mano-
meters, respectively.  CVS blower inlet temperature was continuously recorded
on a Rustrack Model 2133 tiwnuistor probe strip chart recorder.

Gaseous Analysis —

     Bag analysis of HC, CO, C02» and NOX followed the Federal Register sample
conditioning and analysis procedures for the 1975 FTP(13).  Instruments used
for exhaust gas analysis are listed in Table 25.

     Oxygen concentration in undiluted exhaust was determined by sampling at
the inlet to the dilution tunnel  (see Figure 50).  The 02 measurement system
is schematically sliown in Figure  52.
                 *
     S02 mass emissions were determined by continuous measurement and elec-
tronic integration of SC>2 concentration in dilute exhaust, sampled at the
dilution tunnel particulate  filter station (see Figure 50).  The SO2 measure-
ment system is shown schematically in Figure 53.  Output signal from the
SM-1000 UV spectrometer was  integrated electronically and also strip chart
recorded by Disk™ integrator to  provide hard copy output of where S02 emission
occurred in any test segment.  Large purges of S02 in idle periods were
observed in the early tests, and  an electronic switching system was designed
to restart the continuous electronic integration procedure in  synchronization
with  the CVS bag switches.   This  switching system, shown in  Figure 54, per-
mitted the SO2 mass  to  be determined for successive  back-to-back test segments.

Emission Test Procedures

Dynamometer —

     Dynamometer calibration was  established both by recommended Clayton

                                     82

-------
8
             Dilution Air
        From Air Conditioner
                                          Porticulate Collection
                                          (2 Duplicate Systems)     Vent
                                                                  Constant Volume Sanr'er
                                                                                      Bag
                                                                                      Analysis
                                                            Sample Port
                                                                                 Flow
                                                                                 Restriction
               Figure 50. SCHEMATIC OF EXHAUST HANDLING AND
                          PARTICULATE COLLECTION

-------
Figure 51.  ParticuLate Sample Probes

-------
                                                          Table 25


                                          Exhaust Gas Measurement Instrumentation
00
Ul
Gas
CO
CO
C02
CO 2
02
HC
NOX
S02
CO
C02
1IC
Manufacturer
Ethyl-Intertek
Horiba
Ethyl-Intertek
Horiba
Scott
Scott
Scott
Lear-Seigler
Beckman
Beckman
Beckman
Model
URAS 2T
AIA-21-AS
URAS 2T
AIA-21
150
215
125
SM-1000
315
864
400
Type
Instrument
ND1R
NDIR
NDIR
NDIK
Paramagnetic
FID
Chemiluminescence
2nd dcrivitive UV
Spectrometer
NDIR
NDIR
FID
                                                                                     Notes
                                                                         Replaced URAS after test #161
                                                                         Replaced URAS after test #249
                                                                         Used for before/after
                                                                         converter tests

-------
                           Refrigerator
               Raw
             Exhaust
00
a*
                       Water Removal
                                            1CFM
                                             Pump
                                      Ballston
                                       Filter
Strip Chart
Recorder
                                                                   Bypass
             Paramagnetic
              02 Meter
                    Figure 52. OXYGEN  IN RAW  EXHAUST  SAMPLE SYSTEM

-------
Exit
                          Temp
                         Control
                     110°
                            Sample Cell
                                                           Raw Exhaust
                                        Mace Teflon Filter
           Fluoropore Filter Media
Lear-Seigler
 SM1000
   SOZ
                                                     Strip Chart
                 Figure 53. S02  MEASUREMENT  SYSTEM

-------
00
00
                                  FILL BAGS
                                                   CVS
                                                   CVS
                                                  wiring
                                                                  CIRCUITS
 Oplo-
iietotor
                                                                     Logic
                                                                             Pulse
                      Animating between these two sets of CVS switehfo produces a pulse
                      to print the integrated count and reset/restart the counter
                                                                               Negative
                                                                                 Pulse
                         Figure 54.  S02 ELECTRONIC  INTEGRATION SWITCHING SYSTEM

-------
caii brat. io  procedures ai:ci by c-ost -do'.T. procedures as specified in the Federal
Hegi.;ter.  rhre*» compler-* roast-dowi calibrations were -performe-j in rhe course
of tnis we./..  Daily checks on the  50 nuh power absorbtion as port of dyna-
mometer warr*-up were used to verify st.->< If ty cf calibration.  Two Drivers
aides were used, and the-je were zero checked ar.H calibrated at 50 mph as part.
of Lhe daily dynamometer preparation.  A Scott Model  201 drivers aide was used
for FTP testing, and Varian A- 4 drivers aide was used  for the CFDS tests.
Inertia settings were assigned to test vehicles based  on new car certification
test data published in the Federal  Register (40CFR 3/11/75, 41CFR46 3/8/76).

