EPA-650/2-75-054

May 1975
Environmental Protection Technology Series
    PARTICULATE EMISSIONS

            FROM PROTOTYPE

              CATALYST CARS
                           ^
                            ui
                U.S. Environmental Protection Agency
                 Office of Research and Development
                      Washington, D. C. 20460

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                             EPA-650/2-75-054
PARTICULATE EMISSIONS
     FROM PROTOTYPE
      CATALYST CARS
               by

         Dr. Morton Bcltzer

 Exxon Research and Engineering Company
      Products Research Division
       Linden, New  Jersey 07036
        Contract No. 68-02-1279
         ROAP No. 21BCE-02
      Program Element No.  1AA002
 EPA Project Officer:  Dr. Ronald L. Bradow

    Chemistry and Physics Laboratory
  National Environmental Research  Center
   Research Triangle Park, N. C. 27711
           Prepared for

U.S. ENVIRONMENTAL PROTECTION AGENCY
 OFFICE OF RESEARCH AND DEVELOPMENT
       WASHINGTON, D.C.  20460

             May  1975

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                        EPA REVIEW NOTICE

This report has been reviewed by the National Environmental Research
Center - Research Triangle Park, Office of Research and Development.
EPA, and approved for publication.  Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
                    RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environ-
mental Protection Agency, have been grouped into series.  These broad
categories were established to facilitate further development and applica-
tion of environmental technology.  Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related fields.  These series are:

          1.  ENVIRONMENTAL HEALTH EFFECTS RESEARCH

          2.  ENVIRONMENTAL PROTECTION TECHNOLOGY

          3.  ECOLOGICAL RESEARCH

          4.  ENVIRONMENTAL MONITORING

          5.  SOCIOECONOM1C ENVIRONMENTAL STUDIES

          6.  SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS

          9.  MISCELLANEOUS

This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series.  This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation  from point and non-
point sources of pollution.  This work provides  the new or improved
technology required for the control and treatment of pollution sources
to meet environmental quality standards.
 This document is available to the public for sale through the National
 Technical Information Service, Springfield, Virginia 22161.

                 Publication No.  EPA-650/2-75-054
                                 11

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                                TABLE OF CONTENTS


                                                                    Page No.

  Summary 	    1

  I.   Introduction	    4

 II.   Technical Background	    7

      II. 1  Automotive Particulate Emissions	    7 .

      II.2  Exhaust Particulate Sampling System 	    7
            II.2.1  Sampling System Components	    7
                    II.2.1.1  Diluent Air Preparation System	    9
                    II.2.1.2  Flow Development Tunne	11
                    II. 2.1.3  Exhaust Injection System	11
                    II.2.1.A  Isokinetic Probe	11
                    II. 2.1.5  Particulate Collecting Stage	13

            II.2.2  System Performance	13

                    II.2.2.1  Rapid Mixing of Exhaust and Diluent
                              Air	13
                    II.2.2.2  Development of Uniform Flow in the
                              Flow Development Tunnel 	   14
                    II.2.2.3  Tunnel Sampling Losses	15
                    II.2.2.4  Equivalent Emission Rates with
                              Parallel Filters	16
                    II.2.2.5  Temperature Maintenance at the
                              Particulate Collection State	16
                    II.2.2.6  Capabilities for Studying Effect of
                              Temperature on Particulate Collection .   21

III.   Experimental	24

     III.l  Test Vehicles	24
           III.1.1  Vehicle Conditioning Procedures 	   24
           III. 1.2  Catalyst Conditioning Procedures	25

     III.2  Selection of Fuels	,	26

           III.2.1  The Additive Package	26
           III.2.2  Fuel Specifications 	   27

     III. 3  Catalysts	27

     III.4  Test Procedure	29

           III.4.1  Gaseous Emissions 	   29
           III.4.2  Particulate Sampling Procedure	30

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                                    - ii -
                          TABLE OF CONTENTS  (Cont'd.)


                                                                   Page No.

IV.  Results and Discussion	33

     IV.1  Sulfur Compounds in Exhaust Emissions 	  33

           IV. 1.1  S02 in Auto Exhaust	33
           IV.1.2  Dependence of Total Particulate Emission
                   Rates on Fuel Sulfur Content	33
           IV. 1.3  Sulfate Emission Rates	39
           IV.1.4  Exhaust Sulfur Material Balance 	  46

                   IV.1.4.1  Sulfur Material Balance with Mono-
                             lithic Oxidation Catalysts	46
                   IV.1.4.2  Sulfur Material Balance with
                             Palletized Oxidation Catalysts	56
                   IV.1.4.3  Sulfur Material Balance with NO
                             Reduction Catalysts	x. .  . .  57

           IV.1.5  Sulfate Storage on a Pallatized Catalyst System .  58
           IV. 1.6  Bound Water in Exhaust Particulate	61
           IV.1.7  Morphology of Automotive  Sulfate Particulate.  . .  63
           IV.1.8  Non-Sulfate Sulfur Exhaust Particulate	65


     IV.2  Exhaust Metal Particulate Emission Rates	67

           IV.2.1  Metal Oxide Emissions Under 1975 FTP Conditions .  67

           IV.2.2  Metal Oxide Emissions Under Cruise Conditions,
                   Relation to Sulfate Emissions 	  69

           IV.2.3  Emission Rates of Specific Metals 	  69

                   IV.2.3.1  Emission Rates  of Platinum	76
                   IV. 2. 3.2  Emission Rates  of Aluminum	76
                   IV. 2.3.3  Emission Rates  of Lead	76
                   IV.2.3.4  Emission Rates  of Iron	82
                   IV. 2.3.5  Emission Rates  of Nickel	84
                   IV.2.3.6  Emission Rates  of Copper	89
                   IV. 2.3. 7  Emission Rates  of Zinc	89
                   IV.2.3.8  Emission Rates  of Calcium 	  89
                   IV.2.3.9  Emission Rates  of Chromium	89

           IV.2.4  Metal Oxide Emission Rates Following Sulfate
                   Storage Conditioning. ..............  93

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                                   - iii -

                        TABLE OF CONTENTS (Cont'd.)

                                                                  Page No.

    IV. 3  Organic Exhaust Particulate Emissions	    94

          IV.3.1  Carbon Content of Exhaust Particulate 	    94
          IV.3.2  Organic Nitrogenous Particulate 	    98

    IV.4  Size Distribution of Exhaust Particulate	   100

          IV.4.1  Particle Size Distribution, Base Case Vehicle  .   100
          IV.4.2  Particle Size Distribution, Oxidation
                  Catalyst-Equipped Vehicle 	   100
          IV.4.3  Particle Size Distribution, NO  Reduction
                  Catalyst Equipped Vehicle . . ?	   110
          IV.4.4  Particle Size Distribution After Sulfate
                  Storage	   110

V.  References	   115
Appendix A - Analytical Methods	

  A.I  Analytical Determination of Sulfate	   117

       A. 1.1  Reagents	   117
       A.1.2  Titration Apparatus 	   117
       A. 1.3  Standardization of BaCClO^ Solution	   117
       A. 1.4  Detailed Titration Procedure	   118

              A.1.4.1  Effect of Nitric Acid on Measurement
                       of Sulfate	   119
              A.1.4.2  Precautions About Titration Procedure. . .   119

       A.1.5  Sulfate Determinations on Glass Fiber Filters
              Spiked With Known Quantities of H2SO^ 	   120
       A.1.6  Comparison of Titrimetric and Gravimetric
              Procedures on Filters from Vehicle Tests	   121.

  A. 2  Sulfur Dioxide Determination .	   123

  A. 3  Carbon, Hydrogen, and Nitrogen Determinations	   127

  A.4  Characterization of Specific Compounds in Automotive
       Exhaust Particulate	   130

       A. 4.1  Bound Water	   130
       A.4.2  Organic Nitrogen Compounds	   130

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                                   - iv -

                          TABLE OF CONTENTS  (Cont'd.)

                                                                 Page No.


              A.4.2.1  Nitrogenous Particulate. 	   130
              A.4.2.2  Organic Nitrogen Compounds 	   131
              A.A.2.3  Compounds Containing Nitrogen and
                       Oxygen Bonded Together 	   131
              A.A.2.4  Aliphatic and Aromatic Nitro Compounds . .   134
              A.A.2.5  Nitrate, Nitrites, Nitroamines, and
                       Nitrosamines 	   134
              A.A.2.6  Nitriles 	   134

       A.4.3  Organic Sulfur Compounds	   135

              A.4.3.1  Organically Bound Di- and Tetravalent
                       Sulfur	   135
              A.4.3.2  Alkyl and Aromatic Sulfonic Acids	   135

  A.5  Determination of Metallic Components of Exhaust
       Particulate	   137

       A.S.I  Emission Spectroscopy	   137

              A.5.1.1  Preparation of Calibration Standards . . .   137
              A.5.1.2  Assessment of Interaction Effects on
                       Metal Determinations	   149
              A.5.1.3  Effect of Presence of Chromium on
                       Platinum Determination	   150
              A.5.1.4  Calibrations tor High Levels of Iron,
                       Zinc, and Lead	 150

       A.5.2  Platinum Analysis by X-ray Fluorescence 	   150

Appendix B - Modified Anderson Impactor 	   159

Appendix C - Exhaust Splitter 	   162

Appendix D - Basis of Selection of the Sulfur and Nitrogen
   Containing Organic Compounds Which Might Appear in an Auto
   Exhaust	   165

Appendix E - Raw Data	   169
   E.I - List of Raw Data Tables.	   ifiQ
   E.2 - Precision of Total Particulate Emission Measurements . .   204

Appendix F - References Used in the Appendices	   205

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                            LIST OF TABLES
TABLE NO.                        TITLE                         PAGE NO.
  III-l        Specifications of Fuels Used	      28
  III-2        Model and Serial Numbers of
               Catalysts Tested	      29
  IV-1         Average Sulfate Emission Rates (Initial
               and Final 1975 FTP) From NOX Reduction
               Catalyst Vehicle, and Base Case Vehicle ....      43
  IV-2         Comparison of Gaseous Emission Rates of
               Vehicle Equipped with Engelhard Pelletized
               Oxidation Catalyst Operated on 0.019 Wt.  %
               S Fuel	      58
  IV-3         Emission Rate of Indicated Exhaust
               Component, gms/km for Test Runs
               Following Standard Conditioning (A)
               and Storage Conditioning (B)	      59
  IV-4         Storage Experiments, Pelletized Engelhard
               Catalyst, 0.019 Wt. % S Test Fuel	      59
  IV-5         Standard Screening Tests, Pelletized Engelhard
               0.019 Wt. % Test Fuel	      60
  IV-6         Relation of Bound Water to Sulfate
               Emissions	      61
  IV-7         Estimated Maximum Emission Rates of  Non-
               Sulfate Sulfur Exhaust Particulate	      65
  IV-8         Relative Emission Rates, Total Metal
               Oxides to Sulfates for Oxidation
               Catalyst Equipped Vehicles	      75
  IV-9         Maximum Possible Platinum Emission Rates. ...      76
  IV-10        Comparison of Metal Oxide Emission Rates;
               Vehicle Equipped with Pelletized Engelhard
               Oxidation Catalyst, Test Fuel 0.019  Wt. % S .  .      93
  IV-11        Comparison of Carbon and Total Particulate
               Emissions	      95
  IV-12        Estimated Average Maximum Emission Rates
               as Determined by Detection Limits 	      98
  IV-13        Comparison of Total Particulate Emission
               Rates, Andersen Impactor Versus Total
               Filter	     112

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                                  vi

                           TABLE OF FIGURES


FIGURE NO.                       TITLE                      PAGE NO.
  II-l          Exhaust Partlculate Sampler	     8
  II-2          Schematic of Dehumldification Section. ...    10
  II-3          Counter Current Exhaust Injection
                System	    12
  II-4          Dew Point of Diluted Exhaust Vs.
                Air/Exhaust Dilution Ratio 	    18
  II-5          Relative Humidity of Exhaust Dilution Air
                Mixture at Vicinity of Sampling Probes
                During the 1972 Federal Test -
                Driving Cycle	    19
  II-6          Temperature Control System Performance -
                Catalyst-Equipped Car	    20
  II-7          Relative Humidity of Exhaust Dilution Air
                Mixture at Vicinity of Sampling Probes
                During 64 km/hr. Cruise Conditions 	    22
  II-8          Finned Tube Cooling Setup	    23
  IV-1          Dependence of Total Particulate Emission
                Rates, gins/km, on Fuel Sulfur Content
                (Average of Initial and Final 1975 FTP)
                Base Case Vehicle, 4 Monoliths	    34
  IV-2          Dependence of Total Particulate Emission
                Rates, gins/km, on Fuel Sulfur Content
                (Average of Initial and Final 1975 FTP)
                Base Case Vehicle, 3 Pelletized
                Catalysts	    34
  IV-3          Dependence of Total Particulate Emission
                Rates, gms/kxn on Fuel Sulfur Content
                (Average of Initial and Final 1975 FTP)
                Base Case Vehicle, 2 NOX Reduction
                Catalysts	    36
  IV-4          Dependence of Total Particulate Emission
                Rates, gins/km  on Fuel Sulfur Content
                Monolithic Catalyst-Equipped Vehicles
                64 km/hr. Cruise	    36
  IV-5          Dependence of Total Particulate Emission
                Rates, gins/km on Fuel Sulfur Content,
                Pelletized Catalysts, 64 km/hr. Cruise ...    37
  IV-6          Dependence of Total Particulage Emission
                Rates, gins/km on Fuel Sulfur Content
                with NOx Reduction Catalysts,
                64 km/hr Cruise	    37
  IV-7          Dependence of Total Particulate Emission
                Rates, gins/km on Fuel Sulfur Content
                Monolithic Catalyst-Equipped Vehicle
                (96 or 113 km/hr. Cruise)	    38

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                                 vli

                       TABLE OF FIGURES (CONT.)


FIGURE NO.                       TITLE                       PAGE NO.
  IV-8         Dependence of Total Particulate
               Emission Rates,  gms/km on Fuel Sulfur
               Content Pallatized Catalyst-Equipped
               Vehicle (96 or 113 km/hr. Cruise)	     38
  IV-9         Dependence of Total Particulate Emission
               Rates,  gms/km on Fuel Sulfur Content,
               NOX Reduction Catalyst-Equipped Vehicle
               (96 km/hr. Cruise)	     40
  IV-10        Sulfate Emission Rate vs. Fuel Sulfur
               Content (Average of Initial and Final
               1975 FTP)  Base Case and Monolithic Oxidation
               Catalyst-Equipped Vehicle	     40
  IV-11        Sulfate Emission Rates vs.  Fuel Sulfur
               Content (Average of Initial and Final 1975
               FTP) Base  Case and Pelletized Oxidation
               Catalysts	     41
  IV-12        Dependence of Sulfate Emission Rates,
               gms/km  on  Fuel Sulfur Content Monolithic
               Catalyst-Equipped Vehicle
               64 km/hr Cruise	     41
  IV-13        Dependence of Sulfate Emission Rates,
               gms/km  on  Fuel Sulfur Content, Pelletized
               Catalyst-Equipped Vehicle
               64 km/hr Cruise	     42
  IV-14        Sulfate Emission Rates vs.  Fuel Sulfur
               Content, Base Case and Monolithic  Oxidation
               Catalysts  (96 or 113 kra/hr  Cruises)	     42
  IV-15        Sulfate Emission Rates vs.  Fuel Sulfur
               Content, Base Case and Pelletized  Oxidation
               Catalysts  (96 or 113 km/hr  Cruises)	     44
  IV-16        Dependence of Sulfate Emission Rates
               on Fuel Sulfur Content,  Vehicle Equipped
               with NOX Reduction Catalysts,
               64 km/hr Cruise	     44
  IV-17        Dependence of Sulfate Emission Rates,
               gms/km  on  Fuel Sulfur Content, Vehicle
               Equipped with NOx Reduction Catalysts
               96 km/hr Cruise	     45
  IV-18        S02 and Sulfate  Emissions for  Monolithic
               Catalysts  for the 1975 FTP	     47
  IV-19        S02 and Sulfate  Emissions for  Monolithic
               Catalysts  at  64  km/hr Cruise	     48

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                                viii

                       TABLE OF FIGURES (CONT.)


FIGURE NO.                       TITLE                     PAGE NO.
  IV-20         S02 and Sulfate Emissions for Monolithic
                Catalysts at 96-113 km/hr Cruise	    49
  IV-21         S02 and Sulfate Emissions for Pelleted
                Catalysts for the 1975 FTP	    50
  IV-22         S02 and Sulfate Emissions for Pelleted
                Catalysts at 64 km/hr Cruise	    51
  IV-23         S02 and Sulfate Emissions for Pelleted
                Catalysts at 96-113 km/hr Cruise	    52
  IV-24         S02 and Sulfate Emissions for NOX Reduction
                Catalysts for the 1975 FTP	    53
  IV-25         S02 and Sulfate Emissions for NOx Reduction
                Catalyst at 64 km/hr Cruise	    54
  IV-26         S02 and Sulfate Emissions for NOx Reduction
                Catalysts at 96 km/hr Cruise	    55
  IV-27         Equilibrium % Composition-Relative Humidity
                Curve for Aqueous H2S04 at 20°C	    62
  IV-28         Scanning Electron Micrograph of Absolute
                Filter from Andersen Impactor 	    64
  IV-29         Scanning Electron Micrograph of Total
                Filter Containing 125 mg of Sulfate ....    64
  IV-30         Total Metal Oxide Emission Rates, gins/km
                Obtained with Indicated Catalyst, Initial
                and Final 1975 FTP on Each Test Fuel. ...    58
  IV-31         Metal Oxide Emission Rates, gms/km vs.
                Fuel Sulfur Wt. % on Steady State Cruises,
                Engelhard Monolith	    70
  IV-32         Metal Oxide Emission Rates, gms/km vs.
                Fuel Sulfur, Wt. % on Steady State Cruises,
                UOP (1) Monolith	    70
  IV-33         Metal Oxide Emission Rates, gms/km vs.
                Fuel Sulfur, Wt. % on Steady State Cruises,
                UOP (2) Monolith	    71
  IV-34         Metal Oxide Emission Rates, gms/km vs.
                Fuel Sulfur, Wt. % on Steady State Cruises,
                Matthey-Bishop Monolith	    71
  IV-35         Metal Oxide Emission Rates, gms/km vs. Fuel
                Sulfur, Wt. % on Steady State Cruises,
                Engelhard Pellet	    72
  IV-36         Metal Oxide Emission Rates, gms/km vs. Fuel
                Sulfur, Wt. % on Steady State Cruises,
                Grace Pellet	    72
  IV-37         Metal Oxide Emission Rates, gms/km vs.
                Fuel Sulfur, Wt. % on Steady State Cruises,
                Air Products Pellet	    73

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                                 IX

                       TABLE OF FIGURES (CONT.)



FIGURE NO.                       TITLE                   PAGE NO.
  IV-38         Metal Oxide Emission Rates, gms/km
                vs. Fuel Sulfur Wt. %, on Steady
                State Cruises, Grace NOX
                Reduction Catalyst	   73
  IV-39         Metal Oxide Emission Rates, gms/km
                vs. Fuel Sulfur, Wt. % on Steady
                State Cruises, Gould NOX
                Reduction Catalyst	   74
  IV-40         Aluminum Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Initial 1975 FTP	   77
  IV-41         Lead Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Initial 1975 FTP	   78
  IV-42         Lead Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Final 1975 FTP	   80
  IV-43         Lead Emission Rates at 64 and 96 km/hr
                Obtained with Indicated Catalyst	   81
  IV-44         Iron Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Initial 1975 FTP	   83
  IV-45         Nickel Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Initial 1975 FTP	   85
  IV-46         Nickel Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Final 1975 FTP	   86
  IV-47         Copper Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Initial 1975 FTP	   87
  IV-48         Copper Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Final 1975 FTP	   88
  IV-49         Zinc Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Initial 1975 FTP	   90
  IV-50         Calcium Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Final 1975 FTP	   91
  IV-51         Chromium Emission Rates, gms/km
                Obtained with Indicated Catalysts,
                Initial 1975 FTP	   92

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                       TABLE OF FIGURES (GOUT.)


FIGURE NO.                       TITLE                    PAGE NO.
  IV-52         Size Distribution of Total Particulate,
                Base Case Vehicle, 1975 FTP, Run No. 6 .  .    101
  IV-53         Size Distribution of Total Particulate,
                Base Case Vehicle, 113 km/hr Cruise,
                Run No. 9	    101
  IV-54         Size Distribution of Total Particulate,
                Base Case Vehicle, 113 km/hr Cruise,
                Run No. 14	    102
  IV-55         Size Distribution of Total Particulate,
                Base Case Vehicle, 1975 FTP,
                Run No. 15	    102
  IV-56         Size Distribution of Total Particulate
                Base Case Vehicle, 64 km/hr Cruise
                Run No. 29	    103
  IV-57         Size Distribution of Total Particulate,
                Matthey-Bishop Catalyst-Equipped Vehicle,
                64 km/hr Cruise, Run No. 88	    103
  IV-58         Size Distribution of Total Particulate,
                Grace Palletized Catalyst-Equipped
                Vehicle, 64 km/hr Cruise, Run No. 133. .  .    104
  IV-59         Size Distribution of Total Particulate,
                Grace Palletized Catalyst-Equipped
                Vehicle, 64 km/hr Cruise, Run No. 138. .  .    104
  IV-60         Size Distribution of Total Particulate,
                Air Products Palletized Catalyst-Equipped
                Vehicle, 1975 FTP, Run No. 160	    105
  IV-61         Size Distribution of Total Particulate,
                Air Products Palletized Catalyst-Equipped
                Vehicle, 1975 FTP, Run No. 166	    105
  IV-62         Size Distribution of Total Particulate,
                Grace Reduction Catalyst-Equipped Vehicle,
                1975 FTP, Run No. 96	    106
  IV-63         Size Distribution of Total Particulate,
                Grace Reduction Catalyst-Equipped Vehicle,
                1975 FTP, Run No. 101	    106
  IV-64         Size Distribution of Total Particulate,
                Gould Reduction Catalyst-Equipped Vehicle,
                64 km/hr Cruise, Run No. 113	    107
  IV-65         Size Distribution of Total Particulate,
                Gould Reduction Catalyst-Equipped Vehicle,
                1975 FTP, Run No. 120	    107
  IV-66         Size Distribution of Total Particulate,
                Grace Reduction Catalyst-Equipped Vehicle,
                64 km/hr Cruise, Run No 103	    108

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                                   xi


                       TABLE OF FIGURES (CONT.)


FIGURE NO.                       TITLE                     PAGE NO.
  IV-67       Size Distribution of Total Particulate,
              Gould Reduction Catalyst-Equipped Vehicle,
              1975 FTP, Run No. 125	   108
  IV-68       Size Distribution of Total Particulate,
              Engelhard Pelletized Catalyst-Equipped
              Vehicle, Second 1975 FTP After Sulfate
              Storage Conditioning, Run No. 175	   109

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                                  xii

                        LIST OF APPENDIX TABLES


TABLE                           TITLE                          PAGE NO.
 A-l          Comparative Titratlons of Sulfate of Samples
              With and Without Nitric Acid	   119
 A-2          Experiments Demonstrating Influence of
              Ion Exchanger on Sulfonazo III End Points ....   120
 A-3          Comparison of Titrimetric and Gravimetric
              504° Analysis on Parallel Filters 	   121
 A-4          SO2 Measurements at Indicated Oxygen
              Concentrations	   126
 A-5          Composite Effects of C02, 02, and CO
              on TECO S02 Response	   127
 A-6          Estimated Average Maximum Emission Rates
              (gins/km) As Determined by Detection Limit
              of Spot Test on Indicated Vehicle Test	   136
 A-7          Effects of Presence of Other Metals on
              Determination of a Selected Metal
              (0.45 to 4.5 ygms/cm2 Calibration Curve)	   155
 A-8          Platinum-Chromium Interference	   156
 B-l          Comparison of Impactor and Total Filters
              (64 km/hr. Cruise)	   159
 B-2          Distribution of Partlculate in Modified
              Andersen Impactor (64 km/hr. Cruise)	   159
 B-3          Comparison of Impactor and Total Filters
              (96 km/hr. Cruise)	   161
 B-4          Distribution of Particulate in Modified
              Andersen Impactor (96.54 km/hr Cruise)	   161
 C-l          Performance of Exhaust Splitter on Lab Air. . .  .   164
 E-l          Gaseous Emissions Unequipped Mileage
              Accumulation Vehicle 	  170
 E-2          Gaseous Emissions Unequipped Test Vehicle	171
 E-3          Gaseous Emissions Engelhard Monolithic
              Oxidation Catalyst-Equipped Vehicle	172
 E-4          Gaseous Emissions Engelhard Palletized
              Oxidation Catalyst-Equipped Vehicle	173
 E-5          Gaseous Emissions UOP (1) Monolithic
              Oxidation Catalyst-Equipped Test Vehicle 	  174
 E-6          Gaseous Emissions Matthey-Bishop Monolithic
              Oxidation Catalyst-Equipped Test Vehicle 	  175
 E-7          Gaseous Emissions Grace NOX Reduction
              Catalyst-Equipped Vehicle	176
 E-8          Gaseous Emissions Gould NOX Reduction
              Catalyst-Equipped Vehicle	177
 E-9          Gaseous Emissions Grace Pallatized
              Oxidation Catalyst-Equipped Vehicle	178
 E-10         Gaseous Emissions UOP (2) Monolithic
              Oxidation Catalyst-Equipped Vehicle	179
 E-ll         Gaseous Emissions Air Products Palletized
              Oxidation Catalyst-Equipped Vehicle	180

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                                 xiii

                    LIST OF APPENDIX TABLES (CONT.)


TABLE                            TITLE                     PAGE NO.
 E-12        Gaseous Emissions, Test Vehicle Equipped
             With Engelhard Palletized Oxidation Catalyst
             After Catalyst Was Conditioned on a
             0.091% S Fuel for 3200 km on the Federal
             Durability Cycle 	    181
 E-13        Gaseous Emissions, Test Vehicle Equipped
             With Engelhard Monolithic Oxidation
             Catalyst	    181
 E-14        Metal Derived Exhaust Particulate Emissions
             Base Case Runs With Unequipped Mileage
             Accumulation Vehicle Runs (1-15) and
             Unequipped Test Vehicle Runs (16-30) 	    182
 E-15        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With Engelhard
             Monolithic Oxidation Catalyst	    183
 E-16        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With Engelhard
             Pelletized Oxidation Catalyst	    184
 E-17        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With UOP (1) Monolithic
             Oxidation Catalyst 	    185
 E-18        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With Matthey-Bishop
             Monolithic Oxidation Catalyst	    186
 E-19        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With Grace Reduction
             Catalyst	    187
 E-20        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With Gould NOX Reduction
             Catalyst	188
 E-21        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With Grace Pelletized
             Oxidation Catalyst	189
 E-22        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With UOP (2)
             Monolithic Oxidation Catalyst 	   190
 E-23        Metal Derived Exhaust Particulate Emissions
             Test Vehicle Equipped With Air Products
             Pelletized Oxidation Catalyst 	   191
 E-24        Metal Derived Exhaust Particulate Emissions
             Test Vehicle EQuipped With Engelhard
             Pelletized Oxidation Catalyst After
             Conditioning on 0.091% Sulfur Fuel for
             6400 Kilometers on Federal Durability Cycle . .   192
 E-25        Sulfate Emissions Unequipped Mileage
             Accumulation Vehicle	193

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                                   xiv

                    LIST OF APPENDIX TABLES (CONT.)


TABLE                            TITLE                      PAGE NO.
 E-26        Sulfate Emissions Unequipped Test Vehicle . . .   194
 E-27        Sulfate Emissions Test Vehicle Equipped
             With Engelhard Monolithic Oxidation Catalyst. .   195
 E-28        Sulfate Emissions Test Vehicle Equipped
             With Engelhard Pelletized Oxidation Catalyst. .   196
 E-29        Sulfate Emissions Test Vehicle Equipped
             With UOP (1) Monolithic Oxidation Catalyst. . .   197
 E-30        Sulfate Emissions Test Vehicle Equipped
             With Matthey-Bishop Monolithic Oxidation
             Catalyst	   198
 E-31        Sulfate Emissions Test Vehicle Equipped
             With Grace NOX Reduction Catalyst 	   199
 E-32        Sulfate Emissions Test Vehicle Equipped
             With Gould NOX Reduction Catalyst	   200
 E-33        Sulfate Emissions Test Vehicle Equipped
             With Grace Pelletized Oxidation Catalyst. . . .   201
 E-34        Sulfate Emissions Test Vehicle Equipped
             With UOP (2) Monolithic Oxidation Catalyst. . .   202
 E-35        Sulfate Emissions Test Vehicle Equipped
             With Air Products Pelletized Oxidation
             Catalyst	   203
 E-36        Sulfate Emissions After Storage 	   204

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                                 XV
                       LIST OF APPENDIX FIGURES
FIGURE NO.                       TITLE                         PAGE NO.
  A-l           Recovery of Sulfate From Spiked Glass
                Fiber Filter Samples	   122
  A-2           Principle of Operation TECO S02
                Instrument	   124
  A-3           Permatube Drying System 	   125
  A-4           Perkin-Elmer Model 240 C/H/N Microanalyzer.  .  .   126
  A-5           Analytical Scheme for Nitrogen
                Compounds in Auto Exhaust Particulate 	   132
  A-6           Analytical Scheme for Sulfur Compounds
                in Exhaust Particulate	   133
  A-7           Calibration Curve for Nickel	   140
  A-8           Calibration Curve for Aluminum	   141
  A-9           Calibration Curve for Calcium 	   142
  A-10          Calibration Curve for Copper	   143
  A-ll          Calibration Curve for Chromium	   144
  A-12          Calibration Curve for Zinc	   145
  A-13          Calibration Curve for Lead	   146
  A-14          Calibration Curve for Iron	   147
  A-15          Calibration Curve for Platinum	   148
  A-16          False Platinum Response of Quantometer
                Due to Presence of Chromium	   151
  A-17          Calibration Curve for Lead
                (4.5 to 11.25 ygms/cm2)	   152
  A-18          Calibration Curve for Iron
                (4.5 to 11.25 pgms/cm2)	   153
  A-19          Calibration Curve for Zinc
                (4.5 to 11.25 ugms/cm2)	   154
  B-l           Oxidation Catalyst-Equipped Vehicle 	   160
  C-l           Schematic of Exhaust Splitter 	   163

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                                SUMMARY
          A program to measure and characterize exhaust particulate
emissions from a vehicle equipped with a variety of commercial and
prototype catalyst systems was carried out.  Nine catalysts (four
monolithic oxidation catalysts, three palletized oxidation catalysts,
and two NOX reduction catalysts) were screened on three test  fuels.
The oxidation catalysts were representative of those used on 1975
production vehicles; the NOx reduction catalysts, candidates for use in
automotive emission control systems.  The fuels used were an EPA-supplied
reference fuel containing 21% aromatics, that fuel plus an additives
package, and a 46% aromatics fuel with the additives package.

          A rigorous conditioning procedure was carried out on both
catalysts and the vehicle prior to emissions testing to minimize the
effects of prior history on emissions.  The vehicle was then operated
through a series of cyclic and steady state tests on each of the three
test fuels.  Emission rates of CO, HC, NOX, and 862 were measured in
each test mode.  Total particulate emission rates were measured using
the CVS compatible exhaust particulate sampler developed at Exxon
Research.  Particulate samples were analyzed for sulfate, carbon, bound
water, nine metals, organic nitrogenous compounds, and organic sulfur
compounds.

          The following results were obtained with oxidation catalysts:

          •  Total particulate emission rates increased due
             to the production of sulfuric acid aerosol by
             catalytic oxidation of exhaust S02-  This sulfuric
             acid aerosol and its associated bound water, was
             the major component of the particulate emitted.
             As a result, total particulate emission rate varied
             approximately linearly with fuel sulfur content.
             By contrast, particulate emissions from the vehicle
             without catalysts were independent of fuel sulfur
             level.

          •  The mass median equivalent diameter of catalyst
             exhaust particulate decreased relative to the non-
             catalyst case because submicron sulfuric acid
             aerosol was the predominant component of the
             particulate.

          •  Preliminary results of sulfate storage experi-
             ments indicate that released sulfate may have a
             larger particle size than sulfate produced during
             a run.  Under certain conditions, the quantity
             of stored sulfate released may be several times
             that of freshly produced emitted sulfate.  The
             emitted sulfate after storage conditioning may
             have two particle size distributions such that
             stored sulfate has a larger mass median equiva-
             lent diameter than freshly produced emitted
             sulfate.  Further work is needed to substantiate
             these results.

           •  Pelletized  catalysts store sulfate  during certain
             test modes.  Release of  this  stored  sulfate  can
             persist  for several  test runs,  resulting  in
             sulfate  yields  considerably  in  excess  of  100%
             based  on the sulfur  in the  fuel consumed.

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                       - 2 -
•  The differences in particulate carbon content between
   conventional and catalyst-equipped vehicles were smaller
   than expected,  particularly under cyclic operating con-
   ditions, possibly because the presence of an air pump on
   the conventional vehicle lowered particulate carbon
   emissions.  The carbon emission rates for oxidation
   catalyst equipped vehicles operating on 0.019 wt.%
   sulfur fuel ranged from zero to 0.019 gms/km and averaged
   about 30% of the total particulate.  Carbon emission rates
   were independent of fuel sulfur content, the relative
   contribution of this particulate component decreasing
   with increasing fuel sulfur content.

•  The emission rate of some metals was raised as a result
   of oxidation catalysts.  The increment was not enough to
   influence total particulate emissions.

   -  Aluminum emissions were higher, increasing from about
      5 x 10~5 gms/km for the conventional vehicle to rates
      occasionally as high as 4.5 x 10"^ gms/km.  The
      increase may be due to a low level of catalyst attrition.

   -  Iron emissions were substantially higher, increasing
      from about 10~3 gms/km for the conventional vehicle to
      rates exceeding 5 x 10~3 gms/km for oxidation catalyst
      equipped vehicles.  The increased iron emissions are
      probably due to reaction between the sulfate formed
      over the catalyst and the exhaust system.  Iron emissions
      were independent of the amount of sulfuric acid emitted
      indicating that the reaction was wall (iron) limited.

   -  Zinc emissions also increased.  The source of the zinc
      was not determined.

   -  Platinum was not detected in the exhaust particulate
      indicating that the emission rate must be below
      5 x 10~*> gms/km.

With NOX reduction catalysts, it was found that:

•  Particle size distribution of the emitted particulate
   resembles that of a non-catalyst car, if conditions are
   not leaner than stoichiometric, when sulfuric acid aerosol
   is formed.  In the latter case, mass median equivalent
   diameter is similar to that of atn oxidation catalyst-
   equipped vehicle.

•  Nickel emission rates with a Gould NOX reduction catalyst
   equipped vehicle were as high as 2 x 10~3 gms/km.  With a
   conventional vehicle or an oxidation catalyst equipped

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                                 - 3 -


             vehicle,  nickel emission rates averaged about 2 x 10~^ gins/km.
             However,  the increased nickel emission rates obtained with the
             NOX reduction catalyst may have been due to improper operation  of
             the vehicle at stoichiometric or net lean A/F ratios.

          The following results were found to be independent of whether
the vehicle was operated with or without a catalyst:

          •  Calcium emission rates correlated with expected lubricating
             oil consumption rates.  Calcium was not a significant
             exhaust particulate, the emission rate averaging about
             1 x 10~4  gins/km.

          •  Leaded particulate emission rates for the unequipped
             and catalyst-equipped vehicle were similar and were
             equivalent to about 50% of the lead burned.

          •  No nitrogenous organic particulate matter, either
             additive or otherwise derived, was found.

          •  Sulfate was the only sulfur containing exhaust
             particulate found.

          •  Particulate emissions did not increase when the
             fuel aromatic content was increased from 21 to 46%,
             indicating that the carbon particulate emission rate was
             independent of fuel aromatic content.

          The major effect of catalysts used for automotive emissions
control on exhaust particulate emissions are the production of sulfuric
acid aerosol, and some increase in metal derived emissions, mainly those
containing iron.  Sulfates and associated bound water are the predom-
inant components of exhaust particulate, followed by minor quantities
of organic particulate and metal derived particulate.  The relative
contributions of the latter two types of particulate decreases with
increasing fuel sulfur content.

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                           I.  INTRODUCTION
          Automotive particulate emissions are of concern because of
the potentially deleterious effects to health as a result of their accumula-
tion in the atmosphere.  Particulates also reduce atmospheric visibility,
are known to be the cause of increased soiling, and may also function as
photosensitizers in smog forming reactions.  In 1975, approximately
75% of the cars produced will be equipped with oxidation catalysts
in order to control carbon monoxide and hydrocarbon emissions.  In
addition to reducing these pollutants, prototype systems were also
shown to have further beneficial results, namely the reduction of un-
regulated emissions such as aldehydes, reactive hydrocarbons(1), and
polynuclear aromatic hydrocarbons(2) to extremely low levels.

          Particulate emissions from catalyst equipped vehicles however
could differ markedly from that of conventional vehicles.  For example,
thermal and mechanical stresses of the catalyst and/or substrate could
result in the presence of these materials in vehicular exhaust.  Chem-
ical conversion of catalyst and substrate material to a mobile condensed
phase is another possible route for these materials to show up in
vehicular exhaust.  Finally, catalytic conversion of gaseous exhaust
components to particulate matter could produce new exhaust components,
not normally present in the exhaust of conventional vehicles.  Sulfate
aerosol is an example of a catalytically produced exhaust component
not normally present in significant quantities  in exhaust from con-
ventional vehicles.  This aerosol is produced by the catalytic oxidation
of exhaust sulfur dioxide.

          This report describes the first phase of a contract work
program to study particulate emissions from catalyst equipped vehicles
The major objectives of this program are the measurements and characteriza-
tion of exhaust particulate emissions from a variety of catalyst systems
(commercial and prototype) that may be used in automotive emission
control.  To this end, it was necessary  to measure and characterize
particulate emissions from vehicles in their conventional configuration
prior to equipping them with catalysts in order to distinguish between
vehicle and catalyst effect on total particulate emissions.

          The first phase of this contract work was primarily a catalyst
screening program.  The catalysts selected for testing were those most
likely to be used in commercial vehicles.  Nine catalyst systems  (four
monolithic oxidation catalysts, three beaded oxidation catalysts,
and two NO  reduction catalysts) were tested with three  fuels.
          A
          The three fuels used were a reference fuel supplied by EPA,
that same fuel with an additive package, and a high aromatic  fuel
which also contained the additive package.  This fuel selection was
made so that exhaust particulate could be  characterized  as  follows:

(1)  level and  composition of exhaust particulate from the  use of  an
     additive-free  fuel in conventional  and catalyst equipped vehicles.

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                                  - 5 -
(2)  effect of fuel additives on particulate emissions from conventional
     and catalyst equipped vehicles,

(3)  effect of a high aromatic fuel containing additives on particulate
     emissions from conventional and catalyst equipped vehicles.

          Two matched 1974 - 350 CID (5.735 liter) Chevrolet V-8
vehicles equipped with air pumps and exhaust manifold air injection
systems were used.  One vehicle was used for all the particulate
emission measurements, the other for conditioning and aging the catalysts.

          A rigorous conditioning schedule prior to testing was carried
out since it has been shown that particulate emissions, particularly
sulfate emissions, are a sensitive function of vehicle history.  Each
of the catalysts was mounted on the test vehicle and conditioned for
3218 km (2,000 miles) on a Mileage Accumulation Dynamometer (MAD) over
the Federal Durability Cycle using an eight-hour on, eight-hour off
sequence.  The conditioning fuel was different from the test fuel
because of limited supply of test fuels.  Prior to testing with a given
fuel, the vehicle was operated on that fuel for 200 miles on the MAD
using the Federal Durability Cycle, followed by a sixteen-hour cold
soak.

          The vehicle was then operated through the following series of
tests on each of the three test fuels:

(1)  1975 FTP
(2)  One hour idle
(3)  One hour, 64 km/hr (40 mph) cruise
(4)  Two hour, 113 km/hr  (70 mph) cruise or a two hour, 96 km/hr
     (60 mph) cruise
(5)  Overnight soak
(6)  1975 FTP

Gaseous emission rates (CO, hydrocarbon, NO , and SO ) were measured
in each test.  Total particulate emission rites were measured in each
test using the CVS compatible  exhaust  particulate  sampler  developed at
Exxon  (3).

           Analyses of  the particulate  samples were carried out  to  determine
the  emission rates of  the following:

           Sulfate
           Carbon
           Calcium
           Aluminum
           Zinc
           Chromium

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                                   - 6 -
          Iron
          Copper
          Nickel
          Lead
          Platinum
          Bound Water

Chemical analysis was carried out to determine the presence  of  non-
sulfate sulfur particulate matter and for the presence  of  nitrogenous
organic matter in exhaust particulate.   Particulate size distribution
determinations were carried out using an Anderson Particle Sizing
Sampler.

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                                   - 7 -


                       II.  TECHNICAL BACKGROUND

          In this section, automotive particulate emissions will be
briefly discussed, the exhaust particulate sampling system developed
at Exxon will be described, as well as the capabilities of the sampling
sys tern.

II.1  Automotive Particulate Emissions

          In this report, automotive particulate emissions are defined
as any material, other than unbound water, emitted from a vehicle tailpipe
which exists in the condensed state at 32°C (90°F), that is larger than
a small molecule but less than 500 microns in diameter.  Exxon Research
has used this definition of exhaust particulate since it was used by
EPA in a work statement of a 1972 Request for Proposal to "Design,
Develop, Fabricate and Test a Device Compatible with the Constant
Volume Sampling System which will Allow Simultaneous Measurement of
Gaseous and Particulate Emissions from Light Duty Vehicles"(4).

II.2  Exhaust Particulate Sampling System

          The exhaust particulate sampling system has been designed to
collect particulate matter at constant temperature during the 1972 and
1975 Federal Test Procedure, and 64 km/hr (40 mph) cruise conditions.
This system is capable of frequent and convenient operation, and is
compatible with constant volume sampling (CVS) of auto exhaust.
Compatibility is obtained because the particulate sampler requires
only a small portion of the diluted exhaust, the major portion of the
sample is available to the CVS system for the measurement of gaseous
emissions.  Conditions used in the measurement of exhaust particulate
conform to those mandated by the Federal Test Procedures for gaseous
emissions.

          This sampling system uses a small tunnel which means that low
dilution ratios are used, allowing gaseous emissions such as CO, hydro-
carbons, NOX and SC>2 to be measured accurately.  While low dilution
ratios are desirable from the standpoint of CVS gaseous emission
measurements, the collection of a proportional sample of particulate
matter at constant temperature 32°C (90°F) from a sample stream having
a high dew point without causing condensation of water requires an
advanced temperature control system.

     II.2.1  Sampling System Components

          The particulate sampler which has been discussed previously(3,5)
is shown schematically in Figure II-I.    This system has five major
components:

          1.  A diluent air preparation system
          2.  A flow development tunnel
          3.  An exhaust Injector system
          4.  An isokinetic sampling probe
          5.  A particulate measuring device, which in the case shown
              is a 0.2 micron glass fiber filter

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                                     FIGURE II-1
                            EXHAUST PARTICULATE SAMPLER
   INTAKE
 DILUENT AIR
HEAT
EXCHANGER
            DEHUMIDIFIER
                                             FLOW
                                         DEVELOPMENT
                                            TUNNEL
   MIXING
TURBULATORS
                                TO CVS
                                                                ROTOMETER I P"*
                                        <
                                                                            PUMP
i
00
I
                                          EXHAUST
                                          INJECTOR
                        ISOKINETIC
                        SAMPLING
                          PROBE
                                 FILTER
                                HOUSING

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                                    - 9 -
          The overall function of this system is to allow the collection
of particulate matter from an isokinetically sampled portion of
diluted exhaust which has been cooled to 90°F by dilution with chilled,
dehumidified, filtered air.  The function of each of the components in
accomplishing this objective is described below.

          II.2.1.1  Diluent Air Preparation System

          This system consists of a dehumidifier, filter, coupled mixing
baffles, a cooling system, and mixing turbulators.

          The dehumidifier shown schematically in Figure II.2 minimizes
the possibility of condensation occurring in the sampling system during
a run, and is an integral part of the temperature control system.
Diluent air is dried by passage through a filter and a slowly rotating
desiccant wheel containing laminated flat and corrugated asbestos,
impregnated with a regenerable desiccant, Lid.  Dehumidification of
diluent air and desiccant reactivation are concurrent processes, so that
dehumidification can be carried out on a continuous basis.  The de-
humidifier, a Honeycombe Model HC 750-EA is manufactured by Cargocaire
Engineering Corporation is described in their Bulletin No. 07169(6).

          Dehumidified inlet air passes from the dehumidifier to a filter
box containing a paper filter, a bed of activated charcoal, and a second
paper filter.  This assembly is the standard filter box assembly for the
Scott Research Constant Volume Sampler (CVS) unit.  The filter assembly
removes the particulate matter present in the diluent air and reduces
and stabilizes the background hydrocarbon content of the diluent air.

          Because regeneration of the dessicant Is accomplished by
heating, the dehumidified air emerging from the drum is above ambient
temperature.  A pre-cooler situated between the dehumidifier and the CVS
filter cools the dehumidified air stream down to ambient temperature to
remove the additional cooling load Imposed by the dehumidification step
from the final cooling system.  The pre-cooler consists of several rows
of colls through which chilled city water is passed.

          The coupled mixing baffles continuously divide the dehumidified,
filtered air into two portions, one which passes through the cooling
system, and a second portion which bypasses the cooling system.  The
position of the mixing baffles is controlled by a rapid response, deviation-
type controller operating on an input signal from a thermocouple in the
filter housing.  The system is designed to maintain 90°F at the filter
housing, during the 1972 or 1975 Federal Test Procedures, and 64 km/hr
cruise.

          The controller operates by comparing an input signal from
a thermocouple in the filter housing with a set point signal, and
takes corrective action to either raise or lower the output signal until
the set point and thermocouple input are equal.  The controller used was
an Electronic Control System Model 6700 Controller(7).  The output signal

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                  FIGURE II-2
SCHEMATIC OF DEHUMIDIFICATION SECTION
    REACTIVATION AIR

       INLII^"-TER         REACTIVATION
                              FAN
TO FILTER  ^T
  BOX _DV AyD             DESICCANT
   A  DRYA'R REACTIVATION  WHEEL
    1       T   AIR HEATER /.'I
            V js    N    /••
                                  WET AIR OUTLET
                                         A
               M	1  '
            REACTIVATION
               SECTOR
               r   ^   J
    ^^	S
  DRY AIR FAN
                                         HUMID AIR
                                           INLET
                                           FILTER
                                                               o
                                                               i

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                               - 11 -


from the controller is fed to an electric to pneumatic transducer (8)
which in turn activates a pneumatic controller (9) which operates the
coupled baffles.

          The cooling system is an air cooled condensing evaporator which
has a cooling capacity of 33,500 BTU/hour.  The evaporator is a Dunham-
Bush, Model SCO-50C unit(10) containing ten rows of custom-made cooling
coils(11).

          The mixing turbulators insure that chilled air is thoroughly
mixed with the portion of air bypassing the cooling system before the
stream is used to dilute the vehicle exhaust.  The turbulators consist
of six semi-circular  perforated  plates attached to a 1/2" diameter
wall tube at their centers, arranged in a helical series sequence along
the tunnel axis.  This arrangement allows both longitudinal and
latitudinal mixing.

          Maximum flow through the diluent air preparation system is
determined by the cooling capacity of the chiller.  Presently, this
limitation is 450 CFM.

          II.2.1.2  Flow Development Tunnel

          The exhaust and diluent air are mixed and a uniform velocity
profile is developed in the flow development tunnel.  The flow develop-
ment tunnel is a 7.5 ft. long section of a 4-inch diameter Schedule 5
stainless steel pipe.  Neither the length nor the diameter of the flow
development tunnel have been optimized, but as will be shown in another
section, a dilution tunnel of these dimensions is satisfactory for
this purpose.

          II.2.1.3  The Exhaust Injection System

          The raw exhaust is mixed with the diluent air normally used
in the CVS in such a way as to completely mix the two in as short a
time interval as possible.  This is accomplished by injecting
the exhaust in a countercurrent direction to the diluent air stream.
Previous experiments(3) have shown this to be the most efficient way
of obtaining a rapidly mixed, uniformly distributed diluted exhaust sample
stream.  Figure II-3 shows a schematic of the exhaust injector in the
countercurrent position.

         II.2.1.4  Isokinetic Probe

          Isokinetic sampling is required to insure that the particulate
sampled is representative of the particulate in the main stream; that is,
the particulate concentration and size distribution in the probe sample
should correspond  to  that of the main stream.  The probes are designed
so that the sample stream is divided into two parts with a volume
ratio equal  to  the ratio of the cross-sectional areas of the openings
of the sample probes  and the tunnel cross-sectional area.  Hence,

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                          FIGURE II-3
     COUNTER CURRENT EXHAUST INJECTION SYSTEM
      TRICLOVER
    CONNECTIONS
DILUTION
  AIR
RAW EXHAUST
                              TAILPIPE CONNECTOR
       DILUTED EXHAUST
4.3" ID S.S. FLOW
DEVELOPMENT
SECTION
                T^^	_, , aiTLf -T-— ,-LJI I  * f'fl -f'~	-n -r	-.*»'
                      \
                COUNTERCURRENT

                   INJECTOR

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                                 - 13 -


           Area (probe)       _      Flow Rate in SCFM (probe)
           Area (tunnel)      ~      Flow Rate in SCFM (tunnel)

          Another problem to be considered in probe design is minimizing
sample deposition in the probes.  When suspended particulate matter
leaves the tunnel and enters the sampling probe, it is leaving a low
surface to volume region and entering a high surface to volume region.
Relative sample losses by impaction should be greater in the probe
than in the tunnel.  Therefore, the probe should be as short and
direct as possible to minimize the residence time of the particulate
matter in the probe.  The filter housing connected to the probe is
flared out as soon as physically possible to minimize the surface to
volume ratio of the housing and thereby reduce sampling losses by impac-
tion in this portion of the sampling system.

          II.2.1.5  Particulate Collecting Stage

          At present, particulates are collected by filtering the sample
through pre-weighed filters.  In principle, other particulate collectors
such as impactors and other devices, could be utilized with the
particulate sampling system.  In this paper, total particulates are
determined gravimetrically using Gelman Type E glass fiber filters
which have an effective pore size of 0.2 y.

     II.2.2  System Performance

          In order to function properly, the exhaust particulate sampling
system should have the following capabilities:

          (1) Mix exhaust and diluent air rapidly.
          (2) Allow development of a uniform velocity profile in the
              flow development tunnel.
          (3) Minimize sampling losses in the tunnel.
          (4) Give equivalent emission rates with parallel filters.
          (5) Maintain constant temperature at the particulate
              collecting stage.

All of the above have been adequately documented  (3,5) and will be
reviewed  In  this section.

          II.2.2.1  Rapid Mixing of Exhaust and Diluent Air

          Three methods of injecting exhaust into diluent air were
tested:   co-current flow, perpendicular flow, and countercurrent flow.
In each case, the exhaust was injected through a 2 in. O.D. x 0.035 in.
wall stainless steel tube into the flow development tunnel.  The efficiency
of the three injection methods was tested by measuring hydrocarbon concen-
trations  in  the diluted exhaust at a point approximately 7.5 ft. downstream
of the injection point.  Hydrocarbons were chosen as the tracer because
they are  easier to measure than particulates.  If the gaseous components
of the exhaust are not evenly distributed over the flow cross-section,
there is  no  reason to believe that the particulates will be well
distributed.  The ultimate test of uniformity of particulate distribution

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                                  -  14  -
in the tunnel is the consistent attainment of equivalent particulate
emission rates with parallel filters.  The results showed that uniform
distribution was obtained only by countercurrent injection.
          II.2.2.2  Development of Uniform Flow
                    in Flow Development Tunnel

          To insure that samples taken at any point in the tunnel cross-
section will contain the same amount of particulate material, a uniform
radial distribution of particulate material in the tunnel must be obtained.
The small size of the tunnel would make it difficult to obtain reliable
measurements of velocity profiles.  However, it is well known that the
higher the Reynolds Number of turbulent flow, the flatter the velocity
profile(12).  However, over the range of interest for this system, the
effect of this flattening of the velocity profile is negligible.
Consider the system as having a flow of 450 SCFM of air at 90°F.through
a 4.33 in. diameter pipe.

                              V   •  -g*-

          where N    = Reynolds Number
                  D  = pipe diameter = 4.34 in. = 0.361 ft
                  U  = average fluid velocity =  4 ^J"' = 4395 ft/min

                                    5             '' °
                           2.64 x 10  ft/hr

                   P = density = 0.071 Ib/ft

                  /( = fluid viscosity = 0.186 cp = 0.045 Ib/ft-hr

                N_     (0.361 ft) (2.64 x 105 ft/hr) (0.71 Ib/ft3)  =     „.
                 Ke  "               0.045 Ib/ft-hr                   J.3U.UUU

          Equation  (1) shows that the Reynolds Number varies inversely
with diameter  for constant volumetric flow.  Therefore, decreasing pipe
diameter to 1" would increase NRe to 615,000 while increasing pipe
diameter to 16" would decrease NRe  to 40,000.

          One measure of  the flatness of the velocity profile is the ratio
of the mean gas velocity  to the maximum gas velocity.  It has been shown
experimentally that for turbulent flow in smooth pipes(12)
                              s. .(I)
                              U   \R/
1/N
                         (2)

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                                  -  15 -


where u = point velocity
      U = maximum velocity at center
      Y = distance from the wall
      R = pipe radius, and
      N = a constant depending on Reynolds Number

      Schlicting (12) shows that average velocity 11 is,


                                    2N2
                           u =
The following table shows that the effect of changing pipe diameter
over a large range would be negligible.

                       Effect of Reynolds Number
                          on Velocity Profile

               N                   N                TI/U
              23,000              6.6               .807
             110,000              7.0               .816
             500,000              8.0               .837

 It should be noted that Schlicting*s correlation is for a fully
 developed boundary layer which probably does not exist in the tunnel.
 Flow profiles are likely to be flatter than indicated above.

             Another important factor in choosing the diameter of  the
 flow development tunnel is its effect on the length of the  tunnel  and
 the diameter of the probes.  As a general rule, ten pipe diameters
 are usually sufficient to develop a fully turbulent velocity profile.
 The larger the diameter, the longer the tunnel required and the  longer
 the residence time in the flow development section.  Longer residence
 time leads to higher particulate settling and greater inaccuracy in  the
 measurement.  Therefore, the tunnel diameter should be minimized.  How-
 ever, as tunnel diameter decreases, the pressure drop through the  tunnel
 increases and the size of the probes needed for isokinetic sampling
 decreases.  The problems caused by high pressure drop are obvious.
 Smaller diameter probes should be avoided since they provide higher
 surface to volume ratios and result in more loss of particulate by impac-
 tion.  The 4.3 inch diameter pipe in use offers a reasonable compromise
between these various factors.

             II.2.2.3  Tunnel Sampling Losses

             Particulate deposition in the flow development section
was measured by Introducing an artifically produced mono-disperse  (3.5
micron diameter) methylene blue aerosol into the exhaust injector  in
 the same manner as for auto exhaust.   The system was disassembled after
 the run, the tunnel surface washed with methanol and the washings  analyzed
spectrophotometrically.  The sensitivity of the method for methylene
blue is in ppb range.  Analysis showed that tunnel losses are small,
 amounting to less than 1% of the total aerosol introduced.  No dye
was detected in the tunnel section housing the exhaust injector.  About

-------
                                 - 16 -
0.1% of the aerosol was deposited in the tunnel mid-section, and about
0.3% was deposited in the tunnel section housing the probes.  Independent
tests by U.S. Environmental Protection Agency workers with a tunnel of
similar dimensions have confirmed our results regarding tunnel sampling
losses(13).

          II.2.2.4  Equivalent Emission Rates with Parallel Filters

          Since only a small fraction of the diluted exhaust is sampled
for the particulate analysis, at least two parallel probes coupled
to the appropriate filters are needed to serve as internal checks
on the sampling system.  One method of determining whether proper sampling
is achieved relies on the ratio of the weight of particulate collected (W )
by filter A, and the volume flow rate (F.) through probe A.  This ratio
should equal the corresponding ratio of these parameters for filter
B and probe B, that is:


                           WA     WB     WC
                           —  =  —  =  —  = etc.
                            A      B      C

          The particulate emission rates in grams/kilometer (gms/km)
should be the same for all filters in a given run since

                             W   'F   \   W   / F  \
                     gms _    A i  _P	5    B  I P  j = etc.
                     km      F  ^ Akm /   F   \^Akm/
                              A,            o

where Fp is the volume flow rate through the tunnel and Akm the
distance in kilometers accumulated on the particular test procedure.

          Excellent agreement between parallel filters has been obtained
using this sampling system with conventional and catalyst equipped
vehicles operating on a variety of unleaded fuels under cyclic and state
test conditions.  Partial documentation of this agreement has been
previously described(3,5).