Particulate Collection —

     Hot-wire anemometer measurements were used to measure the flow profile  in
the dilution tunnel at the particulate sampling station.  These experiments
verified a flat velocity distribution consistent with fully developed turbu-
lent flow.  Mixing of exhaust gas and dilution air was also characterized by
injecting propane in the exhaust inlet to the tunnel  at a constant rate while
performing a traverse of propane concentration across  the diameter of tunnel
at the particulate sample station.  A uniform propane  profile was observed
indicating satisfactory mixing.  The tunnel was swept  and washed at 6 month
intervals with the debris sent to EPA for analysis.   Fluoropore filters, 0.5
micron pore specification, were used for particulate  sampling throughout this
study.  Flow adjustment was frequently required to maintain constant flow as
filters became progressively loaded.  Vacuum measurements were recorded and
used to correct observed flow to standard conditions.  A dry gas meter was
connected to the exit of this by stem for several tests in order to confirm
the accurate determination of total filter flow.

Constant Volume Sampler —

     The Scott Model 302 constant volume sampler (CVS) was extensively  flow
calibrated using an Autotronics Inc. turbine flrv meter  (Model  1000  flow com-
puter and Series 100 flow transducer) prior to the beginning of this project.
A minute change in calibration was  observed for the one additional  flow
calibration performed during the course of this project to check the system  for
long-term drift.

     Three CVS blower revolution counters were used -on .an alternating basis
as part of the daily propane injection test to check  for any deterioration of
counter accuracy.  Propane injection tests through  test #218 were  by a  gravi-
metric determination using lecture  bottles of propane suspended .from an Ohaus
balance (Model 71032).  Tests beyond #218 used a Horiba critical flow orifice
device (CFO model 201).  A + 5% propane recovery error cutoff was  utilized,
but this error bound was decreased  to + 2% without  any CVS or instrument
calibration changes when the CFO device replaced the  cumbersome gravimetric
method.

Analytic? 1 Instruments —
                  tor  jnalysli  of '1C,  CO,  CO;.  N0X,  and 02 v*re calibrated on
 a riorrlily h«.'i.is  with  laboratory standards.   These standard gases were + 2%
          from '.he mar.<_facL:ir<>  t'.::s*  were. t.alilratfid by the EPA Mobile Sources

                                     89

-------
Laboratory in Ann Arbor,  Michigan.  From these primary calibration gases,
working span gases were establisned for daily use.  Zero, span, and gain
settings were checked as part of the daily preparation before testing, and
between test segments.  Strip chart recordings were used to determine instru-
ment response and provide a hard copy of all calibration, zero, span, and
emission determinations.  NOX converter efficiency was checked as per Federal
Register (40CFR Ft. 86) as part of the monthly calibration.  Instruments were
operated continuously to obtain maximum stability.  The URAS-2T CO instrument
required the removal of t^O and CC^; two banks of Ascarite/Drierite columns
were used for all determination on that instrument.

     The Lear-Seigler SM-1000 second derivative UV spectrometer was set  at
301 nm to detect SO* in dilute exhaust.  The instrument was supplied with a
servo-operated ampule containing SO2 as a calibration.  A series of tests using
gravimetric injection of pure 3O2 to the exhaust  inlet of the  dilution tunnel
analogous to a propane injection test confirmed the operation  of the system.
S02 calibration gas was also used directly in the instrument to set the  instru-
ment calibration factor.  The internal S02 span ampule was calibrated from this
gas calibration and used for a daily span check.  A wet chemical method  for
SO2 determination(14) was also used to check for  interference  from other
exhaust species.  This method absorbs SO2 into 37, H202 as sulfate for subsequent
determination by the BCA system used for determination of particulate sulfate.
Several vehicle tests with parallel Lear-Seigler  and  bubbler tests confirmed
the instrument calibration and the absence of major interference by other
exhaust species.

Laboratory Analysis of Particulate

Filter Handling —

     All particulate samples were collected on 47 mm  diameter  Fluoropore™ 0.5
micron pore size media.  Fresh filters from stock were stabilized overnight in
a dessicator containing drierite prior to initial weighing.  Filters were
weighed on a micro-balance housed in a controlled humidity and temperature
glove box, shown in  Figure 55.  Each filter was placed in a numbered petri dish
upon weighing and transported to  the vehicle test bay in groups of 20 filters.
After completion of  a test segment filters were immediately returned to  the
petri dish.  The eight filters from each completed test  were placed  in a
dessicator containing dilute NH&OH vapors for a minimum  of 1/2 hour, to
stabilize particulate H2SO^ as (NH4>2 SO^.  The ammoniated filters were  then
placed  in a dessicator containing drierite overnight  in  order  to remove  water
associated with  the  particulate H^SO^.  Since  the anxnoniation  step changes the
filter  loading according to the amount of l^SO^ present, subsequent  sulfate
analysis  results were used to compute  the NH^+ mass to be subtracted  from the
total particulate mass  to arrive  at  the mass of water free particulate col-
lected.

    -  Filters were  individually placed  in  50 ml Poly-cons with  20 ml  of  607.
isopropyl alcohol  to solublize sulfate.   The  samples  were mechanically  agitated
 for one hour prior  to  filtering the  extractate  through Whatman #40  filters in
preparation  for  sulfate measurement.


                                    90


-------


Figure 55.  Microbalance  for  Particulate Mass.

                    91

                                    . v..

                                                                      .
                                                                  \

-------
Soluble Sulfate by BCA -.

     The semi-automated barium chloranilate (BCA) method of Tejada and Sigsby
(39) was used for determination of soluble sulfate loadings on the filters.
Figure 56 shows -he system in operation, while Figure 57 is a schematic of the
system.  Detectio.. of soluble sulfate occurs by passing liquid sample through
a column packed with barium chloranilaLc; barium sulfate is then formed, re-
leasing chloranilate which is quantitatively detected by a UV detector set at
310 run.  The instrumentation used here was a Technicon Samplpv IV and Propor-            ,
tioning Pump III, Valcor 5-port air actuated valve, Instrumentation Specialties
Co. high pressure pump, pressure monitor (# 1.590), flow controller (#314), and
absorbance monitor (#UA-5).  A Hewlett-Packard 7100B strip chart recorder in
parallel with a Columbia Scientific Supergntor II programmable integrator
provided necessary output.

     Prepared filter extracts were loaded in the Technicon carousel sample
holder with several blank solvent and calibration samples of (NH^)2SO^.  The             .
BCA apparatus was operated on a 6 min cycle, with 4 rain to fill the sample               '
loop and 2 min to inject the sample.  The BCA column was 1/4 in x 3 in stain-
less steel, the injection loop 1/16 in x 3 in stainless steel, and high
pressure pump rate was 100 ml/rain.  Integrated peak areas from the calibration
standards were used to generate a 2nd o'ier polynomial  fit calibration curve
for each batch of samples (usually 2 complete bar tests).  Soluble sulfate               ,
values  for the samples were computed based on this calibration curve.  XRF               '
and Ion Chromatograph analyses of filter samples indicated that interferences
of other ions with BCA sulfate determinations were negligible for filters in
this study.

Elemental Analyses by XRF —

     Elemental analyses of particuiate were performed on a Siemens wavelength-
dispersive x-ray  fluorescence  (XRF) spectrometer shown  in Figure 5€,  The
basic XRF unit was equipped with a model &•-• x-ray generator and a 10-position
carousel filter holder.  One 47 mm dia ammoniated  filter from the 1-hour 50 raph
cruise  was used  for XRF analyses.  Ten elements were measured; bromine,  lead,
zinc, copper,  iron, sulfur, calcium, phosphorus, aluminum, and manganese.  The
XRF system was calibrated with standards purchased from Columbia Scientific
Industries.  Multiple standards were used  for each element from which a  least
squares calibration line was calculated.   Correlation coefficients for these
calibration  lines were typically 0.999,  indicating excellent linearity  to  the
lower  limit of detectability.  Some additional calibrations were performed  for
light elements  (sulfur, phosphorus, manganese) by  deposition of aerosol  particu-
late on fluoropore  filters.  These filters were  analyzed both by XRF  and atomic
absorbtion to  establish calibration.

Comparison of  BCA,  XRF and Ion Chromatograph Sulfate Methods —

     To check  the  integrity of BCA sulfate results,  the duplicate 50  mph cruise
 filters previously used  for XRF elemental  analysis were analyzed  for  sulfate  by
 ion chromatography(23) at  the  end of  the project.  A valid comparison of sulfate
 values from  simultaneously collected  filters required  an p^lo-irce  for  una\  *.i •          j
                                      92
i

-------
Figure 56.  BOA Apparatus Set-Up.