          II.2.2.5  Temperature Maintenance of the
                    Particulate Collection Stage

          The dehumidifier is a key component of the temperature control
system, particularly since the sampling system is one in which the
air/exhaust dilution ratios are low, unlike other particulate sampling
systems(14,15).  This means that the relative humidity of the diluent
air is a key parameter.  For example, during the steep acceleration portion
of the Federal Test Procedure, the exhaust volume flow rate from a vehicle
equipped with a 350 CID V-8 engine may be as high as 120 CFM.  This means that

-------
                               - 17 -
 dilution ratio would drop below 3 in the sampling tunnel.   If the
 relative humidity of the diluent air was high,  attempts to control the
 filter temperature at 90°F would result in condensation of water vapor,
 with the associated loss of particulate matter.   This is shown in
 Figure II-4 which depicts mixture dew point-dilution ratio dependence
 as a function of the relative humidity of the diluent (24°C)  air.

           The key role of the dehumldifier can readily be seen.   If
 the relative humidity of the diluent air is low,  e.g., below  50%,
 it should be possible to maintain a 32°C (90°F)  filter temperature with-
 out condensation occurring.  It can also be readily seen that in the
 absence of the dehumidifier, on humid days, the dew point of  the mixture
 would exceed 32°C at dilution ratios as high as four, so that condensation
 would invariably occur during the acceleration portions of the driving
 cycle.

          Attempts  to  control  filter  temperatures by  omitting  the
 dehumidification  step  and  chilling  the  diluent air would be difficult
 to  accomplish  since water  condensing  on the coils would  feed back
 latent heat, decreasing  the efficiency  of  the cooler.  Continued
 running would  probably result  in  the  condensed water  freezing  on the
 heat  exchangers,  rendering them inoperative.

          Figure  II-5 shows a  typical trace of the relative humidity
 of  the diluted exhaust in  the vicinity  of  the sampling probes during
 FTP operation with  a catalyst  equipped vehicle.  This  trace is obtained
 by withdrawing a  sample just above  the sampling probes and filtering it
 prior  to monitoring  the humidity.  Filtration is necessary in order
 to protect the rapidly responding humidity  sensor(16).

          It is evidentfthat the relative humidity in  the region of
 the probe closely parallels the changes in  the cycle driving patterns.
At no 'point in the  driving  cycle does the relative humidity at the
 probes reach the saturation level at 90°F.  As the relative humidity
 is lower upstream,  condensation in the  tunnel upstream of  the  probe
 does not occur.

          Figure II-6 shows the temperature-time trace at the filter
during the above run which  is a typical case.  A total flow rate of
about 450 SCFM was used.  A four foot long  2 inch I.D. finned tube
between the tailpipe and the exhaust injector was needed to
suppress temperature spikes above 90°F during the steep acceleration
portion of the driving cycle.  It should be noted that the system is
designed to prevent temperature excursions above 90°F, not to maintain
 that temperature during the course of the entire run.

-------
                                         FIGURE II-4

                              DEW POINT OF DILUTED EXHAUST VS.
                                 AIR/EXHAUST DILUTION RATIO

                              At Indicated Relative Humidities
                                of 75°F (23.90C) Dilution Air
                                                      1 120 CFM @ Accel to 58 mph
                                                      2 Air Pump, EGR
                                                                          900F  (32.2QC) line
1.0
2.0
9.0   10.0
                          Dilution Ratio (Dilution Air/Raw Exhaust)

-------
                       FIGURE II-5
Np
tf»
      RELATIVE HUMIDITY OF EXHAUST DILUTION AIR
   MIXTURE AT VICINITY OF SAMPLING PROBES DURING
        THE 1972 FEDERAL TEST—DRIVING CYCLE
>  100
t

9ul  75


i§  50


><  25

5
d    o
                    nfy\7fVAi^^
 Q.

 E
  *
 Q
 u.1
 UJ
 Q.
                                                                  VO

                                                                   I
                   4   5  6   7   8  9   10

                   TIME, HUNDREDS OF SECONDS
                                              12  13

-------
                   - 20 -
                  FIGURE II-6



      TEMPERATURE CONTROL SYSTEM PERFORMANCE

      	CATALYST-EQUIPPED CAR	
01
n
01
i-
110° -


 90° -


 70° -
450 CFM CHILLED AIR

    SYSTEM WITH

    FINNED TUBE
             TIME DURING THE 1972 FTP

-------
                                 - 21 -
          Figure 11-7 is a typical relative humidity-time trace for
a 40 mph steady state cruise experiment.  The relative humidity surges
to about 25% on start up and slowly decreases with running time.

          Complete temperature control can be obtained at 40 mph by
encapsulating the finned tube in a 4-inch diameter metal cylinder
through which ambient air is pumped in a countercurrent direction
to the flow of raw exhaust.  Figure II-8 shows a schematic of this
additional temperature control feature..  Encapsulating the finned
tube is not necessary for the driving cycle.  At the 40 mph cruise,
however, the temperature would slowly rise above 90°F after about
20 minutes if the finned tube was not encapsulated.

          II.2.2.6  Capabilities for Studying Effect
                    of Temperature on Particulate Collection

          For the purposes of this work exhaust particulate matter is
collected at 90°F.  However, particulate can also be collected at
other selected temperatures so that it would be useful for studying
the effect of temperature on the quantity of particulate collected
should the need arise.

          This is because the set point temperature is essentially deter-
mined by the fraction of the dehumidified air that is cooled.  If
collection at a higher temperature is desired, the fraction of
dehumidified air that goes through the heat exchanger is decreased.
This fraction is determined by the set point temperature and  the actual
instantaneous temperature of the exhaust-dilution air mixture in the
filter housing.

          Thus a range of particulate. collection temperatures is
possible, the lower limit being the dew point of the air-exhaust mix-
ture at the lowest dilution ratios, and the upper limit the minimum
amount of cooled-dehumidified air required to prevent temperature
increases, at low dilution ratios.  To date, this range has not been
investigated.

-------
                              FIGURE II-7
    100
>•  GJ 75
L.M  ^^

9oi5

^OO 50
   o
Ol
cc
       0
             RELATIVE HUMIDITY OF EXHAUST DILUTION
              AIR MIXTURE AT VICINITY OF SAMPLING
            PROBES DURING   64 kph= CRUISE CONDITIONS
                                at 32°C
                         5                 10

                            TIME (MINUTES)
15
                                                                            N>
                                                                            N>

-------
                              - 23 -
                            FIGURE II-8
                       FINNED TUBE COOLING SETUP
Raw Exhaust
                    Outlet
                   HUM i  ii 11 11  I Ml
MIN
                     INI I I Ml II  II I  I
                                 To Exhaust
                                 Injector
              Cooling Fins
                                           Air Inlet

-------
                                - 24 -


                          III.  Experimental
III.l  Test Vehicles
          Two matched 1974 350 CID Chevrolets were used in this program.
These vehicles came equipped with air pumps and exhaust manifold air
injection systems.  The engine specifications listed below were set to
manufacturer's specifications.
                      1974 Chevrolet 350 CID V-8

               Spark plugs               .035 in.
               Points dwell              30° + 1
               Basic Spark Timing        8° BTDC
               Idle Speed                600 RPM, transmission in drive
               Carburetor                Rochester 2 barrel, No. 7044114
               Horsepower                145 at 3600 RPM
               Compression Ratio         8.5:1

     III.1.1  Vehicle Conditioning Procedures

          Both project vehicles when received were drained of the leaded
fuel contained in their fuel tanks.  Their fuel systems were flushed to
remove all traces of the factory fuel.  Both vehicles were then driven
by Exxon Research employees to accumulate about 3200 km (^ 2000 miles)
of commuter type mileage for initial break-in.  The break-in fuel had a
sulfur content of less than 100 ppm and a lead level of about 0.05 gin/gal.
The specifications of the break-in fuel are given in Section III.2.2.
To complete the break-in procedure, the vehicles were then operated for
3218 km on Exxon Research's automated Mileage Accumulation Dynamometer
(MAD) using the Federal Mileage Accumulation Schedule (1).  The 6400
kilometer accumulation had two purposes, to break in the vehicles, and
to purge any traces of lead deposits that could have accumulated in the
vehicle's combustion chambers and exhaust system over the few miles of
vehicle operation during assembly and transportation.

          Both vehicles were run through a complete set of particulate
emission tests on all three test fuels to determine if there were any
major differences between the two vehicles with respect to emissions
(gaseous and particulate), and to establish base case engine particulate
emission rates in order to separate vehicle and catalyst contributions
to total particulate emissions.

          One vehicle was then selected as the mileage accumulation
vehicle, the other as the test vehicle.  Both vehicles and all catalyst
containers were fitted with quick disconnects to facilitate rapid inter-
change of catalyst systems between the mileage accumulation vehicle and
the test vehicle.  The test procedure will be discussed in Section III.4.

-------
                                - 25 -
     III.1.2  Catalyst Conditioning Procedures

          All tests were initiated with the fresh catalysts mounted on
the mileage accumulation vehicle in their proper position (post manifold
or toeboard) depending on the catalyst configuration.  The engine operating
variables (carburetor adjustment, spark timing, points dwell, points gap
and idle speed) were set according to the manufacturer's recommendations.
Each vehicle was periodically tuned; after each catalyst break-in for
the mileage accumulation vehicle, and after the battery of tests on a
given catalyst for the test vehicle.

          The mileage accumulation vehicle was operated on the MAD for
about 2900 km (1800 miles) using the Federal Durability Driving Schedule
and the mileage accumulation fuel.  Mileage was accumulated on an eight
hour on, eight hour off, basis to provide a cold start approximately
once every 320 kilometers.  The assumption was that this procedure would
provide adequate thermal conditioning of the catalyst, and that the
repeated cold starts would also subject the catalyst to some degree of
thermal shock.  After completion of the catalyst aging and conditions,
the catalyst was transferred to the emission test vehicle and operated
for 320 km (200 miles) using the Federal Durability Driving Schedule on
the first test fuel to be used for particulate emission measurements.

          The purpose of the 320 km accumulation was to equilibrate
the catalyst with the test fuel.  It was designed to eliminate any storage
factors associated with the break-in fuel that could Influence particulate
emissions, so that these emissions would be truly reflective of the
particular test fuel.  It is quite probable that a 320 km accumulation
is not of sufficient length to obtain equilibrium, but the time and fuel
constraints placed on what is essentially a catalyst screening program
in the first phase of this contract work did not allow operation for
longer mileage in every test.

          To more fully examine the storage problem, an additional test
was made on a beaded oxidation catalyst system in which after following
the normal test procedure, the catalyst-equipped vehicle was conditioned
for an additional 6400 km (4000 miles) with one of the high sulfur test
fuels to ascertain the effect of sulfate storage on particulate emissions.
This additional test and the results obtained are discussed in Section
IV.1.5.

          Following the conditioning, the emission test vehicle was
cold soaked for 16 to 24 hours prior to starting the particulate emission
test procedure sequence.  Control of the cold soak period allowed
reproducible particulate emissions from the same vehicle.

-------
                                - 26 -
          After completion of the particulate emission measurement test
sequence on a given fuel, the vehicle was returned to the MAD to
accumulate 320 km using the second test fuel.  After appropriate cold
soaking and emission testing, the vehicle was again returned to the
MAD to accumulate 320 km on the third test fuel.  Emission measurements
were made which completed the screening of that catalyst.

III.2  Selection of Fuels

          The contract required that three fuels be used in the tests,
a reference fuel supplied by EPA, that reference fuel plus an additives
package, and a high aromatic fuel to be blended at the Exxon facilities,
which contains the additive package.  The aromatics level of the high
aromatic fuel was selected on the basis of what the likely market place
maximum would be.

     III.2.1  The Additive Package

          The contract required an additive package to be added to the
EPA Reference Fuel and to the high aromatic fuel.  The contents of this
package were to contain the following:

          •  0.05 g Pb/gal. as Motor Mix

          •  Additional sulfur as a mixture of thiophene and
             t-butyl disulfide to raise the sulfur content of
             the fuel to 0.1 wt. %.

          •  A nitrogenous  multi-functional additive, and

          •  A heavy carrier oil or polymer type additive.

          Lead as motor mix was added to achieve a level of approximately
0.05 gms/gallon.  Sulfur was added as a mixture of 50% thiophene, 50%
tertiary-butyl sulfide.

          Lubrizol  596 (LZ596) was the nitrogenous multi-functional
additive used.  This additive, manufactured by the Lubrizol Corporation
was used at the manufacturer's recommended maximum dosage, 25 Ibs. per
thousand barrels (0.27 g/gal.)  LZ596 is a non-polymeric material
containing 2.25-2.75% nitrogen by weight.  It functions as a detergent,
corrosion inhibitor, anti-stall agent, and anti-icing agent.  Further
details on the nature of this material are considered confidential by
Lubrizol, but were filed with the EPA Air Pollution Control Office on
April 28, 1971.

          Paradyne 502 was used for the polymer type additive.  This
material, manufactured by the Exxon Chemical Company was used at the
recommended dosage of 42 Ibs. per thousand barrels (0.45 g/gal.  Paradyne
502 is an approximately 3000 molecular weight polymer which contains

-------
                                  -  27 -
0.75% nitrogen by weight.  It functions as a detergent, anti-rust
agent and deposit modifier.  As in the case of LZ 596, further details
on the na.ture of this additive are confidential but are on file with
the EPA Office of Air Pollution Control as of April 28, 1971

          Because of the limited supply of test fuels for this program,
a separate break in fuel for both vehicles and catalysts prior to testing
was used.  This fuel was to contain 0.05 gm Pb/gal. and less than 100
ppm sulfur, have normal volatility characteristics, and an octane level
of at least 93 RON.

     III.2.2  Fuel Specifications

          Table III-l shows the specifications of the break in fuel and
the test fuels.  Fuel (1) is the EPA reference fuel, fuel (2) that
fuel spiked with the additive package, and fuel (3) the high aromatic
fuel containing the additive package.  Because of the dominant role of
fuel sulfur content on exhaust particulate emissions, the test fuels
will hereinafter be identified by their sulfur content such that:


                        Fuel (1) = 0.019 wt.% S
                        Fuel (2) = 0.110 wt.% S
                        Fuel (3) = 0.091 wt.% S

III.3  Catalysts

          A total of 9 catalysts were tested.  These include 4 monolithic
oxidation catalysts, 3 pelletized oxidation catalysts and 2 NOX reduction
catalysts.  The guidelines for catalyst selection were based on the
probability of its commercial use in the near future and availability.

          The following monolithic oxidation catalysts were tested:

(1)  Engelhard PTX-IIB, hereinafter referred to as Engelhard Monolith.

(2)  Two Universal Oil Products catalysts having ostensibly similar
     properties hereinafter referred to as UOP(l) and UOP<2) respectively.

(3)  Matthey Bishop - hereinafter referred to as the Matthey Bishop
     Monolith.

Three pelletized oxidation catalysts were tested.

(1)  Engelhard pelletized catalyst - hereinafter referred to as Engelhard
     Pellet.

(2)  Grace pelletized catalyst - hereinafter referred to as Grace Pellet.

(3)  Air Products pelletized catalyst - hereinafter referred to as
     Air Products Pellet.

-------
                                  - 28 -
                              Table III-l
ASTM Research Octane
ASTM Motor Octane
Lead (gms/gal)
Weight % Sulfur

FIA Analysis

% Aromatics
% Olefins
% Saturates
ASTM, Gum (mg/100 ml)
RVP (psi)
API Gravity @ 60°F

ASTM Distillation (D86)

IBP
 5% Overhead at °F
10%
20%
30%
40%
50%
60%
70%
80%
90%
FBP
% Loss/% Bottoms
:ations of
Break
in
Fuel
95.5
85.9
0.052
0.006
29.6
5.8
64.6
0.4
8.32
61.1
94
120
131
149
168
190
212
229
247
271
313
383
0.4/1.4
Fuels Used
Fuel
(1)
93.0
84.6
<0.01
0.019
21.3
6.4
72.3
0.0
9.4
60.5
92
115
125
143
162
183
206
223
236
251
291
386
1.0/1.5
Designation
(2)
92.6
83.4
0.063
0.110
25.1
8.5
66.4
0.0
8.58
59.6
95
117
128
149
165
190
214
233
250
274
314
365
0.9/1.3

(3)
98.8
86.5
0.056
0.091
45.8
7.1
47.0
4.4
8.64
52.2
100
125
138
160
177
203
222
248
266
297
340
4.2
2.0/1.0

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                                  - 29 -

         The two NO  reduction catalyst systems were:

 (1)  Grace NOX reduction catalyst - hereinafter referred to as Grace
     Reduction.

 (2)  GEM 68 catalyst made by Gould Inc. - hereinafter referred to as Gould
     Reduction.

         The model and serial numbers of these systems where available
 are given in Table III-2 below.

                              Table III-2
             Model and Serial Numbers of Catalysts Tested
       Catalyst
Engelhard Monolith
UOP(l)
UOP(2)
Matthey Bishop Monolith
Engelhard Pellet
Grace Pellet
Air Products Pellet
Grace Reduction
Gould Reduction
 Model
 Number

513
7471-210
7471-529

8026

260
Serial
Number

407 7011
7-2916

HN 2428
III.4  Test Procedure

          As discussed in the introduction section of this report,
the test procedure consisted of operating a catalyst equipped vehicle
through five separate modes:  an initial 1975 FTP, followed by a
one-hour idle, a one-hour 64 km/hr (40 mph) cruise, a two-hour 112
km/hr (70 mph) or two-hour 96 km/hr (60 mph) cruise.  This was
followed by an overnight cooling and a final 1975 FTP.  The one-hour
idle, and the two cruise modes were all hot start tests.  No attempts
to cool down between these tests were made.

          Fresh, pre-weighed glass fiber filters were used in each test
run to collect particulate for total particulate determination.  A
fresh (unweighed) Millipore filter was used in each run to collect
particulate for metals analyses.  Gaseous emission rates were determined
in each test run for hydrocarbon, carbon monoxide, NO  and SO^ in
diluted exhaust.
     III.4.1  Gaseous Emissions

          Since the exhaust particulate sampler is compatible with the
CVS unit, simultaneous gaseous and particulate emission rates could be
measured on each test mode.  Carbon monoxide was analyzed using an
NDIR analyzer, hydrocarbons by FID, NOX by chemiluminescence and S02
by pulsed UV fluorescence.  The measurement technique for S02 is
discussed in detail in Section A.2 of Appendix A.  The detailed gaseous
emission rates are given In Appendix E.

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                                 -  30 -


     III.4.2  Particulate Sampling Procedures

          Four parallel filter samples were taken during each of the
five test modes. These were as follows:

(a)  Two 142 mm diameter Gelman Type A fiber glass filters coupled to
     probes sampling at 15 SCFM.  These samples were used to check
     internal agreement and allow the determination of total particulate
     emission rates, sulfate emission rates, and for analyses of water,
     carbon, nitrogen, non-sulfate sulfur, and platinum.  The analytical
     procedures for sulfate, water, carbon, etc., are discussed in
     Appendix A.

(b)  One 90  mm diameter Millipore ashless filter coupled to a probe
     sampling at 5 SCFM.  This filter sample was used for determination of
     the emission rates of Ca, Al, Zn, Cr, Fe, Cu, Ni, and Pb.  All of
     these metals were determined by emission spectroscopy.  This
     analytical technique and its adaption for measuring vehicular
     metallic emission rates is discussed in Section A.4 of Appendix A.

(c)  A 1.5 SCFM sample for particulate size determination with an Andersen
     Particle Sizing Sampler.  This sampler was modified to determine
     particle size distribution by weight.  The use of the modified
     sampler is discussed in Appendix B.

          The Exhaust Particulate Sampler is designed to collect particulate
emissions at constant temperature (32°C) during the FTP or 64 km/hr (40
mph) steady state cruise.  However, the system was not designed to have
the capability of handling the heat load generated by 96 km/hr (60 mph)
and 113 km/hr (70 mph) cruise conditions.  In order to maintain tempera-
ture control at the high speed cruise conditions, attempts were made to use
a raw exhaust flow splitter.  The function of this splitter was to reduce
the heat load on the sampling system by venting a known constant fraction
of raw exhaust prior to injection of the exhaust into the flow development
tunnel.  The splitter was designed  to reject 75% of the raw exhaust.

          Experiments with ambient  air substituting for raw exhaust
showed that the splitter worked as  intended.  However, the raw exhaust
from an oxidation catalyst equipped vehicle corroded the velocity sensing
elements of the device so that it was inoperable.  The experiments with
the exhaust splitter are described  in Appendix C.

          Consequently, the high speed cruise runs were carried out
with the entire exhaust injected into the tunnel, which meant that particulate
was not collected at constant temperature for these runs.  This means
that during the high speed cruises, deviations from isokinetic sampling
occur.  The error created by non-isokinetic (or anisokinetic) sampling
has been studied by several investigators(2).  For fine particles, less

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                                 - 31 -


than 10 microns equivalent diameter, the error introduced by deviations
from isokinetic sampling that are less than 20% are negligible.  For
coarse particles (greater than 50 microns equivalent diameter), the error
in measuring particulate approximates the deviation from isokinetic
sampling(26)  The Environmental Protection Agency(27) has suggested
that for  deviations from isokinetic sampling of less than 20%, particulate
mass be corrected by the equation


                           M - I  MS (1 + VV)

where M = the actual mass of particulate
     MS = the mass of particulates in the sample
     Vs = volumetric flow rate of the sample
      V = volumetric flow rate of an isokinetic sample

          The above equation indicates that the error in measuring the
particulate mass will be half the deviation from isokinetic sample
regardless of whether the sampling is supra or subisokinetic.

          In the high speed cruises without temperature control, the
deviation from isokinetic sampling through most of the run is below 10%
so that the error in measuring the particulate mass is below 5%.  This
is the error caused in sampling particulate matter present in a stream
above 32°C (90°F).

          Another source of error caused by temperature excursions, above
32°C is that organic matter that exists as particulate at that tempera-
ture and consequently is collected on the filters may not exist as
particulate at the higher temperatures.  This would apply to some of the
organic components that would exist as particulate matter.  There is no
way of evaluating the error from this temperature effect, although it
is probably small because of the following reason.  The lean carburetion
on both vehicles reduces not only the gaseous emissions but  also the
organic exhaust particulate components.  These vehicles are also
equipped with air pumps and exhaust manifold air injection to further
decrease hydrocarbon and CO emissions by reaction of the oxygen in the
air with the hot exhaust gases.  At the high raw exhaust temperatures,
air injection also reduces the gaseous organic precursors of organic
particulate.  Thus, the formation of organic particulate emission rate
of a conventional 1974 GM vehicle should be considerably below that
exhibitied by earlier vehicle models.  Springer(28) presents evidence
that with a 1970 Chevrolet CID V-8, the total particulate emission rate
is very sensitive to temperature below 20QOF.  Based on Springer's
data, it is estimated that at the maximum of the temperature excursion
during the high speed cruise, the decrease in collected particulate
would be approximately 16%.  However, since it takes a finite time
interval to approach the higher temperatures, the run averaged
temperature effect on particulate losses should be below 16%.

-------
                                  - 32 -
         It would also be expected that with the leaner operation of
a 1974 vehicle coupled with air injection, only the less volatile, less
easily oxidized organic precursors would be more likely to survive.  The
formation of these precursors into particulate matter would occur at high
temperatures, so that their collection at filters would be less sensitive
to collection temperature.  Consequently, it would be expected that with
the vehicles used in this program, the effect of temperature at the particu-
late collection stage on the organic particulate matter collected would be
small enough to be within acceptable limits so that only small errors in
calculated emission rates would result.

          When the vehicle is equipped with an oxidation catalyst, the
organic portion of the exhaust particulate is extensively reduced about
an 80% reduction relative to pre-control vehicles, with the result
that there is little temperature dependent organic particulate pre-
crusors in the raw exhaust.  Consequently, the effect of particulate
collection temperature on organic particulate emissions should be quite
small.

          The collection of sulfuric acid aerosol should be independent
of temperature as long as the collection temperature is below sulfuric
acid dew point.  Thus, if the collection temperature does not exceed
about 90°C (29,30), all of the acid exists as aerosol.  Although the
tunnel residence time is small M).l second), the formation of aerosol
droplets is virtually instantaneous(31).  Particulate collection tempera-
tures during the high speed cruises are well below the sulfuric acid
dew point so that all the sulfuric acid exists as aerosol.

          The collection of the metallic components in the exhaust
particulate obviously are not temperature dependent so that no error
in the measurement of these species occurs as a result of the tempera-
ture increases incurred during the high speed cruise modes.

-------
                                  - 33 -


                        IV.  RESULTS AND DISCUSSION


IV.1   Sulfur Compounds in Exhaust Emissions

     IV.1.1   SO,, in Auto Exhaust

          Although the charge of the contract was the characterization
of exhaust particulate matter, the contract specified that 30 S02
measurements should be carried out.  Sulfur dioxide determinations
were performed in virtually every run however since this compound is
not only the most predominant sulfur containing gaseous species in
auto exhaust, but because particulate sulfate is derived from exhaust
S02.  Thus determination of exhaust 802 coupled with determination
of particulate sulfate allows the determination of the fate of fuel
sulfur, and the attainment or lack of a sulfur material balance allows
one to approximately assess the extent of sulfate storage.  The
phenomenon of sulfate storage is discussed in Section IV.1.5.
Sulfur dioxide was measured using the TECO pulsed fluorescence
analyzer discussed in Appendix A.

          Although other gaseous sulfur compounds may exist in auto
exhaust, they are not related to particulate sulfur compounds (pre-
dominantly sulfate), and exist in quantities too small to have
appreciable effects on sulfur material balance.  The accounting of
fuel sulfur in terms of emitted S0£ and sulfate aerosol is discussed
in Sections IV.1.4.1 and IV.1.4.2.

     IV.1.2   Dependence of Total Particulate Emission
              Rates on Fuel Sulfur Content	

          Figure IV.1 shows the total particulate emission rates
obtained on the averaged 1975 FTP's for the base case vehicle,
and with the vehicle equipped with monolithic oxidation catalysts.
It can be seen that with the unequipped vehicle, the total particulate
emission rate is independent of the fuel sulfur content.  With the
monolithic oxidation catalysts, the total particulate emission rate
is approximately linearly dependent on the fuel sulfur content.

          Similar type of behavior was obtained when the vehicle was
equipped with pallatized oxidation catalyst systems.  However, the
total particulate emission rates were lower than that obtained with
monolithic oxidation catalysts, so that a lower order of dependence
of emission rate on fuel sulfur content is observed as shown in
Figure IV.2.


         The average of the initial and final 1975 FTP total particulate
emission rates (Figures IV-1 to IV-3)  was used as a convenient parameter
to approximately gauge the dependence of these emissions on fuel sulfur
content for the base case and catalyst equipped vehicle.  There is no
rigorous basis for choosing this average.   This is especially so since
there are cases with both the monolithic and pelleted oxidation catalyst
runs where large differences in the initial and final FTP total particulate
emission rates were obtained,  indicating that the vehicle-catalyst com-
bination being tested was not stabilized with respect to particulate
emissions.  Sulfate storage in the pelleted oxidation catalyst equipped
vehicle is an additional complicating factor.  That the total particulate

-------
I
CO
   0.250
tf  0.200
o
•H
CO
CO
•H
cu
4J
CO
1-4
3
O
•H
4J
h
CO
CO
JJ
o
H
   0.150
   0.100
   0.050
                                        - 34 -
                                      FIGURE IV-1

               DEPENDENCE OF TOTAL PARTICULATE EMISSION RATES, gms/km
           ON FUEL  SULFUR CONTENT (AVERAGE OF INITIAL AND FINAL 1975 FTP)
                             Base Case Vehicle,  4 Monoliths
©

O
= Base Case

= Engelhard

= UOP(l)

= UOP(2)

= Matthey Bishop
                      0.025
                                   0.050
                               0.075
                                          0.100
0.125
                               Fuel Sulfur Content, Wt.%
CO

ft

 «t
cu
    0'.250
    0.200
                                      FIGURE IV-2

                DEPENDENCE OF TOTAL PARTICULATE EMISSION RATES, gms/km
             ON FUEL SULFUR CONTENT (AVERAGE OF INITIAL AND FINAL 1975 FTP)
o
•H
CO

"   0.150
6
                       Base Case Behicle, 3 Palletized Catalysts


              O   = Base Case

              V  = Engelhard

              ^  = Grace

                  = Air Products
cu
4J
CO
3
U
s
    0.100
    0.050
                     0.025       0.050        0.075        0.100


                               Fuel Sulfur Content, Wt.%
                                                                        0.125

-------
                               - 35 -

emission rates vary linearly with fuel sulfur content with oxidation
catalyst equipped vehicles,  Figures IV-1 and IV-2,  may be fortuitous,  at
least for the FTP test runs.  Thus, no theoretical  significance should be
attached to the slopes of the lines in Figures IV-1 and IV-2.   While total
particulate emission rates may vary linearly with fuel sulfur  content  with
an oxidation catalyst equipped vehicle over a large variety of conditions,
the case for linearity would best be substantiated  with a thoroughly con-
ditioned particulate emission stabilized test vehicle.  This would be  beyond
the scope of this program.  As stated previously, the intention of the plots
in Figures IV-1 and IV-2 is  to elicit the approximate dependence of particu-
late emissions and fuel sulfur levels as a function of catalyst type.

          By contrast, the total particulate emission rates obtained
when the test vehicle was equipped with NOX reduction catalysts
showed no dependence on fuel sulfur content.  As shown in Figure IV.3,
the particulate emission rates with NOX reduction catalysts are
essentially the same as with the base case vehicle.

          On  the 64 km/hr (40 mph)  cruise  runs,  the  total particulate
emission rates with the unequipped vehicle were  low  and  independent
of fuel sulfur content.  The  total particulate emission  rates with
monolithic  catalyst equipped vehicles were linearly  dependent on  fuel
sulfur levels, and were greater  than what  was exhibited  on  the
1975 Federal  Test Procedures, Figure  IV-4.  It  can  be seen that
significant differences in  the emission rates are exhibited by  the
monolithic  systems tested,  the UOP catalysts emitting about four
times as much exhaust particulate as the Matthey Bishop  catalyst.
Similarly with the pelleted oxidation  catalysts, as  shown  in  Figure IV-5,
total particulate emission  rates also  varied  linearly with  fuel sulfur
content.  The emission  rates  with  the  pelleted systems were lower than
those of the  monolithic  systems, the exception being the monolithic Matthey
Bishop catalyst.

          As shown previously in Figure  IV-3,  the particulate  emission
rates of NOX reduction catalyst  equipped vehicles were invariant
with respect  to fuel sulfur content.  This was not the case when  the
vehicle equipped with these catalysts was  operated at 64 km/hr  for
one hour.  As shown in Figure  IV-6, th£ total particulate emission
rates vary linearly with fuel sulfur content as  in the case of  the
oxidation catalysts.  Total particulate emission rates with the NO
reduction catalysts are lower than what was obtained with any of  x
the oxidation catalysts (monolithic or pelleted  type).

          At the high speed cruises (96 or 113 km/hr), the total
particulate emission rates of the vehicle  equipped with  the various
monolithic catalysts were linearly proportional  to fuel  sulfur  content,
but were lower than that exhibited by  the  same catalysts or the same
fuels at the lower vehicle cruise speeds.  The relative  particulate
emissions of the catalysts is changed in that the second UOP monolith,
which emitted lower levels of particulates than  the  first UOP monolith
at 64 km/hr vehicle cruise speed, emitted  higher level at the
higher speed cruise.  Both UOP monolith equipped vehicles emitted
more particulate than when equipped with the Engelhard or Matthey
Bishop monolith.   These results are shown  in Figure  IV-7.

          With pelleted oxidation catalysts, deviations  from linearity
are observed with the Engelhard and Air Products catalyst systems..
Emission rates obtained with the Grace catalyst equipped vehicle

-------
                                       - 36 -


                                      FIGURE IV-3
1
c
o
•r-l
CO
CO
•l-l
E
CD
4J
CO
 3
 u
t-l
CO
Pu
CO
4-1
O
H
               DEPENDENCE  OF TOTAL PARTICULATE EMISSION RATES, gins/km

           ON FUEL SULFUR  CONTENT (AVERAGE OF INITIAL AND FINAL 1975 FTP)
    0.050
    0.040
    0.030
    0.020
    0.010
                    Base Case Vehicle,  Two NO  Reduction Catalysts
                                       J_
                        0.025         0.050       0.075

                               Fuel Sulfur Content, Wt.%
                                                              0.100
0.125
4

 i
 •»
 0)
 o
•H
 CO
 CO
 0)
 4J
 CO
    0.500
    0.400
     0.300
     0.200
 p
 CO
 (X,


 "co"   0.100
 4J
 O
 H
                                      FIGURE IV-4

                 DEPENDENCE OF TOTAL PARTICULATE EMISSION RATES,  gins/km
               ON FUEL SULFUR CONTENT MONOLITHIC CATALYST EQUIPPED VEHICLE
                                 64 km/hr  (40 mph cruise)
                  O = Base Case

                  • = Engelhard

                    = uop(i)

                    = UOP(2)

                    = Matthey Bishop
                         0.025        0.050        0.075


                               Fuel  Sulfur Content,  Wt.%
                                                               0.100
0.125

-------
                                     -  37  -
                                    FIGURE IV-5

              DEPENDENCE OF TOTAL PARTICULATE EMISSION RATES,  gms/km
                   ON FUEL SULFUR CONTENT, PELLETIZED  CATALYSTS
                             64 km/hr  (40 mph Cruise)
                     Base Case

                     Engelhard
                     Grace
                     Air Products
                       0.025       0.050        0.075

                             Fuel Sulfur Content, Wt.%
                                                0.100
                                                                         0.125
J
m
§,
0)
4J
2
c
o
•H
(0
CO
'e

0)
3   0.100
•H
CO
PL.
o
H
    0.200  _
    0.150  -
    0.050  -
                      FIGURE IV-6

DEPENDENCE OF TOTAL PARTICULATE  EMISSION RATES,  gms/km
  ON FUEL SULFUR CONTENT WITH NO  REDUCTION CATALYSTS
	64 km/hr (40 mph Cruise
 O = Base Case

   = Grace

 A = Gould
                      0.025        0.050       0.075

                             Fuel Sulfur Content, Wt.%
                                               0.100
                                                                         0.125

-------
                                     - 38 -



                                     FIGURE IV-7


               DEPENDENCE OF TOTAL PARTICULATE EMISSION RATES, gins/km

             ON FUEL SULFUR CONTENT MONOLITHIC CATALYST EQUIPPED VEHICLE

                              (96 or 112 km/hr Cruise)	
CO

i,
«   0.400
s

c
o

S   0.300
•r-l
e

cu
u

5   0.200

u
*   0.100
l-l
CO
4J
o
                O = Base Case

                • = Engelhard

                  = UOP(l)

                Q= UOP(2)


                • = Matthey Bishop
                       0.025        0.050        0.075

                              Fuel Sulfur Content, Wt.%.
                                                               0.100
0.125
CO
91
4J
    0.400
o
•H
CO

•g   0.300

w

cu
4J
CO
 U
•H
4J
    0.200
CO
PL.


^   0.100
                                    FIGURE IV-8


               DEPENDENCE OF TOTAL PARTICULATE EMISSION RATES,  gins/km

             ON FUEL SULFUR CONTENT PELLETED CATALYST EQUIPPED  VEHICLE

                	(96 or 112 km/hr Cruise)	
                O = Base Case


                V = Engelhard

                ^ = Grace


                   = Air Products
                        0.025       0.050        0.075

                               Fuel Sulfur Content, Wt.%
                                                              0.100
 0.125

-------
                                 - 39 -

varied linearly with fuel sulfur content.  The high speed cruise
results with the pelleted catalyst systems are shown in Figure IV-8.
Figure IV-9  shows that the total particulate emissions varied linearly
with fuel sulfur content at the high speed cruises when the vehicle
was equipped with either the Grace or Gould N0x reduction catalysts.

          The dependence of the total particulate emission rates on the
fuel sulfur content is due to the production of sulfate aerosol.
This aerosol is produced in the presence of an oxidation catalyst,
and under certain circumstances in the presence of a NOX reduction
catalyst.  The presence of a heterogeneous catalyst is a necessary
requirement. Sulfate production is discussed in the next section.  The
detailed data on total particulate emission rates are given in
Appendix E.

     IV.1.3   Sulfate Emission Rates

          The quantity of soluble sulfate on the total filters was
routinely determined using the titrimetric procedure discussed in
Appendix A.  Figure  IV-10 shows the sulfate emission rates as a
function of fuel sulfur content obtained on the 1975 FTP for the un-
equipped base case vehicle, and when the vehicle was equipped with
each of the four monolithic oxidation catalysts.  The sulfate emission
rates are reasonably linear with fuel sulfur content as in the case
of the total particulate emission rate.  The slopes are about half
that obtained on the total particulate plot.  These results are
consistent with earlier results(3) in which it was found that the
sulfates emitted from an oxidation catalyst equipped vehicle account
for approximately half the total particulate.

          As shown in Figure IV-11 , similar results are obtained with
palletized oxidation catalysts in that the emission rates of sulfate
are approximately linear with fuel sulfur content and account for
about half of the total particulate.  The absolute levels of emitted
sulfate for the pelleted catalyst equipped vehicles are generally
lower than those obtained with a monolithic oxidation catalyst
equipped vehicle.  The differences exhibited between the monolithic
and pelletized catalyst systems on the 1975 FTP can be attributed
to storage of sulfate on the pelleted systems.  Sulfate storage
phenomenon are discussed in Section IV.1.5.

          Figures IV-12  and IV-13  depict the sulfate emission dependence
on fuel sulfur content for both monolithic and pelletized catalysts
vehicles for the 64 km/hr cruises.  In both cases, the sulfate emission
rates vary linearly with fuel sulfur content.  Sulfate emissions from
the base case vehicle are too low to be sensibly plotted on the above
figures.

          The wide range of sulfate emissions for a given fuel sulfur
level shown in Figure IV-12  indicates that significant differences
exist between the various monolithic catalysts.  For example, the vehicle
equipped with the Matthey Bishop catalyst emitted only about one-fourth
of the sulfate emitted with one of the UOP systems.  It should be
realized that only one sample of each catalyst was tested, replicate
testing would be necessary to substantiate the observed differences.
EPA (17), in their own tests, have corroborated the above results so
that there is good reason to believe that the differences observed are
significant.  The sulfate emission rates with the pelleted catalysts
are comparable to the Engelhard monolith and the second UOP monolith
tested.

-------
J
 CO
 i,



3 o.ioo

 o
•1-1
 CO
•? 0.075
                                    FIGURE  IV-9

              DEPENDENCE  OF TOTAL PARTICULATE EMISSION RATES,  gms/km

          ON FUEL SULFUR  CONTENT, NOX REDUCTION  CATALYST EQUIPPED VEHICLE

           	(96 km/hr  Cruise)	
 01
 4-1
 CD
 •—I
 3
 U
 CD
 Pu
 CD
 4J
 o
 H
   0.050
   0.025
               O = Base  Case


               A = Grace


                 = Gould
            D           0.025        0.050        0.075       0.100       0.125

                             Fuel  Sulfur  Content,  Wt.%


                                    FIGURE  IV-10

                    SULFATE EMISSION RATE VS.  FUEL SULFUR CONTENT

                       (AVERAGE OF INITIAL  AND FINAL 1975 FTP)

            BASE CASE  AND MONOLITHIC OXIDATION CATALYST EQUIPPED VEHICLE
J  0.100
J 0.075

-------
                                        - 41 -
J
 01
 3
CO
     0.050
     0.040
     0.030
 c
 o
 •H
 CO
 -2   0.020
 w
 0)
     0.010
                                      FIGURE IV-11
                    SULFATE EMISSION RATES VS. FUEL SULFUR CONTENT
                        (AVERAGE OF INITIAL AND FINAL 1975 FTP)
                     BASE CASE AND PELLETIZED OXIDATION CATALYSTS
                 = Base Case
                 = Engelhard
                 = Grace
                 = Air Products
                       0.025         0.050       0.075
                              Fuel Sulfur Content, Wt.°
                                                          0.100
 0.125
     0.250
                                      FIGURE IV-12
                 DEPENDENCE OF SULFATE EMISSION RATES, gms/km ON FUEL
                  SULFUR CONTENT MONOLITHIC CATALYST EQUIPPED VEHICLE
                 	64 tan/hr (40 mph Cruise)	
J    0.200
01
a
CO
«    0.150
§
f-l
CO
e
u
V
4J
10
CO
0.100
0.050
                = Base Case
                = Engelhard
                = UOP(l)
                = UOP(2)
                = Matthey Bishop
                        0.025       0.050        0.075
                             Fuel Sulfur Content,  Wt.%
                                                         0.100
0.125

-------
                                      FIGURE IV- 13
                     DEPENDENCE OF SULFATE EMISSION RATES, gros/km
              ON FUEL SULFUR CONTENT PELLETIZED CATALYST EQUIPPED VEHICLE
                                64 km/hr (40 mph Cruise) _
0>
01
01
c
o
•H
CO
03
•i-l
0)
4J
CO
3
C/3
    0.100
    0.075
    0.050
    0.025
                      Base Case

                      Engelhard

                      Grace

                      Air Products
                        0.025        0.050       0.075

                              Fuel Sulfur Content, Wt.%
                                                              0.100
            0.125
CO
o>
4J
CO
CO


1

o>
4J
CO
    0.125
    0.100    _
    0.075
    0.050
    0.025
                                      FIGURE IV-14

                    SULFATE EMISSION RATES VS. FUEL SULFUR CONTENT
                     BASE CASE AND MONOLITHIC OXIDATION CATALYSTS
                     	(96 or 113 km/hr Cruises)	
                     = Base Case

                     = Engelhard

                     - UOP(l)

                     = UOP(2)

                     = Matthey Bishop
                       0.025
                                    0.050        0.075

                              Fuel Sulfur Content, Wt.%
0.100
0.125

-------
                                - 43 -
          At the higher cruise speeds 96 or 113 km/hr (60 or 70 mph),
the sulfate emissions from the monolithic oxidation catalyst equipped
vehicles were essentially linear with fuel sulfur content.  These
results are shown in Figure IV-14.  The second UOP system emitted
higher levels of sulfates than did the first one, the reverse of the
emission rates at the lower cruise speeds.  One possible reason for this
type of reversal in relative emission rates is that the vehicle speed
when the second UOP catalyst was tested was 96 km/hr as opposed to 113
km/hr for the first system.  Again, the sulfate emission rates with the
base case vehicle are too low to be sensibly plotted on the figures below.

          Basically similar results were obtained with the pelletized
oxidation catalysts, Figure  IV-15.  The results are shown as straight
lines although there are apparent departures from linearity.  At the
high speed cruises, the sulfate emission rates observed with these
catalysts are comparable to those observed with monolithic catalysts.
This indicates that sulfate storage on the pelletized catalyst system
is not a major factor during high speed cruise.  Consequently, under
these conditions, both types of catalysts exhibit equivalent sulfate
emission rates.

          The total particulate emission rate when the vehicle was
equipped with NOX reduction catalysts did not depend on the fuel sul-
fur content on the 1975 FTP. In fact, as was previously shown in
Figure  IV-3,  the total particulate emission rates obtained with these
catalysts on the 1975 FTP was indistinguishable from the base case
vehicle emission rates. This was the case because under FTP conditions,
the levels of sulfate emitted were comparable to that emitted by the
unequipped test vehicle, Table IV-1.

                                 Table IV-1
            Average Sulfate Emission Rates (Initial and Final
             1975 FTP) from NOX Reduction Catalyst Equipped
            	Vehicle, and Base Case Vehicle	

NOX Reduction            Fuel Sulfur          Sulfate Emission Rate,
  Catalyst                  Wt.%              	gins/km	

    None                    0.019                      0.002
    None                    0.091                      0.002
    None                    0.110                      0.002
    Grace                   0.019                      0.002
    Grace                   0.091                     <0.001
    Grace                   0.110                      0.004
    Gould                   0.019                      0.001
    Gould                   0.091                     <0.001
    Gould                   0.110                     <0.002

           On the steady state cruises however, the total particulate
emission rates with the NOX reduction catalyst equipped test car were
linearly dependent on fuel sulfur content as previously depicted in
Figures  IV-6  and IV-9.    This dependence on fuel sulfur content was
due to production of sulfate under the lean operating conditions
of the cruise test runs.  Figures  IV-16  and  IV-17  show the sulfate
emission rates with both NOX reduction catalysts as a function of fuel
sulfur content.

-------
                                       FIGURE IV- 15
 CO
 I,
 e
 o
 B,
03

-------
                                        - 45 -
                                      FIGURE IV-17

                     DEPENDENCE OF SULFATE EMISSION RATES,  gms/km

          ON FUEL SULFUR CONTENT, VEHICLE EQUIPPED WITH NO  REDUCTION  CATALYSTS

          	96 km/hr (60 mph)Cruise    X	
J
   0.050
   0.040
   0.030
§
•H
e
u
   0.020
«S  o.oio
1-1
3
CO
O   = Base Case


    = Grace


    = Gould
                     0.025
                  0.050
0.075
0.100
0.125
                              Fuel ,Sulfur Content, Wt.%

-------
                                    - 46 -
           Subsequent air/fuel ratio measurements  showed  that  even with
 the  Exhaust Gas Recycle system removed,  the vehicle operated  much of
 the  time at near stoichiometric and net  lean conditions.   It  is  assumed
 that the emitted sulfate was catalytically produced under lean operating
 conditions during the cruise test modes.  Although  the vehicle went net
 lean during the acceleration portions of the FTP, the  duration of the
 lean operating regime is apparently too  transient to produce  significant
 quantities of sulfates.

      IV.1.4  Exhaust Sulfur Material Balance

           The predominant sulfur compounds in vehicular  exhaust  are
 S02  and sulfate particulate.  Consequently, the  fate of  fuel  sulfur
 could be adequately determined by an accounting  of  these two  exhaust
 components.  Figures IV-18  to  IV-26 show the S02 and  sulfate measurements
 for  all catalyst/fuel combinations in terms of the  fraction of gasoline
 sulfur accounted for by the sum of SO2 and sulfate. The detailed data
 are  presented in Appendix E.

           Figure IV-18 shows the S02 and sulfate  emissions for the
 monolithic catalysts for FTP conditions, Figure  IV-19  for the 64 km/hr
 cruise; and Figure IV-20 for the 96 and/or 113 km/hr cruise.   Figure IV-21
 shows the S02 and sulfate emissions for  the pallatized catalysts for FTP
 conditions, Figure IV-22 for the 64 km/hr cruise; and  Figure  IV-23 for
 the  96 and/or 113 km/hr cruise.  Figure  IV-24 shows the  S02 and  sulfate
 emissions for the NOX reduction catalysts for FTP conditions, Figure
 IV-25 for the 64 km/hr cruise; and Figure IV-26  for the  96 km/hr cruise.

           IV.1.4.1  Sulfur Material Balance With
                     Monolithic Catalysts	


           Figure IV-18  shows  the average  total sulfur emissions for
the four monolithic catalysts under 1975 FTP conditions.   The shaded
bars represent the percentage of the  total  sulfur consumed in the
engine  emitted as sulfate,  the  clear bars the percent of fuel sulfur
emitted  as SC^.  With the exception of the Matthey Bishop monolith
system,  the exhaust sulfur material balance is poor.  Much of the
fuel sulfur cannot be accounted  for in exhaust either as gaseous or
particulate components.

           The lack of  a sulfur  material balance is attributed to sul-
fate storage  on  the catalyst-substrate system.  When conversions of
exhaust  S02 is low, adequate sulfur material balances can be  obtained.
For example,  earlier work on conventional vehicles  in which conversions
to sulfate were  less  than one  percent showed  that the fuel sulfur could
be quantitatively accounted  for  predominantly as 502(18).  It may be
inferred therefore that the Matthey Bishop  oxidation catalyst is
less active for  S02 conversion  than the  other monoliths based on  the
higher  S02  emission rates observed with  that  system which was almost

-------
                            FIGURE IV-18
S0n AND SULFATE EMISSIONS FOR MONOLITHIC CATALYSTS FOR THE 1975 FTP
or Sulfate
>-•
o
o
- 90
00
to
^ 80
OJ
JJ
-U
1 70
i-i
3
LO
0)
5 50
D
V)
to
« ^
0
30
20
10
0
Mat they Bishop
-
.



Engelhard


-
*



uj^"i
— •


1




—



5****
__








^
	









§£





UOP(l)














ST^i






$>?



•wMta

ABC ABC AEC
Fuel











= S02

B&i = Sulfate
* S0? not found
uop(2) Fuel Sulfur Content







•^M

^Ov
\A-A
'W
)OC








1
A = 0.019%
B = 0.110
C = 0.091





ABC


-------
                                                   FIGURE  IV-19
                       SO,. AND SULFATE EMISSIONS FOR MONOLITHIC CATALYSTS AT 64 gm/km CRUISE
0)


Jj 100

r-l
3
C/3
 CM

O
•H
B
   90
   80
    70
    60
to

 2  50

•H
;H
 O

 S  40
o
   30
   20
   10
Engelhard

   XX ^\,
   %«
   ^
   ^

              ABC
              Matthey Bishop
                   ABC
                                       UOP(l)
ABC
                                                                       UOP(2)
ABC
                                                                             n
                                            = so*
                                                                                              = Sulfate
                                         *   S02  not  found
                                        Fuel  Sulfur  Content



                                              A  =  0.019%

                                              B  =  0.110

                                              C  =  0.091
                                                                                                     oo

                                                                                                     I
        Fuel

-------
                                                 FIGURE  IV-20

                     L AND SULFATE EMISSIONS FOR MONOLITHIC CATALYSTS AT 96-113 km/hr CRUISE
01

CO
£   10°
 CM
O
to
O
m
     80
     70
     60
     50
     30
     20
     10
             MONO  (I)
              AB
                               MONO  (II)
                                ABC
                                                                 MONO  (III)-2
                                                MONO  (III)-l
                                                   A  B   C
ABC
                                                                                              = so.
                                                                                              =Sulfate
                                                                                          A    S02 not found

                                                                                          **   S02 not measured



                                                                                         Fuel Sulfur Content

                                                                                              A = 0.019%
                                                                                              B = C.110
                                                                                              G = 0.091
                                                                                                                    VO

                                                                                                                    I
          Fuel

-------
                                                     FIGURE IV-21


                           SO  AND SULFATE EMISSIONS FOR PELLETED CATALYSTS  FOR THE 1975 FTP
 
-------
                                                   FIGURE IV-22


                       S0n AND SULFATE EMISSIONS FOR PELLETED CATALYSTS AT 64 km/hr CRUISE
 
-------
                                            FIGURE IV-23
                SO,, AND SULFATE EMISSIONS FOR PELLETED CATALYSTS AT 96-113 km/hr CRUISE
                kJ W«
<4-l
r-l
3
l-i
0
CN
O
CO
(fl
"^
ti
QJ
•H
e
w
H
• -*
V5
a
•H
0
'.I
O
U-l
C
6-5




100


90



80


70
60



50


40



30
20
10
                        Grace
        Engelhard
                                          Air Products
0       ABC
   Fuel
ABC
                                            D.
     S02

     Sulfate

     S02 not found

'<*    S02 not measured


 Fuel Sulfur Content

     A = 0.019%
     B = 0.110
     C = 0.091
                                                                                                     S3

                                                                                                      I

-------
                                          FIGURE IV- 24
            SO,, AND SULFATE EMISSIONS FOR NO  REDUCTION CATALYSTS FOR THE 1975 FTP
      Grace
» 100
CO
3
0
CN
8 so
CO
CO
"8 70
4J
•I-l
B
w 60
3
1 50
0)
CS
•rl
"o 40
en
•g 30
B-S
20
10
0

-
























••^•^



































Go
^MM










Tnc
uld











I^^^H












= so2

^ = Sulfate












                                                                                                     Oi
                                                                                                     UI
     ABC
ABC
FUEL

-------
                                                         FIGURE IV-25
                                         S02 AND SULFATE EMISSIONS FOR NOX REDUCTION
                                                CATALYSTS AT 64 km/hr CRUISE
   100
0)
jj
(U
3
co
 CM
O
CO
eg
T3

-------
                                            FIGURE IV-26
                             S02 AND SULFATE EMISSIONS FOR NOX REDUCTION
                                    CATALYSTS AT 96 km/hr CRUISE
                          Gould

100
0>
Q
"3 90
C/l
I,
H
o
CM 80
o
to
ft
" 70
13
0)
1J
JJ
6 60
w
3
•:j 50
0)
c
3 40
o
CO
3
30
ii 1
0
20
10
0 .
Grace



.


_


_




„.


-


-



-

-
-

^•M^























S2




*


















28
\Af
v$
W




























»


























































£&<
W


= so.
2

























^
^
M^^























1
«8

ys/y
^X8 = Sulfate


* - malfunction at CVS,
S02 reading uncertain




















FUEL
ABC
                          ABC

-------
                                  -  56  -
sufficient  in  itself  to  account  for  the fuel sulfur.  Although the
emitted  sulfate  levels obtained  on the FTP with the UOP(l) catalyst
system were comparable to  that obtained with the Matthey Bishop
catalyst, the  S02  emission rates were considerably lower.  This
indicates that the extent  of  conversion of S02 to sulfate is greater
with  the UOP(l)  catalyst but  that an appreciable portion of the
sulfate  made does  not show up in the emitted exhaust.

            This  is substantiated by  the similar behavior on the 64
km/hr (40 mph) cruises.  Again,  the  total sulfur balance for the
Matthey  Bishop catalyst  is nearly 100%, while the other monolithic
catalysts on the  average  account  for  55 to 75% of the fuel sulfur
consumed.   The sulfate yields from the Matthey Bishop catalyst are
considerably lower ^15%)  than the other monoliths which averaged
about 36% and  ranged  from  12  to 53%.

            On  the  high speed  cruises (96-113 km/hr), the sulfate emis-
sion rates  with  the Matthey Bishop system were comparable to that of
the Engelhard  and  UOP(l) monoliths.  However, the S02 emission rates
with the Matthey Bishop  system were  higher than that observed with
the other catalysts and  again, a better sulfur material balance was
obtained.   These results indicate that although the sulfate emission
rates of the catalyst systems discussed above are comparable, the
actual S02  conversions may be considerably different.

            Although the  two UOP catalysts exhibited similar behavior
on the lower cruise speed  test mode  (in terms of S02 and sulfate emis-
sions),  at  the higher cruise speeds, the UOP(2) system exhibited essen-
tially the  same  S02 emission rates,  but higher sulfate emission rates
than the UOP(l) monolith.

          IV.1.4.2    Sulfur Material Balance With
                      Pelletized Catalysts	

            As  shown in Figures IV-21  to IV-23  still greater deficiencies
in sulfur balances are obtained with palletized catalyst systems.  On
the FTP, Figure IV-21,   only 20-35%  of the total fuel sulfur is
accounted for, the Engelhard and Grace catalysts emitting about 4% of
the fuel sulfur as sulfate, the Air  Products System emitting about
10% of the  fuel sulfur as  sulfate.

            Similar behavior is exhibited on the 64 km/hr (40 mph) cruises.
The sulfur  material balance deficiencies obtained with the pelletized
systems are greater than that obtained on their monolithic counterparts.
Thirty to 60%  of the  fuel  sulfur was accounted for, with the sulfate
yields ranging from 20 to  30%.

            On  the  96  or  113 km/hr cruises the sulfur material balance
was generally better  than what was obtained on the 1975 FTP's or the
64 km/hr cruises.  Sulfate conversions averaged from about 25 to 30%.
The sulfur  dioxide accounted from about 39 to 51% of the fuel sulfur,
which is higher  than  what was obtained on these systems, on either
the FTP or  64  km/hr cruises.  The percent, of the fuel sulfur accounted
for (S02 +  sulfate) ranged from 63 to

-------
                                   - 57 -
          The higher S02 emission rates on the high speed cruises,
indicative of lower SC>2 conversions may be due to the following
factors:

          (1)  The higher space velocities at the high speed
               cruises could result in lower conversions.  Bench
               scale studies(19) assessing the effect of space
               velocity on conversion substantiate this claim.

          (2)  Because of the unfavorable equilibrium (S02 + 1/2 02 ^ 803),
               conversion is less favorable at the higher catalyst
               temperatures which would prevail at the high speed
               cruises.
           The sulfur material balance would be expected to be better
because, in addition to the above, because of the reduced tendency
to store sulfur at the higher cruise speeds (and consequently) higher
catalyst temperatures.  Sulfate storage experiments carried out on this
contract program are discussed in Section  IV.1.5.

          IV.1.4.3    Sulfur Material Balance With
                      NO  Reduction Catalysts	
                        J\             "
           Figure IV-24  shows the average total.sulfur emissions for
the two NOX reduction catalysts under 1975 FTP conditions.  Average
total sulfur recoveries for both systems was about 97%.  Sulfate
emissions amounted to less than 1% conversion.  Under FTP conditions,
the sulfur material balance with these catalysts was similar to that
obtained with the unequipped vehicle.

           Sulfate emissions increased for both catalyst systems on
both cruise test modes, Figures IV-25 and 26.  Conversions based on
emitted sulfates ranged from 4 to 18% on the 64 km/hr cruise.  The percent
of total fuel sulfur accounted for in this cruise mode ranged from 72 to
about 82%, higher than that obtained with the vehicle equipped with the
oxidation catalysts.  The inability to achieve a complete sulfur balance
apart  from experimental error may be due to some sulfate storage
occurring on the NOx reduction catalyst system.

           On the 96 km/hr cruise, the average of the total fuel sulfur
accounted for with both systems was 96%.  The sulfate emission rates
were generally lower than those measured at lower cruise speeds.  Sul-
fate conversions ranged from 1.5 to 15%, averaging about 8 to 9% for
both catalysts over all fuel combinations.  The S02 emission rates were
higher on the higher speed cruise mode.