-------
     Techntcon IV
       Sample
       Holder
uv
Detector
i i


UV
Absorbance
Monitor
Discard
Electronic
  Peak
  Area
Integrator
                 Sample
                 Injector
                 Loop\
                                             	Fill Loop/ Solvent Baseline
                                             	Inject Sample
                            Figure 57
SCHEMATIC FOR AUTOMATED BARIUM CHLORANILATE  SYSTEM

-------
Figure 58.  xrf System for Particulate Analysis,
                    95

-------
able flow differences between the filter used for BCA analysis, and the XRF
filter.  An indication of differences between these filters can be seen in a
comparison of specific total particulate loadings as illustrated by Figure 59.
Most of the points far from the diagonal on Figure 59 represent cases where
one or both of ur' filters plugged during the 50 mph cruise.  These cases were
not included in the pool of data used for BCA-1C comparisons.'

     Figure 60 illustrates the comparison of 1C to BCA sulfate values for those
tests where sulfate responses are above the detectable limit for both instru-
ments and no filter plugging was encountered.

     The same filter was used for elemental sulfur determination by XRF and
sulfur in the form of sulfate by 1C.  A comparison of these results in Figure
61 indicate that essentially all sulfur on the filters was found as sulfate.
For sulfur mass emission rates above 2 rag/mi, 1C sulfur values were larger than
those determined by XRF.
                                                      1
                                                       ft.
                                                        >„
                                                        t
                                     96
                                   \
                                     \

-------
"xrf"
filter
emission;;
                40.0  -
                35.0
                30.0
                25.0
                20.0
                15.0
                10.0
                 5.0
0.0

  0.0

                       (    ••  -•••
                       .• *  ,-•:*
                                      •   .• •
                            S.O      10.0     15.0     20.0     25.0     10.0     1S.O      40.0
                                            EGA filter emissions (mg/mi)

                         Figure 59*  Comparison  of Total Par'-.iculate Emissions for Two Probes,

-------
     Sulfate
„>    by 1C
09    Ong/mi)
                    25.0
                    20.0
                    15.0
                    10.0
                     s.o
                     0.0  U
                      0.0
5.0
10.0          15.0           20.0

       Sulfate by EGA (mg/mi)
2S.O
              30.0
                                         Figure  60.   Comparison of 1C  and  EGA Sulfate Analysis,

-------

Sulfur
  by
  1C
(mg/rai)
                    9.0
                    1.0
                    7.0
                    6.0
4.0
                    1.0
                    2.0
                    1.0
                                ;/
                    0.0

                      0.0
         l.O    2.0     1.0    4.0     ).0     6.0    1,0

                           Sulfur by xrf (mg/mi)
                                                       1.0     9.0
                              Figure  61.  Comparison of 1C and  xrf Sulfur  Analysis.

-------
                                 REFERENCES


 !•   Bradow, R.L., and J.B. Moran,  "Sulfate Emissions  from Catalyst Cars:  A
     Review11.   SAE Technical  Paper  No.  750090,  Society of Automotive Engineers,
     Warrendale,  Pa., 1975.

 2.   Begeman,  C.R., M.U.  Jackson, and G.J. Nebel,  "Sulfatr Emissions from
     Catalyst-Equipped Vehicles".   SAE  Technical Paper No. 741060,  Society of
     Automotive Engineers, Warrendale,  Pa., 1974.

 3.   Trayser,  D.A., et al, "Sulfuric Acid and Nitrate  Emissions from Oxidation
     Catalysts".  SAE Technical  Paper No. 750091,  Society of Automotive
     Engineers, Warrendale, Pa., 1975.

 4.   Creswick, F.A., et al, "Sulfuric Acid Emissions from an Oxidation-Catalyst
     Equipped  Vehicle".   SAE  Technical  Paper  No. 750411,  Society of Automotive
     Engineers, Warrendale, Pa., 1975.

 5*   Pierson,  W.R., R.H.  Hammerle,  and  J.T. Kunmer,  "Sulfuric Acid Aerosol
     Emissions from Catalyst-Equipped  Engines". SAE Technical Paper No. 740287,
     Society of Automotive Engineers, Warrendale,  Pa., 1974.

 6.   Beltzer,  M., R.J. Campion,  and W.L. Petersen, "Measurement of Vehicle
     Parti^culate Emissions".   SAE Technical Paper  No.  740286, Society of
     Automotive Engineers, Warrendale,  Pa.,  1974.

 7.   Bradow, R.L., et al, "Sulfate  Emissions  from  Catalyst and Non-catalyst
     Equipped  Automobiles".   SAE Technical Paper No. 740528, Society of
     Automotive Engineers, Warrendale,  Pa.,  1974.

 8.   Holt,  E.L.,  et al, "0-jntrol of Automotive  Sulfate Emissions".  SAE Tech-
     nical  Paper No.  750683,  Society  of Automotive Engineers, Warrendale, Pa.,
     1975.

 9.   Somers, J.H., et al, "Automotive  Sulfate Emissions - A Baseline Study".
     SAE Technical Paper  No.  770166,  Society  of Automotive Engineers, Warren-
     dale,  Pa., 1977.

10.   Herling,  R.J., et al, "Characterization  of Sulfate and Gaseous Emissions
     from California  Consumer-Owned Catalyst-Equipped Vehicles".  SAE Technical
     Paper(No. 770062, Society of Automotive  Engineers, Warrendale, Pa., 1977.
                                   100

-------
                                 REFERENCES

11.  Gibbs,  R.E.,  et al,  "Emissions from In-Use Catalyst Vehicles".  SAE
     Technical Paper No.  770064, Society of Automotive Engineers, Varrendale,
     Pa.,  1977.

12.  Gibbs,  R.E.,  et al,  "A Study of Fifty-Six In-Use Catalyst Vehicles".  SAE
     Technical Paper No.  780645, Society of Automotive Engineeis, Warrendale,
     Pa.,  1978.

13.  40CFR85; 38FR 16062, June 20, 1973, Effective August 20, 1973, Amended as
     shown in Volume 40,  Code of Federal Regulations, Revised as of July 1,
     1975; 40FR 28066, July 3, 1975; 40FR 33973, August 13, 1975; 40FR 58647,
     December 18,  1975.
     40CFR86; 40FR 27590, June 30, 1975; 40FR 33973, August 13, 1975; 40FR
     58647,  December 18,  1975; 41FR 9878, March 8, 1976; 41FR 29389, July 16,
     1976; 41FR 31471, July 28, 1976.

14.  USEPA,  Ann Arbor, Michigan, "Recommended Practice for Measurement of
     Exhaust Sulfate Emission from Light Duty Vehicles and Trucks".  September,
     1977.

15.  Irish,  D.C.,  and R.J. Stefan, "Vehicle Sulfuric Acid Level Characteriza-
     tion".  SAE Technical Paper No.. 760037, Society of Automotive Engineers,
     Warrendale, Pa., 1976.

16.  Trayser, D.A., et al, "Effect of Catalyst Operating History on Sulfate
     Emissions".  SAE Technical Paper No. 760036, Society of Automotive
     Engineers, Warrendale, Pa., 1976.

17.  Krause, et al, "Critical Factors Affecting Automotive Sulfate Emissions".
     SAE Technical Paper No. 760091, Society of Automotive Engineers, Warren-
     dale, Pa., 1976.

18.  Helme, M.P., and W.J. Pienta,- "Idle Emissions from New York Vehicles; An
     Analysis Over* Five Years".  Presented at 1977 Air Pollution Control
     Association Annual Meeting, Houston, June, 1978.

19.  40CFR85; 38FR 16062, June  20, 1973, Effective August  20, 1973, Amended  as
     .shown in Volume 40, Code of Federal Regulations, Revised as of July 1,
     1975; 40FR 28066, July 3,  1975; 40FR 33973, August 13, 1975; 40FR  53647,
     December 18, 1975.

20.  1975 Gas Mileage Guide, Second Edition, January, 1975, USEPA/FEA,  U.S.
     Dtpc. of Energy, Washington, D.C.  20545.

21.  1076 Gas Mileage Guide, Second-Edition, January, 1976, USEPA/FEA,  U.S.
     Dcpt. of Energy, Washington, D.C.  20545.
                \
22.  1977 Gas Mileage Guide, Second Edition, January, 1977, USEPA/FEA,  U.S.
     Dept. of Energy, Washington,  D.C.  20545.


                                      101

-------
                                  REFERENCES

23.  Sawicki, E.,  J.D. Mulik,  and E. Wittgenstein, "Ion Chzomatographic
     Analysis of Environmental Pollutants".  Ann Arbor Science, Ann Arbor,
     Michigan, 1978.

24.  Wei, J., "Catalysis for Motor Vehicle Emissions".  Advances in Catalysis,
     .24, 57 (1975).

25.  Voltz, S.E.,  et al, "Kinetic Study of Carbon Monoxide and Propylene
     Oxidation on Platinum Catalyst".  Industrial and Engineering Chemistry
     Product Reseat;h and Development, 12, 294 (1973).

26.  Tennant, B.,  and J. Wei,  "Carbon Monoxide Oxidation in a Single Pellet
     Reactor".  Paper 25a, 70th Annual Meeting of American Institute of
     Chemical Engineers, New York, New York, November, 1977.

27.  Hlavacek, V., and J. Votruba, "Experimental Study of Multiple Steady State
     in Adiabatic Catalytic Systems".  American Chemical Society Mvances in
     Chemistry Series Number 133, p. 545, Washington, D.C., 1974.