           At the two cruise modes both NOx reduction catalysts resembled
the oxidation catalysts in that sulfate particulate was emitted, the
emission rate varying in an approximately linear fashion with fuel
sulfur content (Section  IV.1.3).  In addition, the lower conversions
at the higher speeds is probably due to the same factors operating to
reduce conversion over the oxidation catalysts, namely the higher
catalyst temperature and space velocity.

-------
                                      -  58 -
           The resemblance  to oxidation catalysts is due to the
fact that the vehicle in  the cruise modes was operating at stoichiometric
and net lean conditions.  The Gould catalyst contains a small oxidation
catalyst ahead of the Ni-Cu reduction catalyst in order to extend its
life(20).  This oxidation catalyst acts as an exhaust oxygen scavenger.
Under stoichiometric or lean conditions this catalyst would also be
expected to catalyze the  oxidation of exhaust S0? to sulfate.  Similar
considerations apply to the Grace NOx reduction catalyst, which contains
noble metal and therefore could function as an oxidation catalyst for
S02 under near stoichiometric and net lean conditions (21).

     IV.1.5    Sulfate Storage on  a Pelletized Catalyst System

           Previous  studies(3,19) had shown  that sulfate can be  stored
at under cyclic driving  conditions and  released under high speed  cruise
conditions.  To more fully  examine sulfate storage  the following  ex-
periment was carried out.  The  test vehicle  was reequipped with  the
Engelhard palletized catalyst that had  been  previously tested.   The
catalyst equipped vehicle was conditioned  for 3218  km  (2,000 miles)
on the 0.091 wt.% sulfur  fuel using the Federal Durability Cycle.
Following conditioning,  the vehicle was cold soaked for  24 hours, and
then run through  the program test sequence used for screening  the
catalysts namely  1975 FTP,  one  hour idle,  64 km/hr  one-hour  cruise,
96 km/hr two-hour cruise, an overnight  soak, and a  final 1975  FTP.
Unlike  the screening study  in which the conditioning and test  fuel
was of  the same sulfur  content, the test fuel in this case was the
0.019 wt.% sulfur fuel.   Conditioning and  testing as outlined  above makes
it possible  to determine  whether  stored sulfate can be released  under
other than high speed cruise conditions.

          The  CO, hydrocarbon,  NOX, SC>2, total particulate,  sulfate
and metal emission rates  were determined as  in the  previous screening
studies.  Table IV-2 below  shows  that the hydrocarbon and  NOX  emissions
are similar  in both  types of runs (standard  vs storage), but that large
differences  in CO emissions are obtained.

                            Table IV-2

               Comparison  of Gaseous Emission Rates  of
             Vehicle  Equipped with Engelhard  Pelletized
          Oxidation Catalyst Operated on 0.019 Wt %  S Fuel

                        Emission Rate, gins/km
                  on 1975 FTP  (Initial  and Final)

         Standard  Conditioning        Storage Conditioning
          CO       HC       NOy          CO      HC      NOy

         2.53    0.22    1.37         1.23    0.19    1.20
         2.50    0.22    1.32         1.01    0.19    1.09

-------
                                  -  59  -
          The decrease in CO emissions was unexpected and cannot be
satisfactorily explained at present.  Although reduction of stored
sulfate by CO can occur, the increase in SC>2 emissions that was ob-
served was not sufficient to account for the decrease in CO emissions.
The increased S02 emissions after storage conditioning will be con-
sidered shortly.

          As shown below in Table IV-3, larger differences were ob-
served with respect to SC^, sulfates, and total particulate.

                            Table IV-3

                Emission Rate of Indicated Exhaust
             Component, gms/km for Test Runs Fallowing
      Standard Conditioning (A), and Storage Conditioning (B)
Test
Type
75 FTP
64 km/hr
96 km/hr
75 FTP
502 H2S04
A
0.015
0.0
	
0.017
B
0.050
0.016
0.088
0.077
A
0.003
0.001
0.027
0.002
B
0.044
0.119
0.103
0.100
Total
Particulate
A
0.061
0.009
0.115
0.036
B
0.105
0.258
0.239
0.152
          The large increase in total particulate  emission  rates  is
due to Increased sulfate emissions as a result of  release of  stored
sulfate, as shown in Tables IV-4 and IV-5 below.

                           Table IV-4

                 Storage Experiments, Palletized
           Engelhard Catalyst. 0.019 Wt % S  Test Fuel

                             % Fuel Sulfur Accounted For
                                As        As
              Test            Sulfate     SO,      Total

           75 FTP                50        83       133
           64 km/hr             191        38       229
           96 km/hr             157       200       357
           75 FTP               105       126       231

-------
                                 - 60 -
                              Table IV-5

                 Standard Screening Tests, Pelletized
               Engelhard Catalyst, 0.019 wt.% Test Fuel
                               % Fuel Sulfur Accounted For
                               As           As
               Test          Sulfate        SP_2—        Total
             75 FTP            3.2          24.2        27.4
             64 km/hr          1.5           0.0         1.5
             96 km/hr         24.6          35.5        60.1
             75 FTP            2.1          53.3        55.4


           The  64  km/hr  cruise  results are  reminiscent  of earlier storage
studies(3,19) in that  sulfate yields  in excess  of 100%  (based on the
sulfur  content  of  the  test  fuel and fuel  economy are obtained).  However,
these storage tests have also shown that  sustained storage  of sulfate
can result in the  following situations:

           (1)  Sulfate  yields  exceeding  100% can be obtained on lower
                cruise speeds such as 64  km/hr.

           (2)  Sulfate  yields  exceeding  100% can be obtained under
                cyclic driving  conditions.

           (3)  The total exhaust sulfur  out  (S02 + sulfate) can
                exceed 100% although  each component may not.

           (4)  Sulfur dioxide  emissions  alone  can exceed the theoretical
                fuel consumption values as  it did in 96 km/hr cruise
                and the  second  1975 FTP.

           Although sulfate yields exceeding  theoretical values have
been previously observed, that  S02 emissions  could also exceed theoretical
fuel consumption values  was unexpected.   Increased SO   emissions could
occur through several  routes.   Reduction  of a portion of the stored sulfate
could occur by  the following reaction:

                     Stored H-SO, + CO 	=>  S02 + HO  + C0_

           If the  test fuel is  one of low sulfur content, the fraction
of exhaust CO that is  oxidized  need not be  large in order that SO2
yields  exceeding 100%  can occur.  Under these circumstances, the CO
emission rate would be undistinguishable  from that obtained in a standard
run.

          As mentioned previously, the decrease in CO emissions  is  too
great to account for the  increased S02 emission.  A decrease in  CO  emission
rate from 2.5 to 1.0 gms/km by reduction of stored sulfate  would  result in
an increase in S02 emissions of 3.4 gms/km.   This is  far in excess  of  the
total S02 emission rates  observed even with S02 yields  as high as  200%.

           Another possible mechanism operating to produce  greater than
100% yields of  S02 is  the catalytic decoirnnsitron of some of the stored
sulfate as shown below:

-------
                                     - 61 -
                                          S02 + 1/2 02
                     (stored)

It would not be possible to decide which mechanism or if both were
operating to produce S02 emissions exceeding theoretical based on how
the storage tests were conducted.  Separate experiments would be required
to determine the mechanism of increased SO2 production, which were not
called for in the contract.

      IV.1.6  Bound Water in Exhaust Particulate

          Previous work(3) had shown that the water content of exhaust
particulate increases with increasing sulfate content, but that the
ratio of water to sulfate was relatively constant.  Moreover this ratio
corresponds approximately to what would be expected from the equilibrium
% composition-relative humidity relationship at conditions under which the
water analysis took place.  This relationship at 20°C is depicted in
Figure IV-27.

          As shown in Figure II-6 Section II.2.5, the average relative
humidity at the filter during cyclic test conditions is about 20% at
90°F.  This corresponds to 28% relative humidity at room temperature.
The particulate filter is conditioned and weighed in a constant tempera-
ture humidity room (about 45% RH).

          It can be seen from Figure 11-27 that a change from 28% rela-
tive humidity to 45% relative humidity results in minor increase in the
weight fraction of water.  Thus the weight of particulate should when
sulfuric acid present correspond closely to the quantity collected
on the filter during a run.  The relative humidity of the analytical
laboratory although not maintained constant, is probably close to that
in the weighing room, which means that the quantity of water measured
by the Karl Fisher method is a reliable measure of the quantity of bound
water collected on the particulate filters during a test run.  Table IV-6
below shows the quantities of bound water in terms of emission rates as
determined by Karl Fisher titration for the base case vehicle and
several catalyst runs on the 1975 FTP.
                              Table IV-6

             Relation of Bound Water to Sulfate Emissions

                                            Emission Rate, gins/km
                                                 on 1975 FTP
Run    % Fuel                             Total
No.    Sulfur         Catalyst         Particulate   H.SO.     H^O
——    —~~~—              '            ———~—~——   ~ e.  H      L
20     0.019     None                     0.019      0.001    <0.001
46     0.091     Engelhard Monolith       0.226      0.087     0.092
61     0.091     Engelhard Pellet         0.062      0.016     0.013
75     0.110     UOP(l)                   0.090      0.027     0.022
106    0.091     Grace Reduction          0.019      0.001    <0.001
121    0.091     Gould Reduction          0.031      0.001    <0.001
135    0.110     Grace Pellet             0.065      0.034     0.029
151    0.091     UOP(2)                   0.173      0.078     0.085

-------
                                      -  62  -
                                 FIGURE IV-27



                     EQUILIBRIUM % COMPOSITION - RELATIVE

                   HUMIDITY CURVE FOR AQUEOUS HSO/  AT  2QQC
c
o
    100
o
co
o
CO
 CM
sc

c
•H

O
     75
     50
•&
•H
0)
     25
      0
         0
                     25           50            75



                            Relative Humidity,  %
100

-------
                                   - 63 -
It can be seen that the emission rates of water and HoSO* are comparable
and are fairly close to the equilibrium curve shown in Figure IV-27.

       Differences from equilibrium could be due to experimental
errors in the various analytical determinations.  Another reason
for the differences is that not all the sulfate (which is what is deter-
mined by analysis) is present as the free acid, but as rather a portion
may exist as metal sulfates.  The latter would be unresponsive to
environmental relative humidity conditions.  The distribution of sul-
fate could be ascertained by the difference between sulfate determined
by the titrimetric procedure and by titration with base.  Although the
acid-base titrations were not performed, it may be readily inferred
from the close approach to the equilibrium % composition-relative
humidity curve that free sulfuric acid is the preponderant sulfate
exhaust particulate component.  Earlier work(3) has shown that similar
considerations would apply to steady state cruises.

     IV.1.7  Morphology of Automotive Sulfate Particulate

       The morphology of the sulfate deposits on the glass fiber
exhaust particulate filters provides direct visual evidence that the
free acid is the predominant form of sulfate particulate emitted by
oxidation catalyst equipped vehicles.  Figure IV-28 shows an electron
micrograph of a glass fiber filter from a test with a conventional
vehicle in which little sulfate was produced.  This filter was used
as the last stage of the Andersen Impactor and consequently contains
little if any organic particulate matter.

       Figure IV-29 is a micrograph of a total filter from a run
with an oxidation catalyst equipped vehicle.  This filter contained
125 mg of sulfate.  The presence of the free acid can be seen by
the globular deposits on many of the glass fibers and web-like films
that wet many of the fibers.  It will be noted that no crystalline
particulate matter appears to be collected on the filter indicating that
little if any sulfate salts are present.  Globular droplets, and wetting
of fibers are phenomenon that can only be associated with liquids,
providing further evidence that automotive sulfate exists predominantly
as the free acid.

       It is also of interest to note that the parallel lines running
through the micrograph in Figure IV-28 are absent in Figure IV-29.
These lines are image distortions due to the presence of static charges.
They are absent from the micrograph shown in Figure IV-29 because the
sulfuric acid is conductive and can dissipate the static charge.  Thus,
the process of obtaining an electron micrograph itself provides evidence
of the presence of free sulfuric acid.

-------
          - 64 -
        Figure IV-28


   Scanning Electron Micrograph of

 Absolute Filter From Andersen Impactor
l.OOOX 1 MM = 1 MICRON
  10 MICRONS
 * •;'.  >^     -     - - ^
 fw.-  ''',// '*& •«: •"•• "Lr'j'gli^

 ^%^^p
 .;','.  -. -jV '• ..v  -7^.
 - ^'  ,• ••«!"/ .•" iSx^ v»  'J^'1
        Figure IV-29



  Scanning Electron Micrograph of Total

   Filter Containing 125 mg of Sulfate
 1000X, 1 MM = 1 MICRON
= 10 MICRONS
              .

-------
                                   - 65 -
     IV.1.8  Non-Sulfate  Sulfur Exhaust Particulate

           Chemical spot tests were carried out on particulate samples
generated from the 1975 FTP and 64 km/hr  (AO mph) test runs for non-
sulfate sulfur containing particulate matter.  The samples analyzed
included those from runs on the unequipped vehicle,  and when the
vehicle was equipped with the various catalysts screened in the test
program.

           The extreme sensitivity of many of these tests should allow
detection of low levels of non-sulfate particulate matter.  Negative
results establish the maximum emission rate possible based on the
sensitivity of the spot test and the mileage accumulated on the
particular test run.  The spot tests used were those listed in
Feigl(22).  These are discussed in detail in Appendix A.

           The filters were analyzed for  the presence of the following
sulfur compounds:

           thiocarbonyls
           thiols
           sulfides
           disulfides
           isothiocyanates
           sulfoxides
           sulfinic acids
           sulfones

           The selection of the above compounds as possible exhaust
components is based on chemical species known to be present in auto
exhaust which could function as precursors to the above compounds or as
reactants involved in their production.  The basis of this selection
is discussed in Appendix D.

           All tests for the above compounds were negative.  Based on
the sample size taken (0.42% of the active filter area), the emission
rates of the above compounds cannot exceed the values listed in
Table IV- 7 below.

                                  Table IV-7

  ESTIMATED MAXIMUM EMISSION RATES OF NON-SULFATE SULFUR EXHAUST PARTICULATE

                                    	gms/km	
    Compound Type                   1975  FTP              64 km/hr cruise
                                          -4                      -4
Thiocarbonyl                       8 x 10                  2 x 10
Thiols
Sulfides                              "                        "
Disulfides                            "                        "
Isothiocyanates
Sulfoxides                            "                        "
Sulfinic Acids                        "    3                   "    _4
Alkyl Sulfonic Acids               1 x 10~                 2.5 x 10
Alkyl Sulfonic Acids                  "                        "

-------
                                    - 66 -
          In several cases, larger portions of filters were analyzed
for the sulfur compounds listed above.  Negative results were also obtained
in these instances.  It is quite probable therefore that the emission
rates of these compounds if they exist at all in auto exhaust are
probably several orders of magnitude below those rates listed in Table
IV-8.   Limited sample sizes were necessary because of the large number
of different analyses that were made on the particulate filters.

          On the basis of the results, it appears that nc significant
quantities of organic sulfur compounds are emitted froir catalysts under
these test conditions.

-------
                                   - 67 -
IV.2   Exhaust Metal Particulate Emission Rates

          The emission rates of the following metals were measured on
all of the test runs:

          Ca, Al, Zn, Cr, Fe, Cu, Ni, Pb, and Pt.

Although referred to as metals, the above exhaust components with the
possible exception of platinum would not be likely to exist in their
elemental state.  Both analytical methods (emission spectroscopy and
X-ray fluorescence) do not distinguish whether the above exist in the
metallic or combined state.  The analytical techniques are discussed
in detail in Section A.5 of Appendix A.

          It is most likely that the above metals when present In exhaust
exist as oxides, sulfates, or mixed oxy-sulfates.  No attempt was made to
determine the types of metallic compounds.

          The metal derived particulate emissions will hereinafter be
referred to as metal oxides.  This term is used simply for convenience and
to indicate that the metal emissions do not exist as the free metals.  It
is not meant to imply that the oxide is the only combined form of the metal.


     IV.2.1   Metal Oxide Emissions Under 1975 FTP Conditions

          The detailed metal  emission data are presented in Appendix E.
Figure IV-30  shows the metal emission rates on the 1975 FTP's calculated
as total metal oxides for the base case vehicle and for the vehicle  equipped
with the various catalysts.  Both initial and final FTP emission rates
are shown for each fuel sulfur content.

          The total metal oxide emission rates are generally higher  when  the
vehicle is equipped with oxidation catalysts ranging from about 0.0018
to 0.0110 gms/km on the 1975 FTP.  Metal oxide emissions from the NOX
reduction catalysts ranged from about 0.0019 to 0.0064 gms/km.  The
lowest metal oxide emissions were observed with the base case vehicle.
The range in this case was from 0.0002 to 0.0033 gms/km.  There does
not appear to be any dependence of metal oxide emission rate with fuel
sulfur level (or correspondingly sulfate emissions), whether the vehicle
is tested in the conventional mode, or equipped either with oxidation
or reduction catalysts on the 1975 FTP.
          The increased metal oxide emissions from catalyst vehicles
can probably be associated with attrition from the catalyst system.
The differences exhibited between oxidation catalysts and NOX reduction
catalysts may be due to attrition being greater under the leaner conditions
(higher oxidation potential) that would prevail with these systems.

-------
                                                  FIGURE  IV-30
                  TOTAL METAL OXIDE  EMISSION  RATES,  gms/km OBTAINED  WITH  INDICATED CATALYST,
                 INITLAL AND  FINAL  1975  FTP  ON EACH TEST  FUEL;  (	 = INITIAL,  	  = FINAL FTP)
                	> = 0.019% S. O=  0.110% S. • =  0.091%  S	
en
•a
x
o
—I
«
u
01
•u
u
0.0100

0.0090

0.0080 .

0.0070 .

0.0060


0.0050

0.0040


0.0030 |-

0.0020
     0.0010J-   '
              Base
              Case
              A
                0-1
              No
           Catalv-, t
                  Engelhard UOP(l)
                  Monolith  Monolith
UOP(2)
Monolith
                                               O-l
Mat they
Bishop   ^ngelhard. Grace
Monolith
                                                         O-l
Pellet
Pellet
Air
Products
Pellet    Grace
Gould
                                                                                                                       00
                                                                                                                       I
                                            Oxidation Catalvsts
                                                       NO  Reduction
                                                       ™"  X          ~™
                                                         4         ts

-------
                               -  69  -

     IV.2.2  Metal Oxide Emissions Under Cruise
             Conditions, Relation  to  Sulfate Emissions

          As sulfate emissions were higher on the 64 km/hr.  and 96 km/hr.
cruises, it was of interest to see if the metal oxide emission rates  could
be correlated with sulfate emissions  (fuel sulfur content).   Figures  IV-31
to IV-39 show the total metal oxide emission rates as a function of fuel
sulfur content for the 64 and 96 km/hr. cruises.   The sum of the metal
particulates are usually less than 5  to 10% of the sulfate emissions.

          Generally, the sum of the metal emission rates on a given run with
an oxidation catalyst vehicle are  a small fraction of the sulfate emissions.
However, on the FTP's with the 0.019  wt.% sulfur fuel,  the metal emission
rates exceeded the sulfate emission rates.  This is primarily due to the
fact, as discussed above, that metal  oxide emissions are higher on the FTP's
than on steady state cruises.  When this phenomenon is  coupled with the fact
that sulfate storage is more favorable on the FTP than  on the steady state
cruises, it is not surprising that the metal oxide emission rates, however
low, could exceed the H2S04 emission rates when an oxidation catalyst equipped
vehicle is operating on a low sulfur  fuel under cyclic  driving conditions.
Table IV-8 shows the relative emission rates of metal oxide to sulfates for
the vehicle equipped with the various ocidation catalysts on the cyclic and
steady state cruises, operated on the three test fuels.  The FTP values are
the averages of the initial and final FTP's of the test sequence.

          There does not  appear to be  any direct  relationship  between
fuel sulfur content and metal oxide  emissions.   Indeed, with  the exception
of  the Air Products pelleted oxidation catalyst  (Figure  IV-37),  the
metal oxide emissions  from  the vehicle operating  on  the  low sulfur fuel
are generally higher or comparable to  those  observed when a high sulfur
test fuel is used.  These results should  not be  taken  to, mean  that some
type of inverse relationship exists  between metal  oxide  emissions  and
sulfate emissions  (related  linearly  to fuel  sulfur  content), but rather
that other factors are  operating.  No  systematic  assessment of these factors
was made.  However, tentative conclusions may  be  drawn regarding the Influence
of  some of the variables  encountered on metal  oxide emission rates.

          For example,  the  metal  oxide emission rates  are generally
higher on the 1975 FTP's  than on  the steady  state  cruises.  This applies
to both the initial and final FTP's,indicating that accelerations  and
decelerations are  the major factors  responsible  for  the  production of
these types of emissions.

          With several  exceptions, the emission rates  on the  first FTP
were higher than the final  FTP.   This  may be due  to purging of the
exhaust by the first FTP, idle, and  cruise  tests  prior to the
final FTP.  Assuming that purging is responsible  for the  lower emission
rates obtained on  the  final FTP,  the fact that the  FTP emission rates
generally are higher than the steady state cruise  emission  rates supports
the hypothesis that accelerations and  decelerations are  the most important
factors influencing metallic particulate  emissions.

     IV.2.3   Emission  Rates of Specific  Metals

          Analyses for  specific metals were  carried out  in  order to
determine how the  presence  of catalysts alters the  emission pattern  of
metal-derived particulate.  The effect of the  catalyst on metal-derived
particulate matter can  occur by way  of catalyst,  substrate  attrition,
or both, and/or by  reaction between  catalytically produced  exhaust
components and the exhaust  system.   For example,  catalytically produced
sulfuric acid  could react with the walls  of  the  exhaust  system,  with
some of the surface reaction products  then becoming  entrained  in the

-------
                                        - 70 -
CO

oo
en
c
o
•H
CO
CO
•H

-------
in
6
00
CO
e
o
•H
[0
CO

-------
       0.005
                                  - 72 -



                                FIGURE IV-35




                 METAL  OXIDE  EMISSION RATES,  gms/km VS.

               FUEL SULFUR, WT.% ON  STEADY STATE CRUISES



                            Engelhard  Pellet
       0.004
CO


00
in
c
o
•1-1
en
en

•a
w

0)
TJ
•H
X
o
0)
J-l


-------
                                         - 73 -
in
c
o
•l-l
U)
in
w

0)
•o
•H
     0.00020
     0.00150
•g    0.00100
     0.00005
           0
                                     FIGURE IV-37


                      METAL OXIDE EMISSION RATES, gin/km   VS.

                    FUEL SULFUR. WT.% ON STEADY STATE  CRUISES
                                 Air Products Pellet
•  = 64 kra/hr

O  = 96 km/hr
                                     J_
                                              _L
                       0.025
                   0.050
0.075
0.100
0.125
I
    0.00050
    0.00040
oo

at
o   0.00030
•rl
co
in

•a
w
cu   0.00020
"O
•s
o

"«   0.00010
                                     FIGURE IV-38


                       METAL OXIDE EMISSION RATES,  gms/km VS.

                     FUEL SULFUR. WT.% ON  STEADY  STATE CRUISES
                            Grace NO  Reduction Catalyst
      64 km/hr

      96 km/hr
                        l
                                 I
                      0.025
                   0.050        0.075


                  Fuel Sulfur,  Wt.%
              0.100
            0.125

-------
0.00025
                                     - 74 -
                                 FIGURE IV-39

                   METAL OXIDE EMISSION RATES,  gms/km VS.
                 FUEL SULFUR.  WT.% ON STEADY STATE  CRUISES
0.00100
     Gould NO  Reduction  Catalyst

64 km/hr cruise
96 km/hr cruise
0.00075
                                                    ,o	o-
0.00050
      0
                    JL
             _L
 -L
                  0.025
            0.050        0.075

           Fuel Sulfur,  Wt.%.
0.100
0.125

-------
                                - 75 -
                              Table IV-8

              Relative Emission Rates, Total Metal Oxides
         To Sulfates for Oxidation Catalyst Equipped Vehicles
     Catalyst
       Total Metal Oxide Emissions as % of
   Sulfate Emissions on Indicated Vehicle Test
% Fuel
Sulfur
Engelhard Monolith
Engelhard Monolith
Engelhard Monolith

UOP (1)
UOP (1)
UOP (1)

UOP (2)
UOP (2)
UOP (2)

Matthey Bishop
Matthey Bishop
Matthey Bishop

Engelhard Pellet
Engelhard Pellet
Engelhard Pellet

Grace Pellet
Grace Pellet
Grace Pellet

Air Products Pellet
Air Products Pellet
Air Products Pellet
0.019
0.110
0.091

0.019
0.110
0.091

0.019
0.110
0.091

0.019
0.110
0.091

0.019
0.110
0.091

0.019
0.110
0.091

0.019
0.110
0.091
75 FTP

 212
  10
   8

 367
  10
  25

  88
  13
   7

 367
  19
  11

 325
  55
  63

 215
  42
  29

  63
  10
  19
64 km/hr.

    7
    1
   10
    2
    2

   80
   10
   <1
    1

    4
    2
96 km/hr.

   40
    2
    2

    5
   <1
    2

    4
    6
   <1
    1

   15
    2
    2
    1

-------
                                 - 76 -
exhaust  stream.  This  could  result  in an increase in the metallic
content  of  exhaust  particulate  relative to conventional vehicles.

          IV.2.3.1   Emission Rates of Platinum

          Portions  of  the glass fiber filters were analyzed for platinum.
In no case  was platinum  detected.  Based on the detection limits of
0.35 ygms/cmS platinum  emission rates must be below the following
values for  the vehicle tests shown below in Table IV-9.

                             TABLE IV-9
               MAXIMUM POSSIBLE PLATINUM EMISSION RATES

                                      Maximum Possible
                                      Platinum Emission
                     Test               Rates, gms/km

               1975 FTP                  5.6 x 10~5
               64 km/hr., 1 hr.          1.6 x 10~5
               96 km/hr., 2 hrs.         5.2 x 10~6
          IV.2.3.2   Emission Rates of Aluminum

          Figure IV-40  shows the aluminum emission rates on the initial
1975 FTP for the base case vehicle and for the vehicle equipped with the
nine catalysts, for each of the three test fuels.  It can be seen that
the aluminum emission rates are generally higher when the vehicle is
equipped with a catalyst indicating that some attrition of the catalyst
substrate may have occurred.  The maximum emission rate observed was
with the Engelhard pelleted catalyst system, 0.00045 gms/km, which was
about six times greater than the maximum rate observed with the
unequipped vehicle.

          The inability to detect platinum is consistent with the
observed aluminum emission rates.  For example, even at the highest
aluminum emission levels observed,about 0.001 gms/km, the platinum could
be as much as 5~6% of the aluminum content and still be below our
platinum detection limits.  Since the platinum content is well below
1% of the substrate, it should not be detected in auto exhaust particulate.

          IV.2.3.3   Emission Rates of Lead

          Figure IV-41  shows the lead emission rates for the base case
vehicle, and when the vehicle was equipped with each of the nine
catalysts on the initial 1975 FTP for each test fuel.

-------
                                                         FIGURE  IV-AO

                                  ALUMINUM EMISSION RATES, gms/km OBTAINED WITH  INDICATED
                             CATALYST. INITIAL 1975 FTP. • = 0.019% S.  Q=  0.110%  S.  •= 0.091% S
M

B,
tO
ft
CO
CO
•H
g
u
B
•i-l
0.00050


0.00045


0.00040


0.00035


0.00030


0.00025


0.00020


0.00015


0.00010


0.00005
                 Base
                 Case
                    Engelharc
                    Monolith
UOP(l)
Monolith
UOP(2)
Monolith
Matthey
Bishop
Monolith
Engelhard
Pellet
Grace
Pellet
Air
Products
Pellet
Grace
Gould
               No
              Catalyst
                                             Oxidation Catalysts
                                                                NOX Reduction
                                                                  Catalysts

-------
                                                    FIGURE IV-41

                            LEAD EMISSION RATES,  gins/km OBTAINED WITH INDICATED CATALYST,
                               INITIAL FTP,  • = 0.0197. S, O = 0.110% S. •  = 0.091% S
CO
cu
o
•H
CO
(0
•H

A

•O
CO
0)
0.0020


0.0018.


0.0016.