28.  Kuo, J.C.W., et al, "Mathematical Modeling of CO and HC Catalytic Con-
     verter Systems"*  SAE Technical Paper No. 710289, Society of Automotive
     Engineers, V.'arrendale, Pa., 1971.

29.  Harnet, J.L., "Analytical Evaluation of a Catalytic Converter System".
     SAE Technical Paper No. 720520, Society of Automotive Engineers,
     Warrendale, Pa., 1972.

30.  Smith, T*G.,  J. Zahradnik, and J.J. Carberry, "Non-Isothermal Inter-
     Intraphase Effectiveness Factors for Negative Order Kinetics - CO
     Oxidation over Pt".  Chemical Engineering Science, 30. 763 (1975).

31.  Hegedus, L.L., S.H. Oh, K. Barren, "Multiple Steady States in an
     Isothermal, Integral Reactor: ' The Catalytic Oxidation of Carbon Monoxide
     over Pt - Alumina".  Paper llOb, 70th Annual Meeting of American Institute
     of Chemical Engineers, New York, New York, November, 1977.

32.  Finlayson, B.A., and L.C. Young, "Mathematical Models of the Monolith
     Catalytic Converter:  Part III:  Hysteresis  in Carbon Monoxide Reactor".
     Paper HOa, 70ch Annual Meeting of American  Institute of Chemical
     Engineers, New York, New York, November, 1977.

33.  Cutlip, M.B., and C.N. Kenney, "Elementary Step Model and Multiplicity
     in Surface Rate Processes".  Paper 55b, 69th Annual Meeting of American
     Institute of Chemic I Engineers, Chicago, Illinois, November, 1977.

34.  Barnes, G.J., and J.C. Summers, "Hydrogen Sulfide Formation Over Auto-
     motive Oxidation .Catalysts".  SAE Technical  Paper No. 750093, Society
     of Automotive  Engineers, Warrendale, Pa., 1975.


                                    102

-------
                                  REFERENCES

35.  Cadle, S.H., and P.A. Mulawa, "Sulfide Emissions from Catalyst-Equipped
     Cars".  SAE Technical Paper No. 780200, Society of Automotive Engineers,
     Warrendale, Pa., 1978*

36.  Bradow, R.L,, and F.D. Stump, "Unregulated Emissions from Threc-Way
     Catalyst Cars".  SAE Technical Paper No. 770369, Society of Automotive
     Engineers, Warrendale, Pa., 1977.

37.  Somers, J.H., et al, "Sulfuric Acid Emissions from Light Duty Vehicles".
     SAE Technical Paper No. 760034, Society of Automotive Engineers, Warren-
     dale, Pa., 1976.

38.  Ingalls, M.N., K.J. Springer, and R.D. Lawrence, "Automotive Sulfates -
     A CVS Compatible Sampling System".  SAE Technical Paper No. 780644,
     Society of Automotive Engineers, Warrendale, Pa., 1978.

39.  Sigsby, J., and S. Tejada, "Determination of Soluble-Sulfate from CVS-
     diluted Exhaust:  An Automated Method".  NIEHS Symposium "Health
     Consequences of Environmental Controls", Durham, N.C., April, 1974.
                                    103

-------
                                APPENDIX A


     A punched-tape computer output of the project data base has been provided
to EPA.  Request for copies of this tape should be directed to Mr.  Peter
Gabel", MD-46, MSERB, EMCD, ESRL,  EPA,  Research Triangle Park, North Carolina.
Table 26 is a copy of a typical vehicle test output from the punched tape,
and Table 27 defines the variable  identifiers from Table 1.
                                                                                      . J

-------
                                                                        1
                 TABLE 2fc




Compute i: Output for Typical Emissions  Test
•itil CAT i,A1L CAF *t- .'.AKE A-.GLLL MILEAGE HiAFS CALS
lul 9 7/2o/7t> l»7i i-LV.-.OU'ih J-uri 2151U.O 3o4.6 o io . 3
*'.F 50-C CFCS 1 CFL£ 2
V-MX 91.82 161.65 94.03 662.45 258.91 259.00
KH 0.90 0.90 0.*2
DF 6.80 12.50 8.85
hC TG 16.82 8.85 5.67
CO TG 511.27 211.21 77.55
NOX .1C 5.93 9.C3 11.20
C02 TG 2287.04 2459.58 2251.97
hC G/H 2.58 0.00 0.00
CO G/H 64.90 0.00 O.OC
NOX C/M 2.4C 0.00 0.00
C02 L/f. 610.22 0.00 0.00
MC 11. 99 0.00 O.CO
LAC 1 STALL 0
CFCS 3 CFCS 4 CFC.L 5
V-MA 256.12 258. 66 258.66
Kh G.S2 O.S2 0.9-1
Lf t.12 8.11 b.26
IX 1C &.4e 9.58 9.62
Co -1C, 124. OC 124.10 122.00
l.tX 'iC 27.22 2o.68 ^7.14
CCI 1C 6815.41 6*02. ID /Oil. 91
III C,/:. 0.70 U.71 0.72
CO C/I-. S.1S S.21 9.C6
NuX C/K 2.02 l.»b 2.C1
0,2 C^ 51C.O- 511. 2', 524.71
i.FO 16. bS 16. tl lb.4l
lit SOC IFC£ 1
Sc2.C/hC\CLE 2.11 10. tS 17.17
SO2 l(/i-j CiC. + ID O.OC 22.47 57.12
i lUtL £ A£ 502 2.46 IS. 10 84. Ob
{•AHT ^AES rc/h 0.00 28.03 1.56
£04 tC/1; CYCLE O.CO 4.8'i 0.37
% FULL £ AS S04 O.OC 5.07 0.37
ClitCK IN FtLL
Ci.i.EK 2.0 i i t.T C.OiC
ILLt SFL 650.0 td C/IAL C.OC7
iLbL 1U. 1.0 f C/CAi O.bOL
I DLL liC &CG.G ft.V.t-. S.40G
IDLE CC 7.0 A.t.l. 56.400
Sh MN t.O ^t.NSI'l^ 0.745
£f / AX 1C.U l.B.f- fcS.L'CO
10CO IX 120.0 10 & 121'. COC
IbOC CO i.o 5u fc 221. OCC
FULL ACV l^.u <>C % 1'iS.OUC
lilbj-C IX 12C. 1 Lfr -.C^.bLL
hlS?C CO 0.0 . N G/GAL C.UOo
0, 92 0 . 92
6.12 8.26
4.95 9.06
3.78 122.57
65.44 28.42
25172.17 6996.62
0.09 0.67
0.07 9.08
1.31 2.11
503.44 518.27
17.62 16.60

hFLT
1. 00
0.0.0
U.CO
0.00
O.CO
0.00
C.CO
b.OO
0.00
c.ou
0.00
0.00
OLi 2 CFCS 1 CrtS 4
10. b9. 30.58 30.71
48. 8U 46.24 47. 60
70.76 69.09 7G.*4
O.CO O.OC C.OO
O.OG 0.00 0.00
O.CO 0.00 0.03
XKF ^/K
(A££ U5.E57
E? O.OC7
Fo 0.012
zt. c.o:o
CL O.OGU
FL O.CGC
£ 1.406
CA 0.017
F L.016
AL OiOCC
. N U.COO

G.92
8.12
9.29
121.35
29.49
7106.48
0.69
b.99
2.18
526.41
16.15














CfL£ 5
1C. 11
45. Cb
65.55
0.00
C.CO
0.00






































hFtT
C.OO
O.CO
0.00
0.00
O.OC
C.CO













                     105

-------
        Item
Test
Car
Datf.
Mileage
Hours
Gals
v-mx
KH
DF
HC TG
CO TG
NOX TG
O>2 TG
HC G/M
CO G/H
NOX G/H
C02 G/M
MFC
S02 MG/M Cycle
S02 MG/M Cycle- + ID
% Fuel S as S02
Part MASS MG/M
SO* MG/M Cycle
% Fuel S as 804

OWNER
IDLE SPD
IDLE TIM
IDLE HC
IDLE 'CO
SP MIN
SP MAX
1000 HC
1000 CO
FULL ADV
HISPD HC
HISPD CO
           TABLE 27
Computer Output Parameter List
 	Description
 Serial number of test
 Test group vehicle number
 Date of test
 Odometer at date of test
 Reading from under-hood hour meter
 Reading from under-hood fuel meter  ?
 CVS v-mix (m3)         '             '
 Humidity correction factor
 Dilution factor
 Total grams from particular test segment
zf.ro values
    missing
indicate
data
   ii     ii     ii      n
 Emission rate ga/mi
                                     it
                                     ii
            n
            it
 Carbon balance fuel economy
 SO2 Emissions rate (mg/mi) - cycle only
 S02 Emission rate (mg/mi) - cycle + idle purge
 7. Fuel sulfur emitted as S02, includes idle purge
 Total Particulate emission, gravimetric (mg/mi)
 Sulfate emission by BCA (mg/mi)
 % Fuel Sulfur emitted as sulfate

 Identifies vehicle source: 0 = AEL, 1 = Red Cross,
   2 = NYS Thruway, 3 = NYS Office of General Services,
   A = NY Telephone Co., 5 = private
 Vehicle idle speed
 Spark advance BTDC, negative values indicate retard
 HC concentration at idle, ppm hexane
 CO concentration at idle (%)
 Lowest spark firing voltage (K volts)
 Highest spark firing voltage (K volts)
 HC concentration at 1000 rpm
 CO concentration at 1000 rpm
 Spark advance at 2500 rpm minus initial advance
 HC concentration at 2500 rpm, ppm hexane
 CO concentration at 2500 rpm, 7.