0.0014-

0.0012


0.0010


0.0008


0.0006


0.0004


0.0002
             Base
             Case
                      Engelhard
                      Monolith
                             UOP(l)
                             Monolith
UOP(2)
Monolith
                                           A
(0.005)
                                                     Matthey
                                                     Bishop
                                                     Monolith
Engelhard,
Pellet
Grace
Pellet
Air
Products
Pellet
Grace
                                                                                               A
Gould
                                                                                                                       oo
                                                                                                                       I
             No
           Catalyst
                                                Oxidation Catalysts
                                                                                            NOX Reduction
                                                                                              Catalyst

-------
                                 - 79 -
          With  the  exception  of  the FTP's with  the Matthey-Bishop
 monolith  and  the  Engelhard  pelleted system,  the lead  emission  rates
 of  the  vehicle  equipped with  the other catalyst systems was  indis-
 tinguishable  from those of  the base case vehicle.  It would  be expected
 that  the  lead emission rates  would be independent of  whether or not
 the vehicle was equipped with a  catalyst since  the leaded  particulate,
 unlike  the other  metallic participates, is ultimately fuel derived.
 Previous  studies  with production vehicles operating on leaded  fuels
 have  shown that the lead emission rate measured at any instant of
 time  in the life  history of a vehicle is not necessarily representative
 of  the  average  amount of lead emitted over its  lifetime  (23).

          Figure  IV-42  shows the lead emission rates for  the  base case
 vehicle,  and  for  the catalyst vehicle on the second FTP.   It can be
 seen  that, in general, the  lead  emissions are lower on the second FTP
 of  the  test sequence.  The  lead  emission rate from the Engelhard pelleted
 catalyst-equipped vehicle is  still higher than  the base case vehicle
 or  when the vehicle is equipped  with the other  catalysts,  excepting
 the Engelhard monolith.

          The higher lead emissions from the Engelhard pelleted catalyst-
 equipped  vehicle  may be due to its greater storage capability  than other
 catalytic systems,so that it  emits more leaded  particulate than the
 other systems when  conditions are favorable  for release.   The  increased
 lead  particulate  emissions  exhibited by the  Engelhard monolith-equipped
 vehicle may be  due  to an unrepresentative erratic release.

          The high  lead emissions obtained with the Engelhard  monolith
 could also be related to failure of a previous  Engelhard system as a
 result  of misfire under high  speed cruise.  This resulted  in catalyst
 temperature above 1100'C for  about 10 minutes.   The test was terminated,
 new plugs installed, and the  vehicle checked out.

          A 1975  FTP the following day (Run No.  35, Appendix E) showed
 that  the  catalyst had become  deactivated as evidenced by considerably
 higher  CO, hydrocarbon, and S02  emissions than  the initial FTP (Run No.
 31, Appendix  E)•  The lead  emission rates on the FTP  with  the  deactivated
 catalyst  were the highest obtained in all the test runs except  for one
 run with  the Matthey-Bishop catalyst.  The leaded particulate  may have
 been  driven off the catalyst  substrate during failure of the catalyst
 deposited downstream, and a portion emitted on  the FTP run with the
 deactivated catalyst.

          The lead emission rates shown in Figures IV-42 to IV-43
are for the vehicle re-equipped with a new Engelhard monolith which was
 subjected to an accelerated conditioning in order to remain on schedule.
The higher lead emission rates observed with this catalyst may be due
 to entrained exhaust lead deposits that were present in the exhaust
system as a result of failure of the  previous catalyst.

-------
FIGURE IV-
LEAD EMISSION RATES, gms/km OBTAINED WITH INDICATED CATALYST,
1975 FTP, • = 0.019% S,O = 0.110% S, • = 0.091% S
(* Filter of Second FTP for Matthey Bishop Sent to EPA for Analysis)



0.00100

0.00090
J
1 0.00080
&

S 0.00070
&
g 0.00060
•H
CO
CO
6 0.00050
"O
3 0.00040

0.00030

0.00020
0.00010


Base
Case



_

.


_

.


-

- N
• •
i
J
i
'
i
No
Catalyst
Engelhard
Monolith

R
I \
;\
I k
i
i
i
i
1
l
l
£










UOP(l)
Monolith













i
\
\
\ •
\ /
d




UOP(2)
Monolith















\
\

V



f\--l J — A_

Matthey
Bishop
Monolith













•ifc
J>
*Jf\
^U




ion Catalyi
Engelhard
Pellet

t
1
l
l
1
i
i
1
i
1
1
1
l
1 f

&








Grace
Pellet



















\ /


Air
Products
Pellet
















P
^ /
V


Grace















l
i
» r
\ /
»/
b


Gould















f
l
l
l

•r'


NO Reduction
3CS Catalyst
                                                                   00
                                                                   o

-------
                                                      FIGURE  IV-43
                              LEAD EMISSION RATES AT  64 AND 96 km/hr CRUISE OBTAINED WITH

                            INDICATED CATALYST. •= 0.019% S.    Q= 0.110% St  •  = 0.0917.  S
    0.00100 -
4
CO
I
0)
00
c
o
•H
CO
M
•H
e
w

•o
CO

-------
                                  - 82 -
          Figure IV-43 shows the lead particulate emission rate for all
catalyst-fuel combinations on the 64 and 96 km/hr. cruises.  It can be
seen that excepting both the monolithic and pelleted Engelhard catalyst
runs, the lead emissions from the other catalyst runs were indistinguishable
from the base case vehicle runs.

          Generally,  the emitted lead was considerably less than 50%
of the  lead burned.   For example, with the unequipped vehicle, the
emitted lead accounted for 10 to 23% of the lead burned on the FTP's.
With the Engelhard pelletized oxidation catalyst, the emitted lead
accounted for about 33% of the  lead burned.

          This agrees well with other workers  (23) using a leaded fuel
containing 3 grams of lead per  gallon as motor mix.  These workers
found that the emitted lead accounted on the average for about 48% of
the lead burned.  It  is reasonable to expect that if only about half
of a much higher lead input can be accounted for, the emitted lead
levels  in our work should account for still smaller fractions of the
lead input.  For example, with  the Grace pelletized oxidation catalyst-
equipped vehicle, an  average of about 9% of the input lead could be
accounted for in the  emissions  for the 6 FTP's.

          IV.2.3.4    Emission Rates of Iron

          Figure IV-44  shows the iron emission rates obtained on the
first 1975 FTP for the unequipped vehicle, and for the vehicle equipped
with the various catalysts.  As in the previous sections, the results
are shown for each of the test fuels.

          It can be seen that the emission rate of particulate iron is
generally higher when the vehicle is equipped with oxidation catalysts
than for the unequipped vehicle and the NOX reduction catalyst-equipped
vehicle.  This suggests that the increase in iron emissions above the
levels  of the unequipped vehicle may be due to reaction of the exhaust
system with catalytically produced sulfuric acid.  However, it will be
noted that the iron emission rate appears to be Independent of the fuel
sulfur  content (or sulfate emission level).  This may be due to a
surface limited reaction of iron in the walls of the exhaust system
with catalytically produced sulfuric acid.  The increased iron emissions
above the usual levels associated with engine and exhaust system wear
is probably due to both factors (usual attrition plus reaction with
sulfates) operating.

-------
                                                          FIGURE  IV-44

                                 IRON  EMISSION RATES,  gins/km OBTAINED WITH INDICATED CATALYST
                                  INITIAL  1975 FTP.  • =  0.019% S, O = 0.110% S,  • = 0.091% S
                                             (0.0049)
J
CO
5

o
•H
•a
0)
•1-1
 o
     0.00250
0.00200
0.00150
     0.00100
     0.00050
              Base
              Case
                                                                                  (  0.0049)
                   Engelhard
                   Monolith
UOP(l)
Monolith
   r
                                                 o-a
                                             UOP(2)
                                             Monolith
Matthey
Bishop
Monolith
Engelhard
Pellet
Grace
Pellet
                                                    Air
                                                    Products
                                                    Pellet
Grace
                                                                                                      \
Gould
                                                                                                                      oo
                                                                                                                      OJ
                No
              Catalyst
                                             Oxidation Catalysts
                                                                NOx Reduction
                                                                •  Catalysts  ~

-------
                                 - 84 -
          IV.2.3.5   Emission Rates of Nickel

          Figures IV-45  and IV-46  show the nickel emission rates
on the first and second FTP's respectively for all vehicle-catalyst-
fuel combinations.  It can be seen that the nickel emission rates are
independent of fuel sulfur content.  The nickel emission rates of
the base case vehicle was the same as when the vehicle was equipped
with each of the seven oxidation catalysts, and with the Grace NOX
reduction catalyst.  Dramatic increases in the nickel emission rates
were observed when the vehicle was equipped with the Gould NOx
reduction catalyst.

          These results with the Gould NOx reduction catalyst are
similar to what was obtained in earlier pre-contract work with
Gould NOx reduction catalysts (3).  The nickel emission rates from
the Gould NOX reduction catalyst-equipped vehicle on the 1975 FTP
ranged from 1 x 10~3 to values exceeding 2 x 10~3 gins/km.  Earlier
results on a somewhat different Gould NOx reduction catalyst showed that
on the 1972 FTP, nickel emission rates ranged from 2 x 10~3 to
8 x 10-3 gms/km.

          The nickel emission rates on the steady state cruises were
lower than FTP emission rates, as all metal derived particulate emissions
were.  However, differences between the Gould catalyst-equipped vehicle
and the base case vehicle, and the vehicle equipped with the other
catalyst systems are readily discernible.  Steady state cruise nickel
emissions with the Gould catalyst-equipped vehicle are 2 to 5 times
higher than that observed with the other systems.

          Preliminary A/F measurements on the test vehicle equipped with
the Gould catalyst indicates that removal of the air pump was sufficient
to produce net rich conditions as required for proper operation.  However,
detailed A/F measurements performed after the catalyst was conditioned
and run through the program test sequence showed that the vehicle was
operating in the lean mode.  The increased nickel emissions, therefore,
may be the direct result of improper lean operation.

          IV.2.3.6   Emission Rates of Copper

          Figures IV-47  and IV-48  shows the copper emission rates on
the initial and final FTP's respectively for all catalyst-fuel combinations.
The FTP copper emission rates are generally below 6 x 10~4 gms/km.  Some-
what higher rates are observed with the Engelhard monolithic and pelleted
catalyst system.  These differences, if significant, may simply reflect
the different levels of trace metals in the various catalyst systems.

-------
                                                     FIGURE IV-45

                            NICKEL EMISSION RATES, gins/km OBTAINED WITH INDICATED CATALYST,
                            INITIAL 1975  FTP. • =  0.019% S. O = 0.110% S. • = 0.091% S
     0.00250
J
CO
a
0>
6
•1-1
en
09
Q>

O
•rl
a
     0.00200
     0.00150
     0.00100
     0.00050
              Base
              Case
                        Engelhard
                        Monolith
               No
             Catalyst
UOP(l)
Monolith
                                   A,
UOP(2)
Monolith
Matthey
Bishop
Monolith
Engelhard. Grace
Pellet
1
Pellet
Air
Products
Pellet
                               Grace
                              Gould
                                                                                                                     00
                                                                                                                     U1
                                                 Oxidation Catalysts
                                                                NO  Reduction
                                                                  XCatalysts

-------
                          FIGURE IV-A6

NICKEL EMISSION RATES, gms/km OBTAINED WITH INDICATED CATALYSTS,
    FINAL 1975 FTP. • = 0.019% S.  O = 0.110% S.  • = 0.091% S


0.00100
0.00090
^ 0.00080
m
g>
. 0.00070
r^
S 0.00050
•H
^ 0.00040
0)
u
£ 0.00030
0.00020
0.00010
n
Base
Case
-
-
^


—

_


_

_


—
- +-0-*

No
Catalyst
Engelhard
Monolith
















»-c/

UOP(l)
Monolith
















•-0-B

UOP(2)
Monolith
















•-0-B

f\-- J J — j

Mat they
Bishop
Monolith















•~o-*

:ion Catal)
Engelhard
Pellet
















V

Grace
Pellet
















0-B

Air
Products
Pellet















•-o-m

Grace

















•-0-B

Gould

•-0-B

















NO Reduction
scs Catalysts
                                                                                          00

-------
                                                         FIGURE IV-47

                               COPPER  EMISSION RATES,  gms/km OBTAINED WITH INDICATED CATALYST
                                INITIAL  1975  FTP.  • =  0.019% S. O = 0.110% S. •  = 0.091% S
      0.00100
(U
4-1
c
O
•t-4
a
in
•H

MJ
u
0.00050
                Base
                Case
                    Engelhard UOP(l)    UOP(2)
                     Matthey  Engelhard  Grace
                    Monolith
Monolith
                  No
               Catalyst
Monolith
Bishop
Monolith
                                                         ^Filter
                                                          sample
                                                          sent  to
                                                          EPA
Pellet
Pellet
Air       Grace
Products
Pellet
                                                              Gould
                                                                                                                   oo

                                                                                                                    I
                                              Oxidation Catalysts
                                                              _NOx  Reduction
                                                                 Catalysts

-------
                          FIGURE  IV- 48
COPPER EMISSION RATES,  gins/km OBTAINED  WITH INDICATED CATALYST

 FINAL 1975  FTP. •= 0.019%  S. O =  0.110%  S.B= 0.091% S



0.00100

0.00090

j 0.00080
| 0.00070
oT
£ 0.00060
•2
c
-S 0.00050
M
l/l
lrl
J3 0.00040
H
£ 0.00030
o
0
0.00020
0.00010
0
Base
Case

•k

••


•»

^

^
^^
^l
- O-«
-
No
Catalyst
Engelharc
Monolith















UOP(l)
Monolith

















UOP(2)
Monolith














V
Matthey
Bishop
Monolith

*Filter
sample
sent to
EPA









Oxidation Catalys
Engelhard
Pellet





f
/
/
^
\ /
\/
\/
M
vy

Grace
Pellet














V.
Air
Products
Pellet













O-«
Grace















7
Gould















r
NQ, Reduction
Catalysts
                                                                                             oo
                                                                                             00

-------
                                    -  89 -
          IV.2.3.7   Emission Rates of Zinc

          Figure IV-49  shows the zinc emission rates on the initial
1975 FTP for all catalyst fuel combinations.  Although there seems to
be no correlation between zinc emissions and fuel sulfur level, there
does appear to be some correlation with the level of sulfate produced
by a given catalyst.  The lowest zinc emission rates were obtained
with the base case vehicle and the vehicle equipped with the NOx
reduction catalysts, where little, if any, sulfuric acid is observed.
There is not a one-to-one correspondence on a single run between the
sulfuric acid emission and zinc emission rate.  This could be due to
the generally erratic pattern of metallic vehicular emissions.  Thus,
for example, the high zinc emissions observed in a given run may be
zinc that corroded or reacted with sulfuric acid in an earlier or
previous run.  At other times, much of the emitted zinc may be that
which had reacted with sulfuric acid generated in the same run.  The
source of the zinc emissions has not been traced, although the muffler
system is a likely source.  Zinc is also present in the lubricant.

          IV.2.3.8   Emission Rates of Calcium

          Calcium emission rates observed on the FTP shown in Figure
IV-50  are independent of fuel sulfur level.  With minor differences,
the calcium emission pattern and level are the same both for all the
catalyst systems and the base case vehicle.  This would be expected if
the calcium containing exhaust particulate was derived from the lubricating
oil.

          On the FTP's the calcium emission rates were of the order
of 1 x 10-4 to 2 x 10"^ gms/km.  The lubricating oil used contained
about 0.16 and 0.21 wt. % calcium, equivalent to about 1.7 gms calcium
per quart.  Typical oil consumption rates for new vehicles is about
0.2 quart per 1600 km.

          The calcium emission rate corresponding to this consumption
rate is about 2.1 x 10~4 gms/km.  This is in excellent agreement with
the calcium emission rates shown in Figure IV-50,  indicating that
25% to virtually all of the calcium associated with the consumed
lubricating oil is emitted as exhaust particulate.  As with the other
metal derived exhaust particulate, steady state cruise calcium
emission rates are lower than the FTP values, accounting for about
10 to 15% of the calcium.

          IV.2.3.9   Emission Rates of Chromium

          The chromium emission rates obtained on the initial FTP are
shown in Figure  IV-51.  It can be seen that the chromium emission rates
are Independent of fuel sulfur content.  Both Engelhard catalyst systems
(monolith and pelletized) and the first UOP catalyst tested generally

-------
                                                   FIGURE IV-49

                            ZINC EMISSION RATES, gms/km OBTAINED WITH INDICATED CATALYST,
                             INITIAL 1975 FTP    • = 0.019% S. O = 0.110% S.»= 0.091% S
   0.00200
(0

&  0.00150
 ti
0)

3
w
•2  0.00100
I
u
   0.00050
             Base
             Case
         0    No  '
            Catalyst
                       Engelhard
                       Monolith
UOP(l)
Monolith
UOP(2)
Monolith
Matthey
Bishop
Monolith
Engelhard  Grace
Pellet
Pellet
Air
Products
Pellet
                    Grace
Gould
                                                                                                                       vo
                                                                                                                       o
                                                Oxidation Catalysts
                                                               NOX  Reduction
                                                                  Catalysts

-------
                         FIGURE IV-50

CALCIUM EMISSION RATES, gms/km OBTAINED WITH INDICATED CATALYSTS,
     INITIAL FTP. • = 0.019% S, O = 0.110% S, • = 0.091% S


0.00100
0.00090
4 0.00080
CO
1
0.00070
A
0)
4J
5 0.00060
c
0
•H
S 0.00050
'e
w
g 0.00040
•r-4
o
•£ 0.00030
o
0.00020
0.00010
Base
Case
-
-
_


-


_


-


-


_

V*-
No
Catalyst
Engelhard
Monolith



















A
UOP(l)
Monolith



















V.
UOP(2)
Monolith



















^*
nv^/ia

Mat they
Bishop
Monolith


















^LjffL^f
^j j~^
tion Catal
Engelhard
Pellet



















J
Grace
Pellet



















^
Air
Products
Pellet


















•-0-*
Grace




















^
Gould




















~-
NOX Reduction
3 Catalysts






I
VO
M

'













-------
                                                    FIGURE IV-51

                          CHROMIUM EMISSION KATES, gins/km OBTAINED WITH INDICATED CATALYSTS
                             INITIAL 1975 FTP. • = 0.019% S.O= 0.110% S, •= 0.091% S
     0.00050
I
 M
     0.0004C*.
e
o

u
     0.00030U
     0.0002C .
     0.00010
           c
             Base
             Case
Engelhard
Monolith
UOP(l)
Monolith
UOP(2)
Monolith
Matthey
Bishop
Monolith
Engelhard
Pellet
Grace
Pellet
Air
Products
Pellet
Grace
Gould
                                                                                                                      VO
                                                                                                                      to
               No
            Catalyst
                        Oxidation Catalysts
                                                               _NO  Reduction
                                                                  Catalysts

-------
                                 -  93 -
showed somewhat higher emissions than the base case vehicle, or the
vehicle equipped with the other catalyst system.

          Elemental analysis on a monolithic Engelhard catalyst carried
out at Exxon several years ago showed that chromium was present, so
that the Engelhard catalyst systems may be a source for the low chromium
emissions observed.  These analyses also showed that copper was another
elemental constituent such that the copper to chromium ratio averaged
about 8 to 1.  The ratio of the emitted copper to chromium for the
Engelhard monolith was found to range from about 4 to 7.5 in reasonably
good agreement with the analysis supporting the hypothesis that these
metals are catalyst derived.

          No such analytical data is available for the Engelhard
pallatized catalyst or the UOP monolithic system.  It is probable,
however, that in these cases, the catalyst systems are also the sources
of the low level chromium emissions.

      IV.2.4  Metal Oxide Emission Rates Following
              Sulfate Storage Conditioning	
          Metal emission rates were measured on the test sequence carried
out following the 3200 km conditioning on the Federal Durability Cycle
of the Engelhard palletized oxidation catalyst-equipped vehicle.  The
detailed metals emission results are given in Appendix E.

          Although sulfate and S02 emissions exceeded the theoretical
values based on test fuel consumption, the metal emission pattern
following storage conditioning was essentially unchanged from that
observed after standard conditioning and testing.  Table IV-10 shows
the comparison of the total metal oxide emission rates for the two
sets of conditioning and test sequence.

                             TABLE IV-10

               Comparison of Metal Oxide Emission Rates;
    Vehicle Equipped with Pelletized Engelhard Oxidation Catalyst,
           	Test Fuel 0.019% S	

                           Metal Oxide Emission Rate,
                           	ems/km	
                Test        Standard        Storage
                Type          Runs            Runs

              1975 FTP      0.0060          0.0070
              64 km/hr.     0.0008          0.0004
              96 km/hr.     0.0040          0.0004
              1975 FTP      0.0090          0.0030

          The large difference exhibited at the 96 km/hr. cruise are
not believed to be of significance in view of the generally erratic
behavior of metallic emissions previously discussed.

-------
                                   - 94 -
IV.3  Organic Exhaust Particulate Emissions

          The organic portion of exhaust particulate was to be measured
in terms of its carbon content using the semi-microcombustion technique
described in Appendix A, Section A.3.  Although this technique also could
measure the hydrogen content of exhaust particulate, it was not used
since it would include the hydrogen present in the particulate as
water of hydration.  Our earlier work has shown that most of the hydrogen
in particulate is present as water of hydration which can be determined
separately by the Karl Fisher method discussed in Appendix A, Section
A.4.1.  Organic hydrogen determined as the small difference between two
larger numbers (semi-microcombustion  minus Karl Fisher hydrogen) would
be an extremely inaccurate number.  Consequently, the semi-microcombustion
technique was not used to determine organic hydrogen.

          The presence of organic nitrogen in exhaust particulate was
determined using sensitive spot tests.  These tests are discussed in
Appendix A, Section A.A.2 and the results in Section  IV.3.3.   Organic
sulfur compounds in exhaust particulate are discussed in Section IV.1.6.

      IV.3.1  Carbon Content of Exhaust Particulate

          Previous tests had shown that the semi-microcombustion
technique may not be sufficiently sensitive to determine organic
particulate as carbon, particularly in the case of oxidation catalyst
equipped vehicles.  The Type A Gelman glass fiber filters used in this
program although ostensibly free of organic binder gave somewhat high
and variable carbon blanks, which averaged in terms of equivalent emis-
sion rates, 0.0014 gms/km for the 1975 FTP, 0.0004 gms/km for the 64
km/hr  (40 mph) cruise and 0.0001 gm/km for the 96-112 km/hr (60-70
mph) cruises.  As applied to analysis of the carbon content of exhaust
particulate laden filters, this method is at best semi-quantitative.

          Carbon analysis was performed for the base case runs, and for
the 1975 FTP and 64 km/hr cruises for the catalyst equipped vehicle.
The detailed results are given in Appendix E.  Table IV-11 below
compares the organic carbon particulate with the total particulate for
the base case vehicle on the 1975 FTP and 64 km/hr test runs on all three
fuels.  This vehicle was the one which in subsequent tests was equipped
with the various caralysts that were screened on this program.

          For discussion purposes, the catalysts in Table IV-H are
tabulated with respect to type, not the chronological order in which
it was screened.

          For the base case vehicle, the carbon content of the exhaust
particulate ranged from 25 to 60% of the total particulate.

          Carbon particulate from the Engelhard monolith equipped
vehicle with several exceptions were lower than the base case vehicle,
ranging from essentially zero to at most 11% of the total particulate.

-------
                       - 95 -
                    Table  IV- 11
Comparison of Carbon and Total Particulate Emissions
                                            Emission Rate,
                                               gins /km as
Run
No.
16
18
20
21
23
25
26
28
30
36

Test Type
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
% Fuel
Sulfur
0.019
11
11
0.110
ti
n
0.091
II
11
0.019

Catalyst
None
n
n
"
n
n
n
n
"
Engelhard

Carbon
0.002
0.001
0.005
0.007
0.002
0.006
0.007
0.003
0.009
0.002
Total
Particulate
0.015
0.002
0.019
0.014
0.004
0.010
0.014
0.005
0.014
0.031
38
40
41
43
45
46
48
50
66
68
70
71
73
75
76
80
141
143
145
146
148
150
151
153
155
81
83
85
86
88
90
91
93
95
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
                        Monolith
             0.110
               II
               II

             0.091
             0.019
             0.110
               it
               n
             0.091

             0.019
             0.110
               it
               n
             0.091
             0.019
             0.110
               n
             0.091
               n
  n
  n
  n
  it
  n
  n
UOP(l)
  II
                          II
                          II
UOP(2)
  n
                          n
                          ti
  n
  tt
Matthey Bishop
  n       it
  n
  n
  it

  n
  n
  it
n
n
it
0.000
0.000
0.002
0.005
0.014
0.014
0.005
0.015
0.019
0.005
0.015
0.015
0.006
0.012
0.014
0.014
0.012
0.000
0.001
0.001
0.002
0.001
0.001
0.006
0.005
0.014
0.004
0.015
0.015
0.004
0.014
0.014
0.004
0.015
0.018
0.043
0.169
0.262
0.150
0.226
0.192
0.131
0.029
0.037
0.035
0.104
0.490
0.090
0.134
0.042
0.023
0.025
0.014
0.070
0.363
0.151
0.173
0.356
0.134
0.028
0.014
0.021
0.086
0.118
0.050
0.069
0.087
0.040

-------
                                   -  96  -
                            Table IV-11  (Cont'd.)
Run
No.

 55
 Test Type
75 FTP
60
61
63
65
126
128
130
131
133
135
136
138
140
156
158
160
161
163
165
166
168
170
96
98
100
101
103
105
106
108
110
113
115
116
121
123
125
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
75 FTP
40(1)
75 FTP
40(1)
75 FTP
75 FTP
75 FTP
40(1)
75 FTP
% Fuel
Sulfur

0.019

0.110
0.091
0.019
  n
  n
0.110

  M
0.091
               0.019

                 n

               0.110


               0.091


               0.019
                         0.110
                           II
               0.091
                 n
                 n
               0.019

                 n
               0.110
               0.091
                 n
                 n
                                                         Emission Rate,
                                                            gms/km as
  Catalyst

Engelhard
 Pellet
                                     II
                                     II
                                   Grace Pellet
                                     MM

                                     II

                                     II

                                     II

                                     II
                                  II

                                  II

                                  II

                                  II

                                  II

                                  II

                                  II
                                   Air Products
                                    Pellet
                                   Grace NOV
                                           A
                                    Reduction
                                   Gould NOX
                                    Reduction
Carbon
0.015
0.015
0.015
0.015
0.014
0.013
0.004
0.012
0.014
0.005
0.017
0.013
0.004
0.011
0.002
0.001
0.000
0.002
0.003
0.002
0.002
0.004
0.001
0.000
0.000
0.000
0.000
0.000
0.000
0.002
0.004
0.016
0.004
0.006
0.014
0.016
0.004
0.018
Total
Particulate
0.036
0.083
0.062
0.201
0.064
0.044
0.016
0.026
0.027
0.117
0.065
0.066
0.140
0.051
0.034
0.020
0.010
0.051
0.149
0.106
0.043
0.099
0.123
0.007
0.005
0.017
0.016
0.133
0.019
0.020
0.118
0.041
0.005
0.013
0.025
0.031
0.089
0.019

-------
                                    - 97 -
          There are differences not understood between the  two UOP oxi-
dation catalysts.  The UOP(l) system shows a carbon emission rate generally
higher than the base case vehicle, whereas the UOP(2) system shows with one
exception lower carbon emissions that the base case vehicle.  A suggested
possible explanation is that the emission pattern of carbonaceous exhaust
particulate may be similar to the metal oxide emission pattern.  Thus,
a portion of the carbonaceous material collected during the UOP(l) runs
may have been re-entrained carbon deposits and not freshly made carbon-
aceous material.  The base case tests regarding carbon emissions may
be atypical in that the emissions were coursing through a clean exhaust
system.  Thus, an appreciable fraction of the carbonaceous particulate
matter produced in the base case runs may have deposited on the walls
of the exhaust pipe and re-emitted in subsequent test runs.  Although
both catalysts met the stringent CO and hydrocarbon standards, the UOP(l)
catalyst vehicle consistently showed higher CO emissions.  This may
also be a factor involved in the different levels of carbonaceous
particulate by the two UOP catalyst systems.

          The carbon emission rates on the FTP's for the Matthey Bishop
catalyst equipped vehicle are consistently higher than the base case
vehicle whereas the emission rates under cruise conditions are generally
lower.  The higher carbonaceous particulate emission rates on the FTP
may not only be due to the cold starts, but also to the effect of
vehicle aging in terms of carbonaceous deposits, which may be released
and re-entrained during the acceleration and deceleration portions
of the driving cycle.

          A similar carbon emission pattern to the Matthey Bishop
system was observed with the Engelhard and Grace palletized catalyst
equipped vehicle.  Presumably these patterns are due to similar but
undetermined factors operating in each case.

          The carbonaceous exhaust emission rates with the Air Products
catalyst equipped vehicle are the lowest that have been obtained of all
the oxidation catalysts that have been screened.

          The lowest carbon emission rates regardless of the catalyst
type screened were obtained with the Grace NOX reduction catalyst.  A
possible explanation is that the order of catalyst testing may have a
greater effect on transient carbonaceous emissions than the catalyst
itself.

          The particulate emissions from the Gould NOx reduction
catalyst equipped vehicle are predominantly carbonaceous with the exception
of a 64 km/hr cruise, run 123 Table IV-11.  The operating conditions
in that run were sufficiently lean to produce sulfuric acid at an emission
rate of 0.034 gms/km.  If it is assumed that the H^SO, particulate is
about a 50 wt.% aqueous solution, then the particulate emission rate

-------
                                   - 98 -
for run 123 excluding H2SO^ and bound water is 0.021 gms/km.  The
carbon particulate now constitutes 25% of the residual particulate.

          In general, the interpretation of the organic particulate
emissions from the catalyst equipped vehicle is difficult since the
test sequence was designed for a gross characterization of exhaust
particulate, rather than for the elucidation of the detailed mechanism
of organic particulate formation and emission.  For example, there is
no way to assess the effects if any of the test sequence on the resultant
organic particulate emission rates.  In addition, the screening program
was not designed to separate cold start effects from cycling effects,
both of which could markedly influence organic particulate emission
rates.

     IV.3.2  Organic Nitrogenous Particulate

          Chemical spot tests were carried out on particulate samples
generated from the 1975 FTP and 64 km/hr (40 mph) test runs for
nitrogenous organic material.  As in the case of non-sulfate sulfur
particulate analysis, the samples analyzed included those from runs
on the unequipped vehicle, and when the vehicle was equipped with  the
various catalysts screened on the test program.

          Low levels of nitrogenous particulate matter should be
readily detectable due to the extreme sensitivity of the tests.  Negative
results would establish the maximum emission rate possible.  This
maximum rate is based on the test sensitivity, the mileage accumulated
on the particular test run, and the fraction of the filter area
selected  for testing.  The spot tests used are listed in Feigl(22),
and are discussed in detail in Appendix A, Section A.4.2.

          Table IV-12 below shows which nitrogenous organic compounds
were tested for, and the maximum emission rates for the 1975 FTP and
64 km/hr  cruise based on negative results.

                              Table IV-12
                ESTIMATED AVERAGE MAXIMUM EMISSION RATES
                    AS DETERMINED BY DETECTION LIMITS
                                       gms/km, on Indicated Test
	Compound Type	          1975 FTP           64 km/hr  Cruise
Organic Nitrogen                   1 x 10~5              2.5  x  10"
Compounds with                     2 x 10~*              5  x  10~5
 Nitrogen-oxygen bonds
Aliphatic and Aromatic             -   in~^              7  «
               _                    J .X J.U                / .
 Nitro Compounds
Primary Aliphatic Nitro            2 x 1Q-4              5  x  1Q
 Compounds                              _,                      _4
Aromatic Nitro Compounds          6 x 10~               1.5  x  10
Nitrates, Nitrites                 3 x 10~4              8 x  10~6
Aliphatic and Aromatic                    -3                 x  1Q-3
 Nitriles                                 »                      ~
Aliphatic Nitriles                 4 x 10                1 x  10

-------
                                  - 99 -
          The selection of the compound types In the above table as
possible exhaust particulate components is based on chemical species
known to be present in auto exhaust which could function as precursors
or as reactants involved in their production.  The basis of this selec-
tion is discussed in Appendix D.  Two of the three test fuels contained
nitrogenous additives such that the nitrogen content of the fuel due to
these additives is only about 3 ppm by weight.

         All tests for the nitrogenous compounds listed in Table IV-12
were negative.  No nitrate other than normal filter background  (M).l
Ugm/cm^) was detected.  There are two tests for nitrate which have
detection limits of 0.5 and 0.07 ygms of nitrate, respectively.  The
less sensitive test was always negative, the more sensitive one always
positive when a 0.39 cm2 section of filter was tested.  The background
nitrate level corresponds to an emission rate for the 1975 FTP of about
3 x 10~5 gms/km, the detection limit of the more sensitive test for
nitrate.  The nitrate emission rate corresponding to the detection limit
of the less sensitive test which was always negative is 2 x 10"^ gms/km.
Thus, it may be inferred from the above discussion that the detected
nitrate is the background nitrate on the filter.

          It is not surprising that none of the nitrogen containing
compound types were found in exhaust particulate.  The major reason
is that there is not enough of the nitrogenous additives present in
the fuel to produce sufficient quantities of exhaust nitrogen compounds
to have a two-phase (vapor plus liquid) co-existence.  Only the liquid
form would be collected as particulate matter, and it cannot exist as
liquid under the test conditions.  This is discussed in detail in Appendix
D which also includes a sample calculation for demonstration.

          Only high molecular weight nitrogenous organic compounds
could exist as particulate matter under vehicle test conditions, and it
is unlikely that these wo'uld survive the combustion process intact.
Consequently, the only mechanism whereby organic nitrogen compounds
could be present as exhaust particulate would be if they were strongly
absorbed by exhaust particulate.  The failure to detect these compounds
indicates that absorption of appreciable amounts of these compounds
on exhaust particulate does not occur.

-------
                                   - 100 -

IV.4   Size  Distribution  of Exhaust Particulate

          Size  distribution of  the exhaust particulate was determined
using  the modified Andersen Impactor in parallel with the other sampling
probes.  The  results  obtained with the impactor were considered valid
only if  the normalized total particulate emission rates obtained with
the impactor  (sum of  weight gains of the impactor stages and final
filter)  agreed  with the  total filter particulate emission rates.  Accept-
able internal agreement  between the impactor measured emission rates
and total filter measured total particulate emission rates were obtained
in about 20%  of the runs.  It is believed that the major source of the
discrepancy was due to improper placement of the final filter in the
impactor.   This filter holder could not be sealed in the filter holder, so
that large  portions of aerosol  could be lost by improper placement.  The
rapid  disassembly and reassembly of the impactor that was required on
the days when 4 tests were conducted on the vehicle may have contributed
to many  instances in  which the  final filter was misaligned.  Periodic
checks showed that variable flow rates and visible leaks around the
collection  surface were  not sources of error.

          The nature  of  the program was such that considerable time
lags occurred between sample generation and weighing of the impactor
plates.  Consequently, the extent of the discrepancy was not noted
till late in  the program.  However, it should be noted that those cases
where  agreement was obtained included FTP's.  Table IV-11 shows the com-
parison  of  the  total  particulate emission rates obtained with the impactor
and the  total filter. The asterisk marked runs denote those in which the
agreement between the impactor  and the total filter were sufficiently
close  so that the impactor results could be considered valid.  Figures
IV- 52  to IV- 67  show the  log normal distribution plots for the asterisk
marked runs.

     IV.4.1  Particle Size Distributions. Base Case Vehicle

          For the base case vehicle runs, Figures IV-52 to IV-56 the pre-
dominant fraction of  the particles are under 2 microns.  For the FTP's
shown  in Figures IV- 52 and IV- 55, the cumulative % mass of particles less
than 2 microns  ranged from 91.5 to 95%.  For the hot start cruises,
the cumulative % mass of particles less than 2 microns, Figures IV-53, IV-54
and IV- 55,  the cumulative 7. mass shifted to a range of 96 to 98.6%.  The
major difference between the cold start cyclic testing and the hot start
cruises  is  most likely the result of greater production of organic
particulate during the cold start.  A comparison of the organic emissions
(as carbon) Section IV.3.1,  shows that the hot start cruises for the
base case vehicle consistently  produces lower levels of these emissions.

     IV.4.2  Particle Size Distributions, Oxidation
              Catalyst Equipped  Vehicle	

         With oxidation catalyst equipped vehicles,  the cumulative %  mass
of particles  less than 2 microns shifted from 98.2 to 99.7%,  Figures  IV-57
to IV-61.   This means that exhaust particulate from oxidation catalyst
equipped vehicles is  smaller than that emitted from a conventional vehicle.
Virtually none of the particles are in the size range above 2 microns.
There is not  sufficient data to show trends  in operating conditions or fuel
sulfur levels.  However, in the cases with the oxidation catalyst  equipped
vehicle, the sulfuric acid aerosol accounted for  about  50%  of the  total
particulate.  Thus,  taking into account the  bound water associated with the
acid,  the particulate is predominantly sulfuric acid aerosol.

-------
   10.0
                         Figure IV-52
           Size Distribution of Total Particulate,
            Base  Case  Vehicle. 1975 FTP, Run No. 6
                                     Figure IV-53
                       Size  Distribution of Total Particulate,
                    Base  Case  Vehicle,  113 km/hr Cruise. Run No.
 01
 g
 M
 0)
 4J
 (U
a
.H   1.0
u
CO
PL,
CO

•rl

1
    0.1
                                                                     10.0
            §
            M
            U
               1.0
            U
            •H
            4J
            t-l
            CO
            On
           •H
               70          90          98      99.5
                Cumulative % ,
-------
  lo.o:
                       Figure  IV-54
          Size Distribution of Total  Particulate,
      Base Case Vehicle  113 km/hr  Cruise,  Run No.
                                      Figure IV-55
                         Size  Distribution of Total Particulate,
                         Base  Case Vehicle, 1975 FTP Run No.  15
CO
a
o
M
0)
•H  1.0

M
to
c
0)
1-1
n)

•H
I
   0.1
                                                                    10.0
                                                                  M
                                                                  u
3


-------
   10.
                        Figure IV-56
           Size  Distribution of Total Particulate,

      .Base Case Vehicle.  64 km/hr  Cruise.  Run No. 29
                                    Figure  IV-57
               Size Distribution of Total Particulate,  Matthey Bishop
               Catalyst-Equipped Vehicle. 64  km/hr Cruise.  Run No. 88
0)

O
l-i
u

                                                                  4J
                                                                  CO
                                                                 •H
                                                                 Q
            U
            M
            cd
                                                                 <0
                                                                    1.0
             70          90          98      99.5

                 Cumulative %^"Particle Diameter
99.9
                                                                    0.1
                                                                                                                           o
                                                                                                                           LO
70          90          98     99.5
    Cumulative %^Particle Diameter
                                                                 99.9

-------
                      Figure  IV-58

 Size Distribution of Total Particulate,  Grace Pelletized

 Catalyst-Equipped Vehicle. 64  km/hr Cruise.  Run No.  133
  10.0
w
c
o
a

§
<0
•rt
Q

0)
iH
U
(0

Oi
IS


•H




1
1.0
   0.1
                                                                                       Figure IV-59

                                                                 Size Distribution of Total Particulate, Grace Pelletized

                                                                 Catalyst-Equipped Vehicle, 64 km/hr Cruise, Run. No. 138
                                                                   10.0
                                                              m


                                                              g
                                                              M
                                                              O
                                                              M
                                                              •H

                                                              a
                                                                 u

                                                                 •H
                                                                 4J
£  i.o
                                                                 R)
             70          90          98      99.5

                  Cumulative  %
-------
                        Figure IV-60
     Size Distribution of Total Particulate, Air Products
  Pelletized Catalyst Equipped Vehicle 1975 FTP Run tlo. 160
  10.0
CO
a
o
7}  1.0
to
d,
c
0)
   0.1
                                     Figure IV-61
               Size Distribution of Total Particulate, Air Products
            Pelletized Catalyst Equipped Vehicle 1975 FTP Run No. 166
             10.0
           EO

           I
           O
                                                                 H
                                                                 V
                                                                 0)
                                                                 H
                                                                 O
           H
           a
           P-
           u
           G
           U
                                                                 I
                                                                 s
              1,0
              o.i
                                                                                                                            o
                                                                                                                            Oi
              70          90         98      99.5
                  Cumulative %
-------
                         Figure IV-62
   Size Distribution of Total Particulate, Grace Reduction
       Catalyst  Equipped Vehicle,  1975 FTP Run No. 96

  10.0
 o

 u
•H
S
 
-------
                         Figure IV-64
    Size Distribution of Total Particulate, Gould  Reduction
    Catalyst-Equipped Vehicle, 64 km/hr Cruise, Run Ho.  113
   10. Oi	
 (A

 I
 
-------
                         Figure  IV-66
  Size Distribution  of  Total  Particulate,  Grace Reduction
  Catalyst Equipped  Vehicle.  64 km/hr  Cruise  Run No.  103

  10.0
M

s
o
M
0)
Q


-------
                                         - 109 -
                                     Figure  IV-68


                   Size Distribution of Total Particulate,  Engelhard

                         Pelletized Catalyst Equipped  Vehicle,

             Second  1975 FTP After Sulfate Storage Conditioning. Run No.
                                                                    175
     10.0
 CO
 C
 o
M
0)

-------
                                      - 110 -
          In one case with an Air Products catalyst Run No. 160, Figure
IV-60, the cumulative % mass of particles less than 2 microns was 93%,
atypical for oxidation catalyst equipped vehicles.  This run was an
FTP with the low sulfur fuel with considerable sulfate storage.  Although
the sulf ates accounted for 40% of the total particulate, the total
particulate emission rate was sufficiently low (0.010 gins/km) that the
metal oxide emission rate was 30% of the total rate.  Thus it is quite
possible that the relatively large contribution of metal derived exhaust
particulate could have altered the particle size distribution.

     IV.4.3  Particle Size Distribution, NO  Reduction
             Catalyst Equipped Vehicle	

          With NOX reduction catalyst equipped vehicles, the particle size
distribution on the FTP's generally resembled the base case vehicles.
For these tests, the cumulative % mass of particulates smaller than 2.1
microns equivalent diameter ranges from 88 to 98%, Figures IV-62 to IV-66.
On the cruises, the particle size distribution resembles that of the
vehicle equipped with the various oxidation catalysts.  For example
with a Grace reduction catalyst equipped vehicle on a 64 km/hr cruise,
the cumulative % mass of particulate less than 2.1 microns was 99.6%
(Figure IV-66) .  This was because of lean vehicle operation over a noble
metal catalyst with a high sulfur fuel.  The sulfuric acid emission rate
in this case was 0.065 gms/km,  and accounted for almost 50% of the total
particulate.  Under these circumstances, it is not surprising that the
particle size distribution resembled that produced by oxidation catalyst
equipped vehicles.

     IV.4.4  Particle Size Distributions After Sulfate Storage

          Figure IV-67 shows the particle size distribution obtained on
the second 75 FTP of the sulfate storage test run sequence.  The dis-
tribution deviates considerably from the log normal distributions exhibited
on the standard oxidation catalyst screening runs Figures IV-57 to IV-61.
It can be seen from Figure IV-67 that unlike the standard screening tests
with the oxidation catalyst equipped vehicle,  the cumulative % for particle
equivalent diameters of less than 0.43 microns is about 40%.  In this run,
the particulate sulfate emissions exceed 100% based on fuel consumption
values as a result of release of stored sulfate (Section IV.I.5). This
released sulfate may have a larger particle size  than sulfate produced
during the run.  The quantity of stored sulfate that is released must be
several times that of freshly produced and emitted sulfate.  Thus, the
emitted sulfate as a result of storage conditioning may have two particle
size distributions such that the stored sulfate has a larger mass medium
equivalent diameter than freshly produced emitted sulfate.

          This can be surmised by the simple expedient of assuming that
the size range of released sulfate is between 0.43 and 0.65 microns, and
that it would not be present in a standard screening run, a log normal

-------
                                   - Ill -
distribution more nearly resembling that obtained on the standard screening
test with an oxidation catalyst equipped vehicle.  This plot (backing out
the weight increment on the seventh impactor stage) is shown in Figure IV-64
(open circles).  This approach means that about 60% of the emitted sulfate
was released from storage.  Although the above arithmetical manipulation
is not conclusive proof of the presence of larger particle size sulfuric
acid, it does substantiate the possibility of its existence.  Analysis
of the stages would be required to verify the altered distribution of
sulfuric acid particle size as a result of release of stored sulfur.

-------
                     - 112 -
                 Table IV-13
  Comparison of Total Particulate Emission
Rates,  Andersen Impactor Versus Total Filter
Total Particulate
Emission Rate, gms/km
as Measured by

Run
No.
6
9
11
14
15
16
18
19
20
29
36

38
40
41
43
45
46
48
50
51

53
55
56
58
60
61
63
65
66
6.8
70
71
73
75
76
78
80


Test Type
75 FTP
112 km/hr
75 FTP
112 km/hr
75 FTP
75 FTP
64 km/hr
112 km/hr
75 FTP
112 km/hr
75 FTP

65 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP

64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75. FTP

% Fuel
Sulfur
0.110
ii
0.091
ii
ii
0.019
ii
ii
ii
0.091
0.019

0.019
0.019
0.110
it
ii
0.091
ii
n
0.019

n
ii
0.11
II
II
0.091
11
n
0.019
n
n
0.110
II
II
0.091
n
n


Catalyst
None
n
n
n
n
n
•
n
n
n
Engelhard
Monolith
n
n
n
n
ii
n
n
n
Engelhard
Pellet
n
ii
n
n
n
ti
n
n
UOP(l)
n
n
n
ti
n
n
n
n
Impactor
Stages +
Final Filter
0.026*
0.012*
0.018
0.007*
0.018*
0.009
0.0021
0.002
0.013
0.004*
0.012

0.005
0.006
0.068
0.004
0.007
0.005
0.006
0.008
0.009

0.001
0.003
<0.001
0.003
0.005
0.003
0.201
0.002
0.002
0.011
0.005
0.012
0.342
0.013
0.005
0.149
0.009

Total
Filter
0.026
0.009
0.030
0.008
0.022
0.015
0.002
0.003
0.019
0.004
0.031

0.018
0.043
0.169
0.262
0.150
0.226
0.192
0.131
0.061

0.009
0.036
0.059
0.246
0.083
0.062
0.002
0.201
0.029
0.037
0.035
0.104
0.490
0.090
0.134
0.462
0.042

-------
            - 113 -
    Table IV-13  (Cont'd.)
Run
No.
81
83
85
86
88
90
91
93
95
96
98
100
101
103
105
106
108
110
111
113
115
116
118
120
121
123
125
126
128
130
131
133
135
136
138
140
141
143
145
146
148
150
151
153
155
Test Type
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
74 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
7. Fuel
Sulfur


0.019
0.110
  II

  It

0.091
  ii

  n

0.019


  n

0.110
  II

  II

0.091
  n

  ii

0.019


  n

0.110
  It

  II

0.091
0.019
  n



0.110
  II

  It

0.091
  n

  ti

0.019
0.110
  n
  n

0.091
  n

  n
           Catalyst
         Matthey
          Bishop
         Grace Reduction
            n

            n

            M
         Gould Reduction
           n
           n
           n
         Grace Pellet
         UOP(2)
           n
           n
Total Particulate
Emission Rate, gms/km
as Measured by
Impactor
Stages +
Final Filter
0.012
0.009
0.021
0.047
0.092*
0.011
0.030
0.058
0.011
0.006*
0.003
0.006
0.015*
0.125*
0.007
0.008
0.118
0.011
0.017
0.005*
0.008
0.009
0.072
0.016*
0.008
0.054
0.020*
0.006
0.008
0.009
0.016
0.172*
0.038
0.018
0.133*
0.011
0.013
0.018
0.007
0.041
0.014
0.011
0.012
0.012
0.026
Total
Filter
0.028
0.014
0.009
0.086
0.118
0.050
0.069
0.087
0.040
0.007
0.005
0.017
0.016
0.133
0.019
0.020
0.069
0.041
0.041
0.005
0.013
0.025
0.116
0.016
0.031
0.089
0.019
0.044
0.016
0.026
0.027
0.177
0.065
0.066
0.140
0.051
0.023
0.025
0.014
0.070
0.363
0.151
0.173
0.119
0.134

-------
                                  -  114  -
                          Table  IV-13  (Cont'd.)
Run
No.
156
158
160
161
163
165
166
168
170
171
173
175
Test Type
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
74 FTP
75 FTP
64 km/hr
75 FTP
75 FTP
64 km/hr
75 FTP
                        % Fuel
                        Sulfur
            Catalyst
                         0.019    Air  Products
                           II         II



                         0.110       "
                           M         ri

                           it         n

                         0.091
  n

0.019

  n
  n
                                 Engelhard
                                  Pellet**
Total Particulate
Emission Rates,
as Measured
Impactor
Stages +
Final Filter
0.011
0.005
0.009*
0.007
0.013
<0.001
0.036*
0.060
0.023
0.020
0.054
0.132*
gms/km
by

Total
Filter
0.034
0.020
0.010
0.051
0.149
0.106
0.043
0.163
0.123
0.105
0.258
0.152
**  Runs 171-175 are  sulfate  storage  runs.

-------
                                   - 115 -
                             V.   REFERENCES
 (1)  E.  E. Wigg,  "Fuel-Exhaust Compositional Relationships in Current
      and Advanced Emission Control Systems," presented May 11, 1972
      at  Midyear Meeting of American Petroleum Institute's Division of
      Refining, New York, New York.

 (2)  Cross, G. P., "The Effect of Fuel and Vehicle Variables on Poly-
      nuclear Aromatic Hydrocarbon and Phenol Emissions," SAE Paper
      720210, January 1972, Detroit, Michigan.

 (3)  M.  Beltzer,  R. J.  Campion, and W. L.  Petersen, "Measurement of
      Vehicle Particulate Emissions," SAE Paper 740286, February-March,
      1974, Detroit, Michigan.

 (4)  Work Statement of Request for Proposal DU-72-B407, Commerce Business
      Daily, January 26, 1972.

 (5)  M.  Beltzer,  Environmental Health Perspectives, 10, 121 (1975).

 (6)  Bulletin No. 07169, "HoneyCombe Industrial Dehumidifiers,"
      HoneyCombe Industrial Division, Gargocaire Engineering Corporation,
      Amesbury, Massachusetts.

 (7)  Electronic Control Systems, Fairmont, West Virginia.

 (8)  Electric to Pneumatic Transducer, Model No.  T5129, Fairchild
      Industrial Products Division, Winston-Salem, North Carolina.

 (9)  Pneumatic Controller, Model and Size B-51XC4, Conoflow Corporation,
      Blackwood, New Jersey.

(10)  Dunham-Bush  Corporation, West Hartford, Connecticut.

(11)  Coolenheat Incorporated, Linden, New Jersey.

(12)  H.  Schlicting, "Boundary Layer Theory," New York, McGraw Hill Book
      Co., Inc., pp. 504-5(1960).

(13)  R.  L. Bradow and J. B. Moran, "Sulfate Emissions from Catalyst
      Cars-A Review," SAE Paper 750090, February 1975.

(14)  K.  Habibi, Env. Sci. and Technol., 4, 239 (1970).

(15)  J.  B. Moran and 0. J. Manary, Interim Report PB 196783, "Effect
      of  Fuel Additives on the Chemical and Physical Characteristics of
      Particle Emissions in Automotive Exhaust," NAPCA, July 1970.

(16)  Instruments  for Measurement and Control of Relative Humidity,
      Brochure B-ll and Form D-ll, Phys-Chemical Research Corporation,
      New York.

-------
                                     - 116 -


(17)   Private communication, R. Bradow, EPA.

(18)   L.  S. Bernstein, "Statement on Automotive Sulfate Emissions to EPA
      Hearings on Delay of the 1977 CO and HC Automotive Emission
      Standards," January 29, 1975.

(19)   M.  Beltzer, e_t _al., "The Conversion of SC^ on Automotive Oxidation
      Catalysts," SAE Paper 750095, February, 1975.

(20)   R.  J. Fedor, e£ al. , "Durability Experience with Metallic NO  Catalysts,"
      SAE Paper 741081, October, 1975.                            x

(21)   Private communication, W. S. Briggs, Grace.

(22)   F.  Feigl, Spot Tests in Organic Analysis. 7th ed., Elsevier Pub-
      lishing Company, 1966.

(23)   K.  Habibi, e_t _ali. , "Characterization and Control of Gaseous and
      Particulate Exhaust Emissions from Vehicles," presented at APCA,
      October 8-9, 1970.

(24)   H.  P. Schuchmann and K. J. Laidler, J.  Air Poll. Control Assoc.,
      22:52 (1972).

(25)   H.  H. Watson, Am. Ind. Hyg. Assoc. Quarterly 15, 21 (1954).

(26)   S.  Badzioch, J. Inst. Fuel, 33, 106 (1960).

(27)   EPA, peronnel communication.

(28)   G.  S. Springer, "Engine Emissions, Pollutant Formation and
      Measurement," p. 195, Plenum Press (1973).

(29)   H.  Goksrfyr and K. Ross, J. Inst. Fuel, 35:177 (1962).

(30)   E.  S. Lisle and J. Sensenbaugh, Combustion, 36:12 (1965).

(31)   G.  R. Gillespie and H. F. Johnstone, Chem. Eng. Prog., 51:74  (1955).

-------
                                   -  117 -


                                APPENDIX A

                            ANALYTICAL METHODS

A.I  Analytical Determination of  Sulfate


           In  earlier  in-house work on sulfate  emissions,  sulfate was
determined  gravimetrically by a modification of  the  standard  gravimetric
method  for  sulfate, ASTM Procedure 01099(1).   This has  been  superceded
by a titrimetric  procedure for sulfate  using a color indicator.
Sulfonazo  III £4,5-dihydroxy-3,6-bis(o-sulphophenylazo)-2,7  naphthalene-
disulfonic  acidj.  The  procedure  has  been  adapted from  that  of  Budesinsky
and Krumlova(2).

          The soluble  sulfate collected by the filter in  the  exhaust
particulate sampler is  leached from  the filter with  dilute nitric  acid.
The  leach solution is  heated to boiling to drive off excess  nitric
acid, filtered to remove  insoluble material, passed  through  an  ion-
exchange column to remove interfering cations, and then buffered
with methenamine  to a  pH  of 3-4.   The resulting  solution  is  titrated
with barium perchlorate using Sulfonazo  (III)  as the indicator.

     A.1.1  Reagents

          The reagents  used are as follows:

          1.  Barium perchlorate  standard  solution 0.01N
          2.  Barium perchlorate  standard  solution O.OOlN
          3.  Hexamethylenetetramine  (57, aqueous)
          4.  Sulfonazo III indicator (0.1 g/100 ml  HjO)
          5.  Ethyl Alcohol, absolute
          6.  Acetone
          7.  Nitric acid (2"/e aqueous)
          8.  Dowex 50  W-X8 cation exchange resin  (50-100 mesh)

     A.1.2  Tltratlon Apparatus

          The following apparatus  was  used in  the titrations-

          1.  Ion exchange  column, 1  cm x  25 cm.
          2.  Burettes  (at  least  0.05 ml div)
          3.  Low range pH  paper  - J. T. Baker Dual-Tint pH  1.0-4.3.

     A.1.3  Standardization of BaCClO^)? Solution

          The barium perchlorate  solution  is standardized by  titration
against previously standardized O.OlN sulfuric acid  as  follows:

          (1) 5 mis of  O.OlN sulfuric acid is  pipetted  into a 125-ml
Erlenmeyer  flask.

-------
                                    - 118 -
          (2) 45 mis of deionized water and 2.5 mis 2% nitric acid
are added.

          (3) Adjust the pH as described in the Procedure and titrate
with barium perchlorate solution.

          (4) Calculate normality.

                                          mis H^SO,   x N    H«SO,
                       N   Ba2
A. 1.4  Detailed Titration Procedure

           (1) Cut and  place  1/4  sectionof filter  in  100-ml beaker.
(1/2 filter can be  used  for  lower  levels  of SO,).

           (2) Add 3.0  mis of  2%  nitric acid, wetting the  filter  section
completely.

           (3) Add 20 mis of  deionized water.

           (4) Place small glass  stirring  rod in beaker and cover with
watch glass.

           (5) Digest samples  on  hot  plate and  allow  to boil  for  5
minutes •

           (6) Cool  beakers and filter  liquid through glass wool  into
the ion-exchange column  containing ~7. 5 g of Dowex 50 W-X8 cation
exchange  resin, collecting sample  in 125  ml Erlenmeyer flasks.

           (7) Wash  beaker with 3 x 5 ml portions  of  deionized water.
Add washings  to column.  After each  washing, squeeze liquid  from the
filter by pressing  it  against the  wall of the  beaker with the stirring
rod.

           (8) Place the  flask on a hot plate and  evaporate  to approximately
5 mis .

           (9) Adjust the pH  of the remaining solution to pH  4 using
57, hexamethylenetetramine .

          (10) Add  10 mis ethyl alcohol and 25  mis acetone to the flask.

          (11) Add  3 drops  Sulfonazo III  indicator.

          (12) Titrate  with  O.OlN barium  perchlorate  solution.  (If
sulfate  content  is  low,  use  0.001N barium perchlorate.)   If  the  sample

-------
                                     - 119 -
requires more than 10 mis of barium perchlorate to reach the end point
the results are unreliable and should be discarded.  Another portion
of filter should be treated as in steps 1-7.  Solution should he col-
lected in 100 ml volumetric flask.  An appropriate size aliquot is
taken and the test is continued with step 8.