              106

-------
                                  TABLE 27
                                 (continued)

                       Computer Output Parameter List

	Item	     	Description	

S % WT                  Sulfur content wt %
FB                      Lead content gm/gal
P                       Phosphorous content gm/gal
R.V.P.                  Reid Vapor Pressure (Ib)
A.P.I.                  API gravity at 60°F
DENSITY                 Density at 15°C (gm/cn3)
IBP                     Distillation Analysis (°F)
10%                          "          "
50%                          »          »
90%                          "          "
EP                           "          »
MN                      Manganese content (gm/gal)

MASS                    Total ^articulate emission rate for xrf
                          filter (mg/mi)
Br, Pb, etc.            Emission rate (mg/mi)
                                                   i
                                                   i

                                                    V.
                                    107
                                \

                                  \

-------
                                  TECHNICAL REPORT DATA
                           (Please read Instruction! on the re\ erse before completing)
I. REPORT NO.

 EPA-600/9-79-047
                             2.
                                                           3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
                                                           5. REPORT DATE
 SULFVTE AND  PARTICULATE EMISSIONS FROM TN-USE  CATALYST
 VEHICLES.  Regulated/Unregulated Emissions and Fuel
 Economy.	
                                                                      1Q7Q
             6. PERFORMING ORGANIZATION CODE
7. AUTMOniS)
                                                           8. PERFORMING ORGANIZATION REPORT NO.
 R.   . Gibbs.  G. P.  Wotzak. S. M. Bver. and  N.  P.  Kolak
9. PERFORMING ORGANIZATION NAME AND ADDRESS
                                                           10. PROGRAM ELEMENT NO.
 New York State  Department of Environmental  Conservation
 Division of Air Resources
 50 Wolf Reid
 Albany. NY  12233             	
             11. CONTRACT/GRANT NO.
                   R803520-01
12. SPONSORI JG AGENCY NAME AND AOpRESS
 U.S. Environmental  Protection Agency
 Office of Research  and Development
 Office of Health  and Environmental Assessment
 Environmental  Criteria and Assessment Office (MD-52)
                    1"** NC  27711	
             13. TYPE OF REPORT AND PERIOD COVERED

                      Final	
             14. SPONSORING AGENCY CODE


                 EPA/600/00
16. ABSTRACT
      An  emissions  and fuel economy study  of  56 catalyst cars in consumer  use  and
 maintenance has  been performed by repeated testing of the cars over a two and one-half
 year period.   This report summarizes analyses  of the data base, and includes  results
 on  idle  CO levels, mass emissions of HC,  CO, NO , sulfate, S02 and total  particulate;
 total  particulate  elemental analyses, catalyst activity, and fuel economy.  Test cycles
 used were  the 1975 FTP, one-hour 50 mph cruise, Congested Freeway Driving Schedule,
 Highway  Fuel  Economy Test, and idle,30 and 50  mph cruise for catalyst activity tests.
 Fuel economy data  for over-the-road driving  are also presented from on-board  totalizing
 fuel and engine  hour meters on each car.

      Idle  CO Indicative of maladjusted carburetors (> 1*) was found to  correlate with
 FTP CO emissions,  purge of stored sulfur  in  the form of S02 from catalysts, anc
 decreases  in catalyst activity at idle in comparison to 30 and 50 mph activity results
 Particulate sulfur emissions accounted for only 3.7% of fuel sulfur for the 256 CFDS
 tests  in the data  base.  Over-the-road fuel  economy was most closely represented by
 the FTP  (city) value.
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.IDENTIFIERS/OPEN ENDED TERMS
                           c. COSATI Field/Group
18. DISTRIBUTION STATEMENT
  DISTRIBUTE TO PUBLIC
                                              19. SECURITY CLASS /Titit Keporlj
                                                UNCLASSIFIED
                           21. NO. Of PAGES
                                 120
20 SECURITY CLASS /This pagt)
  UNCLASSIFIED
                                                                         22. PRICE
EPA Form 2220-1 (Rev. 4-77)   PREV.OUS EDIT.ON is OBSOLETE
                                               108

-------