          A.1.4.1  Effect of Nitric Acid on Measurement of Sulfate

          Because nitric acid is used as the leaching agent, several
experiments to ascertain the effect if any of nitric acid on the
determination of sulfate were carried out.   The test matrix, shown in
the following table,shows that there is no effect of nitric acid on the
titration.
                                Table A-l

                 Comparative Titrations of Sulfate of
                 Samoles With and Without Nitric Acid
   Sample
Contains
HN03
Yes
No
Yes
No
ml
Theory
5.0
5.0
5.0
5.0
0.012 N Ba(Cl04)2
to Titrate
Ac t ua 1
4.9
4.7
4.7
4.8

Ami
-0.1
-0.3
-0.2
-0.2
          A. 1.4. 2  Precautions About Titration Procedure

          The above procedure was arrived at after experimental work
identifying sources of error and the means to minimize or eliminate
these errors was worked out.  Reliable results can be obtained if the
following precautionary measures are taken:

          (1) Keep HN03 at minimum
          (2) Keep water in sample at minimum
          (3) pll is very critical f/4.0)
          (4) Use blank for color comparison of end point
          (5) Change Dowex frequently (approx. 3 samples)
          (6) If sample is basic - adjust with Nitric Acid

          For example, it was shown that not only is the ion-exchange
step necessary to eliminate interference, but that it is necessary to
insure that the capacity of the ion-exchange bed is not close to
exhaustion.  It was also shown that it is necessary to use a new batch
of ion-exchange resin rather than a regenerated batch.  Positive
deviations were obtained when titrating the effluent from a regenerated
ion-exchange bed.  The results of the tests described above are shown in
Table A-2.

-------
                                 -  120 -
                               Table A-2

                 Experiments Demonstrating  Influence of
                Ion  Exchanger on  Sulfonazo  m End Points
                    Mis. Titration
Mis.
   Blank
   0.5
   0.75
     .00
     .50
2.00

2.00
1.50
1.00
    Blank
    0.2
    0.5
    0.1
    0.8
    1.0
    2.0
              Theory

              0.0
              0.5
              0.75
                ,00
                .50
2.00

2.00
1.50
1.00
                0
              2.0
              5.0
              1.0
              0.8
              1.0
              2.0
Actual

 0.1
 0.5
 0.65
 1.0
 1.25
 1.45

 2.2
 1.75
 1.1
               0.15
               2.10
               4.95
               1.45
               0.80
               1.00
               1.90
Ami

+0.1
 0
-0.1
 0
-0.25
-0.55

+0.20
+0.25
+0.10
             +0.15
             +0.10
             -0.05
             +0.45
              0
              0
             -0.10
                                      Same column for
                                        all samples
                                      0.012 N Ba(C104)2
                                                       New Dowex each
                                                            sample
                                                       0.012 N  Ba(Cl04)2
           0.0012 N Ba(C104)2
           New Dowex
           0.012 N Ba (C104)2
    Blank
     ,1
     ,1
     ,2
     ,2
    2.0
    2.0
                0
                .0
                .0
                .0
                .0
                .0
               0.25
               2.
               2,
               2.
               3.
               1.
   10
   00
   90
   00
   30
              2.0
               1.40
+0.25
+1.10
+1.00
+0.90
->-l.00
-0.7
-0.6
Regenerate Dowex with
1:5 HC1
0.0012 N Ba(Cl04)2

0.012 N Ba (C104)2
           As  shown  above,  the  Dowex ion  exchanger  has  to  be  changed
 frequently, and that  large errors  result if  one  attempts  to  work with
 a  presumably  regenerated  ion exchanger.   Satisfactory  results  can  be ob-
 tained  if  the Dowex resin  is changed after every two to three  determinations,
A. 1.5  Sulfate Determinations on Glass Fiber Filters
       Spiked with Known Quantities of H2S04

          A series of  filters were spiked with known  quantities  of  H2S04
using  1.000 N H2S04  and a  5  yl  syringe and with 0.0112 N H2S04 solutions.
The  filters were  leached with water,  the leach solution worked up for

-------
                                   - 121 -
 for analysis as discussed in Section A.1.4.  Figure A-l shows a plot
 of added sulfate versus sulfate recovered by titration.  It can readily
 be seen that analysis of sulfate on the filters is as reliable as
 analysis of solutions containing known quantities of sulfate.  The next
 step was to determine if this method is workable with filters containing
 actual auto exhaust since the presence of organic exhaust particulate
 matter on these filters could possibly introduce substances which
 interfere with the color change of the titrimetric procedure.  To deter-
 mine if such interferences existed, the procedure was then checked against
 the gravimetric determination of sulfate on parallel filters from
 actual vehicle test runs since the presence of organic materials would
 have no effect on the latter determination.

 A.1.6   Comparison  of  Titrimetric and Gravimetric
 	Procedures  on  ^ilters  fro") Vehicle Tests

          Comparisons were then made between the titrimetric and
 gravimetric analytical procedures on particulate filters from actual
 vehicle runs.  The titrimetric analysis was carried out on quarter sec-
 tions of the filters, the gravimetric on an entire parallel filter.
 The particulate filters were generated from vehicles equipped with
 pelletized and monolithic catalysts, operating on fuels of sulfur
 levels  ranging from 0.004 to 0.14 wt %.  Both cyclic and steady state
 test modes were used.  The results  are shown in Table A-3.

                               Table A-3
               Comparison of Titrimetric and Gravimetric
               	S0,= Analyses on Parallel Filters	

                   (Actual Vehicle Runs, Sample Data)
   Run Type

40 mph, 1/2 hr.
1975 FTP
1975 FTP
40 mph, 1 hr.
1975 FTP
60 mph, 20 min.
   Fuel
Sulfur, 7,

  0.14
  0.065
  0.056
  0.004
  0.14
                      I
  0.004
   I
  0.14
   I
  0.004
 Catalyst
   Type

Pelletized
Monolith
   SO^  Emissions, g/mi.
Titrimetric   Gravimetric
   0.036
   0.012
   0.0099
   0.004
   0.306
   0.296
   0.176
   0.053
   0.023
   0.029
   0.259
   0.294
   0.265
   0.009
   0.011
   0.011
Regression analysis on 26  comparison sets showed:
0.040
0.011
0.0081
0.004
0.287
0.288
0.173
0.061
0.020
0.020
0.239
0.253
0.247
0.007
0.008
0.008
           Titrimetric SO
           1.029 Gravimetric SO.
                         > .     A. • * ' ^ ^ tll.«VA.IIIt»kfcLW> I_J VS t
                         4                        4

                        Standard Deviation = 0.01
                       0.00085

-------
                                      - 122 -
                                     Figure A-l

                              Recovery  of  Sulfate From
                         Spiked  Glass  Fiber  Filter Samples
     10.0


      9.0


      8.0
«     7.0
13
 a!     6.0
 *J
iH
£
"£     5.0
 *j
 cd

I     4.0


 a-    3.0


      2.0


      1.0
                                                  Ideal Sulfate
                                                  Recovery Line
                      2345678

                        y gins Sulfate/Filter by  Titration
                                                                      10

-------
                                  - 123 -
A. 2  Sulfur Dioxide Determination

          Sulfur dioxide in diluted automotive exhaust was measured
using a Thermo Electron Corporation  (TECO Model 40) Sulfur Dioxide
Analyzer(3).  This device operates on a pulsed-fluorescence  UV
absorption principle as follows.  A gas sample is submitted  to a source
of pulsed ultraviolet  light through a monochromatic filter.  Sulfur
dioxi.de molecules energized to an excited state by the high  intensity
light source, return to the ground state bv emitting a monochromatic
light, which passes through a narrow-band filter, and  impinges upon the
light sensitive surface of a photomultiplier tube.  The  intensity
of this radiation is directly proportional to the SO-  concentration.

          This measurement method was chosen because of  the  following
reasons:

(1)  It is more convenient than wet chemical, conductimetric, or
     coulometric methods.

(2)  Both continuous and integrated measurements of SO-  in diluted
     exhaust can be made.

(3)  Measurement of S02 emission rates could be incorporated as part
     of the gaseous emission measurements routinely obtained using
     diluted exhaust collected by the CVS system.

The  operating principle of the TECO analyzer is depicted schematically
in Figure A-2.

          To eliminate the possibility of water adsorbing and condensing
in the sample chamber on the walls and optical filters,  the water in
the sample stream was removed upstream to the TECO analyzer.  Initially,
Drierite was used to remove the water but it was found that at the 5
to 10 ppm level of S02, the Drierite absorbed all the SO--

          The water removal problem was solved by using  the Permatube
Drying System(4) shown in Figure A-3.  This system dries the sample
stream by passing it through a bundle of tubes which are permeable
to water but essentially impermeable to S02•  Water is purged by
countercurrent flow of dry air or nitrogen.  The effectiveness of the
permeable system in reducing the water level of a humid  sample stream
below 10 ppm 1^0 while retaining the S02 in the sample has been
established by our Analytical Division. The Model PD-500-72  Perma Pure
Dryer according to the manufacturer (4) has the capability of taking a
feed having a 120°F dew point and extracting sufficient water at a 4 to
6 SCFH feed rate to reduce the dew point of the effluent to -25°F.

-------
                     Figure A-^  Principle of Operation
                           TECO S02 Instrument
 PULSATING
ULTRAVIOLET
    LIGHT
                      FILTER
                    SAMPLE
                   GAS OUT
                                              SAMPLE GAS CONTAINING S02 IN
                                                 PHOTOMULTIPLIER
                                                 TUBE
                                                       ELECTRONICS
NJ
4S

-------
                            Figure A-3

                       Permatube Drying Systern
HIGH PRESSURE
WET FEED
INLET
j—**-  LOW PRESSURE WET PURGE GAS OUTLET

 I                    /-  SHELL     HEADER
          HEADER  L PERMEABLE TUBE BUNDLE
                        LOW PRESSURE
                        DRY PURGE GAS
                        INLET
HIGH  PRESSURE
 DRY PRODUCT
       OUTLET
                                                                   EXPANSION  VALVE
                  Ul
                  I

-------
                                 - 126 -
          Our own tests with dry [.802 *n ^2 anc* *n air]  have shown
that no differences in TECO readings were obtained when  the sample is
introduced directly into the analyzer, or when it passes through
the dryer prior to entry into the analyzer.

          A millipore filter is used upstream to the dryer to prevent
any particulate matter from entering and eventually clogging the
dryer, and for that matter, from possibly entering and contaminating
the analyzer.

          It has been found that C02, CO, and Q£ are strong quenching
agents, while N2 exhibits a negligible quenching effect.  The
instrument response is therefore sensitive to background gas composition.
Absolute values of S02 concentrations necessitate calibration of the
instrument in a background representative of the sample  to be analyzed.

          For example, prior to a laboratory study on S02 conversion
as a function of oxygen concentration, it was necessary  to assess the
effect of oxygen quenching(5).  Various amples were made by preparing
bell jar mixtures containing 30 ppm S02, 12% C02» varied amounts of oxygen,
and nitrogen as the balance gas.  Measurements of the SOo concentration
of these mixtures indicate an approximate 1 ppm reduction in instrument
S02 response for each 2% increment in oxygen concentration, as shown
below.

                               Table A-4

                     S02 Measurements at Indicated
                       Oxygen Concentrations(a)
Oxygen
Concentration
(%)
0
1
2
4
6
TECO S02
Response
(ppm)
29.7
28.8
28.4
26.8
26.2
                  (a)  Basic Mixture, 30 ppm S02, 12% C0_, balance N_.

          The quenching effects of CO and C02 was also measured using
mixtures of 30 ppm S02 in pure CO and C02•  In C02, the response to
30 ppm of S02 was 1.7  ppm, that in CO only 8.5.  Measurements were then
carried out on bell  jar mixtures of 30 ppm of S02 in background air
containing different concentrations of CO, 02, C3Hg, and C02-  The
results given below  show that instrument response is sensitive to overall
concentration of quenching species.  Therefore data obtained where the
total background concentration

-------
                                  - 127 -
                               Table A-5

                       Composite Effects of C02, 02 and
                          CO on TECO SOp Response	

                           Total Quencher
  Mixture             Species Concentration (%)           Instrument
 Composition              [COJ  +  |pj  +  [CQl             Response (ppm)

30 ppm S0_
1.42% 02
0.09% CO
0.051% H2                        ^-U                         28
445 ppm C-jHg
12.5% C02

30 ppm SO
4.78% 02
14.3% C02                        23'A                         23
4.33% CO
348 ppm C_H_
         J O
of quenching species changes significantly from the calibration gas
quencher level should be corrected for the inherent changes in instrument
response.

          For vehicle work,  quenching  effects are minor.   Quenching  by
exhaust  O>2 and CO  is negligible  for  a  CVS air diluted sample due to
dilution.  Although the oxygen  concentration increases with dilution,
it presents a reasonably  constant quench background and  can be  taken  into
account  by calibration of dilute  S02  in air mixtures.  Properly  used,
the precision of this instrument  is about 0.5  ppm SO,.

A.3  Carbon. Hydrogen, and  Nitrogen Determinations

          Carbon, hydrogen,  and  nitrogen was measured by  gas chromatography.
A  portion of the glass fiber  filters  was inserted into the combustion
tube of  a Perkin-Elmer Model  240  C/H/N  microanalyzer.  A schematic
of the detection system of  this device  is shown in Figure A-4.

          Combustion of the  samples occurs in pure oxygen.  The  products
of combustion are carried into  a  reduction zone which includes:  silver
tungstate on magnesium oxide, silver  oxide and silver tungstate  on
chromosorb P, silver vanadate,  and silver gauze.  The purpose of this
reduction zone is to insure that  combustion is complete  and that inter-
fering combustion products  (such  as 502) are removed. The gas leaving
the reduction zone  contains only  C02, H20, N2, and He.

-------
                                     - 128 -


                                   FIGURE A-4


                   PERKIN-ELMER MODEL  240 C/H/N MICROANALYZER
                        • COMBUSTION
                                 .REDUCTION
                                          MIXING VOLUME

                                                PRESSURE SWITCH

                                                     SAMPLE VOLUME
                                                                DETECTORS
                                               TRAPS i
          Simplified Diagram of Combustion Train and Analytical System
FROM
SAMPLE
VOLUME
H20    HP

SENS    REF
C02    C02
SENS    REF
         H20 +
                              O
                              He+C0.,+
                      a
     r-
     I  HjOTRAP  I
     | (RETAINS H20) |
                                             I COjTRAP  I

                                             | (RETAINSCOj))
                        a
                                                                              (He)
a)
                                                 N2
                                                SENS
                                                                               REF
                                                                 FROM
                                                                 He  SOURCE

-------
                                  - 129 -
         These gases are flushed into a closed, spherical glass
mixing volume and additional helium added until the pressure reaches
1500 mm Hg.  The contents of the mixing volume remain there for 90 sec.
in order to reach a homogenous composition.  When mixing is complete,
the contents of the mixing volume expand through the sample volume
detectors and out to the atmosphere.

         Three pairs of thermal conductivity cells, in series, are used
for detection - one pair each for water, carbon dioxide, and nitrogen.
The platinum filaments of each cell pair are connected differentially
in a bridge circuit so that any difference in the contents of the two
cells will result in an electrical signal.

         A magnesium perchlorate trap between the first pair of cells
absorbs any water from the gas mixture before it enters the second cell
so that the signal obtained from the corresponding bridge circuit is
proportional to the amount of water removed.  Likewise, an absorbing
trap between the second pair of cells results in a signal proportional
to the carbon dioxide removed.  The last pair of cells detects nitrogen
by comparing the thermal conductivity of the remaining sample gas to
that of pure helium.

         The normal sample size used with the C/H/N analyzer is 2 mg
and accuracy of 0.3% is obtainable.  This places the minimum detectible
amount of C, H, and N at~>6/(g.  Only a portion of the filter can be used
because of the small combustion tube in this unit.  If 25% of the
filter were used the minimum detectible emission rate would be ~ 6 x 10"^
g/ml of C, H, or N on the 1975 FTP or-2.5 x 10~5 g/km of C, H, or N on
the 2 hr., 70 mph cruise mode.

         It should be noted that the hydrogen measurement obtained by
this technique includes hydrogen present in the particulate in water
of hydration.  The amount of water of hydration can be determined separately
using the Karl Fisher titration technique.   It would not be justified
to determine water routinely by Karl Fisher titration and also deter-
mine total hydrogen by the semi-micro combustion technique.  This is
because data we have collected in previous work(6) show  that
most of the hydrogen in particulate is present in water of hydra-
tion.   To then determine organic hydrogen as the small difference
between two large numbers would result in a highly inaccurate value.

-------
                                    - 130 -
 A. 4  Characterization of Specific compounds in Automotive
 _ Exhaust Particulate __

      A.A.I  Bound Water

          Bound water is determined by the Karl Fisher titration technique.
 This technique makes use of Che fact that water enters  many reactions  such
 as the redox reaction:

                    I2 + S02 + 2 H20 - >  2 HI  + H2S04

          If this reaction is carried out in a  non- aqueous medium it can
 be used to quantitatively determine water.  The reaction actually used is
           H2° + I2 + S°2 + CH3OH + 2 py —> CH HS04 + 2  Py.HI

whose Py = Pyridine.   The Karl Fisher reagent  is  prepared from anhydrous
methanol, anhydrous pyridine,  iodine and  sulfur dioxide.   A small sample
of  the filter is  soaked in anhydrous methanol  then  titrated with  the
Karl Fisher reagent to an end  point determined by the appearance  of excess
iodine.

          The procedure used at Exxon is Based  on  ASTM E203(7).  The
titration is carried out to an electrometric end  point using a commercial
titration assembly in which the titration is automatically stopped
at  the end point (8).   The least detectible amount of water is  about
10  Vgms, although accuracy will suffer if 100  ygms  of H20 is not  obtained.
If  one-fourth of  a filter is used for analysis, 100 ygms  of H20 corresponds
to  a water emission rate of 6.8 x 10~4 gms/km  for a 1975  FTP.

      A. A. 2  Organic Nitrogen Compounds

           A. 4. 2.1  Nitrogenous Particulate

          Chemical spot  tests were carried out on particulate samples
generated from the  1975 FTP and 64 km/hr  (40 mph)  test runs for
nitrogenous particulate and non-sulfate sulfur containing particulate
matter.   The samples analyzed were  from runs with the unequipped
vehicle,  and with the vehicle equipped with  the catalysts that were
tested in the  contract  program.  The spot tests used were adapted  from
Feigl(8).

          The sensitivity  of many of  these tests is such that low  levels
of nitrogenous and  non-sulfate particulate matter should be readily
detectible.  Negative  tests for a given compound or compound type
establishes  the maximum emission rate possible based  on the sensitivity
of the spot  test, the mileage accumulated on the particular test  run,
and the  size of the filter portion  used for  analysis.  Because of  the
many analyses  that  were conducted on the particulate  filters, only a
small portion  (0.385 cm2) was selected  for a given spot test.  Thus, the
maximum  emission rate (ERM) » in gms/km  for a given organic compound based
on a negative  test  result is:

-------
                                    -  131 -
                        ERM
    DL    = chemical detection limit in grams
    A (km) = distance accumulated on the particulate in kilometers
    F!    = volume fraction of diluted auto exhaust sampled
    F2    = fraction of active filter area used for the chemical
            spot test

          Obviously by varying Fj and F2 ,  the maximum emission rate can
 vary over a wide range.   The volume fraction of diluted exhaust sampled
 Fj, is fixed by our sampling tunnel and probe dimensions consistent
 with isokinetic sampling.   Larger filter areas could be used for analysis
 if the need arose.  Presently 0.42% of the active filter area (0.39 cm2)
 is used for each chemical spot test.   Maximum emission rates based on a
 filter area of 0.39 cm2  generally range from 10~5 to 10~3 gms/km for the
 1975 Federal Test Procedure, and 10~6 to 10~3 gms/km for the 64 km/hr
 one-hour cruise.  As mentioned above, the filter area selected for testing
 was based solely on practical considerations.  The range of maximum
 emission rates based on  this area are generally considered insignificant,
 unless some unusually toxic or reactive component was involved.  Figures
 A-5 and A-6 depict the analytical test scheme for what are considered to
 be chemically logical, possible exhaust nitrogenous and sulfur (excluding
 sulfate) containing exhaust components.  The nitrogen compounds tested
 for were:

                nitroparaff ins, nitroaromatics
                organic nitrates, nitrites, nitroamines, and nitrosamines
                aliphatic and aromatic nitriles


          A. 4. 2. 2  Organic Nitrogen Compounds

         The detection method used is described in Feigl, pages 90-92.
This test is valid for any type of nitrogenous organic compound.  The
detection limit is 0.02 to 0.03 fgm of nitrogen.  Using a circular cut
of filter 0.39 cm2, the detection limit corresponds to emission rates
of 1 x 10-5 gtr.s/km for the 1975 FTP and 2.5 x 10~6 gms/km for the 64
km/hr, one-hour cruise.  If necessary, still  lower emission rates could
be determined by simply taking larger filter areas for analysis.

          A. 4. 2. 3  Compounds Containing Nitrogen and
          _ Oxygen Bonded Together _

         The method used is described in Feigl, pages 93-94.  The detection
limit is about 0.1 to 0.2/
-------
               Figure A-5
Analytical Scheme for Nitrogen Compounds
       in Auto Exhaust Particulate
                            Exhaust
                          Particulate
           Organic
           Nitrogen
           Compounds
Inorganic Nitrogen
     Compounds
 NH4+, N02~, N03~
j,
Oxygenated
Nitrogen
Compounds

1
1
Aliphatic
and
Aromatic
Nitro
Compounds





1

Primary
Aliphatic
Nitro
Compounds
1




Aliphatic
and
Aromatic
Nitroles

W





Nitrates
Nitrites
Nitroamines
Nitrosamines







Aliphatic
Nitriles




J>
Aromatic
Nitro
Compounds



                                                                                      l*J
                                                                                      N)

-------
                                          Figure A-6

                            Analytical Scheme for Sulfur Compounds
                                    in Exhaust Particulate
                                                   Exhaust
                                                 Particulate
             I
        I
      Organically Bound
     di and Tetravalent
           Sulfur(l)
         1
    Alkyl and
Aromatic Sulfonic
     Acids(2)
     Sulfates
fColorimetric or''
(^Gravimetric
f
 Selenium Test
if di and Tetra-
 valent Sulfur
Tests Positive
                                                                                I
                                                                               M
                                                                               U)

                                                                                I
           Positive Se
                     Sulfur in
                    Presence of
                     Selenium

-------
                                   - 134 -
          Thus,  negative tests  for these  compounds correspond to an upper
 emission  rate  of about 2 x 10~4 gms/km for the  1975 FTP and 5 x 10~5 gins/
 km  for  the  64  km/hr,  one-hour  cruise.   The following compounds can be
 detected:

          C  - Nitro compounds
          N  - Nitro compounds
          C  - Nitroso  compounds
          N  - Nitroso  compounds
          Hydroxamic acids
          Oximes
          Azoxy and hydroxyl amine compounds
          Nitrates
          Nitrites
          Nitramines
          Amine Oxides

          A.4.2.4  Aliphatic and Aromatic Nitro Compounds

          The  detection method  used is  described in Feigl, pages 295-297,
 included  tests for primary aliphatic nitrocompounds.  The detection
 limits  for  general nitrocompounds were about 0.5 to l/
-------
                                 - 135 -
           The  detection method used  for aliphatic  nitriles  is described
 in Feigl,  pages  265-266 is  sensitive in 2.5  to  150 ygm  range.  These
 detection  limits correspond to an emission range rate of  10~3 to
 6  x 10~2 gms/kra  for  the 1975 FTP, and 2.5 x  10~4 to 1.5 x 10~2 gms/km
 for the 64 km/hr,  one-hour  cruise.   Most of  the aliphatic nitriles can
 be detected  2  to 20  ygm range.

     A.4.3  Organic  Sulfur  Compounds

           A.4.3.1  Organically Bound Di-and  Tetravalent Sulfur

           The  methods used  are described in  pages  82 and  85 in Feigl.
 Compounds  which  contain di- and tetravalent  sulfur are:

           thiocarbonyls
           thiols
           sulfides (open and cyclic  thioethers)
           disulfides
           thiocyanates
           isothiocyanates
           sulfoxides
           sulfinic acids

           The general test  (pages 82-83) for the above  compounds can
detect about 2 ygm quantities corresponding  to  a 1975 FTP emission rate
of 8 x 10"  gms/km, and 2 x 10~* gms/km for  the 64  km/hr, one-hour
cruise.  This test does not distinguish between the  above compounds.
Because selenium is reputedly present on the filters, the general test
procedure would be modified as described on pages 83-84 to eliminate the
possibility of obtaining a  false positive result for di- and tetravalent
organic sulfur compounds.

          A.4.3.2  Alkyl and Aromatic Sulfonic Acids

          The test procedure used is described  in pages 85-86 of Feigl
The detection limits are about 2.5 Vgms of material  corresponding to a
1975 FTP emission rate of 1 x 10-3 gms/km, and 2.5 x 10-4 gms/km for
the 64.36 km/hour, one-hour cruise.   Sulfates do not interfere with the
tests for sulfonic acids.

          Table A-6 shows the averaged maximum emission rates based on
chemical detection limits for both organic nitrogen and organic sulfur
compounds.

-------
                                 TABLE A-6
            ESTIMATED AVERAGE MAXIMUM EMISSION RATES (gms/km)

AS DETERMINED BY DETECTION LIMIT OF SPOT TEST ON INDICATED VEHICLE TEST

Compound Type
Organic Nitrogen
Compounds with Nitrogen and Oxygen Bonded
Together
Aliphatic and Aromatic Nitro Compounds
Primary Aliphatic Nitro Compounds
Aromatic Nitro Compounds
Nitrates, Nitriles
Aliphatic and Aromatic Nitriles

Aliphatic Nitriles
Di- and Tetravalent Organic Sulfur Compounds
Alkyl and Aromatic Sulfonic Acids

1975 FTP
1 x 10"5
2 x 10~4

3 x 10~4
2 x 10~4
6 x 10~4
1.2 x 10~4
4.4 x 10"3
_3
4 x 10
8 x 10"4
1 x 10~3
64 km/hr
One-Hour Cruise
2.5 x 10~6
5 x 10~5

7.5 x 10~5
5 x 10~5
1.5 x 10~4
3 x 10"5
1.1 x 10"3
_3
1 x 10
2 x 10~4
2.5 x 10~4
                                                                                             I

                                                                                             M
                                                                                             U)


                                                                                             I

-------
                                   - 137 -
A.5  Determination of Metallic Components of Exhaust Particulate

     A.5.1  Emission Spectroscopy

          A procedure was developed to measure the emission rate of
the metals listed below by emission spectroscopy:

          calcium, aluminum, zinc, chromium, iron, copper, nickel,
          lead.

Emission spectroscopy was chosen as the analytical technique not only
because of its high sensitivity, but because it alone of the most various
alternative analytical procedures considered, allows most of the metals
to be measured by a single analytical procedure carried out on a single
sample without resorting to separations.

          Nickel and copper vehicular exhaust emissions have been deter-
mined in earlier work by differential pulse polarography(9).  This
technique is extremely sensitive and in many instances can measure
metallic cations (in solution) in the ppb range. Differential pulse
polarography could also be extended to measure exhaust chromium,
iron, zinc and lead.  Several sample preparations would be required
however prior to polarographic analysis since some of the metal
cations are best determined in alkaline medium, others in acidic
medium, etc.  In addition this technique cannot be used to determine
calcium and aluminum, necessitating the use of two additional, and
separate analytical procedures.

          This spectrochemical method is based on the fact that all
elements when vaporized and excited in an electric arc emit light
energy at a series of wavelengths characteristic of that element.
The emitted radiations for the sought for elements are separated by
a grating, isolated and focused on the cathode of a photomultiplier.
The photomultiplier transforms the radiant energy into electrical
energy which is stored on a condenser of extremely low leakage
rage.  The charge on the condenser is related to the concentration
by means of standard samples.  This method has been in use at Exxon
for some time in measuring trace metals in organic materials such as
polymers and rubbers, and in a wide variety of materials such as slags,
ashes, and minerals.


          A.5.1.1  Preparation of Calibration Standards

          Standards were prepared by spiking filters so that the levels
for each metal ranged from 0.45 to 4.5 ^gms/cm2.  The spiking solutions
used were Matheson, Coleman and Bell Atomic Absorption 1000 ppm

-------
                                  -  138 -
Standard Solutions.  A separate set of standards containing 4.5 to
11.25 /fgmslcm2 were prepared for Pb, Fe, and Zn, since it was found
that the levels of these metals on the exhaust particulate filters
frequently exceeded 4.5^gms/cm2.  Additional standards were prepared
to simulate the combination of metals likely to be present on exhaust
particulate filters.  The surface concentrations of the metals in the
mixture ranged from 0.45 to 4.5/^gms/cm2.  Samples high in Ni and Cu,
but low in other metals were also prepared.  In all cases, recovery
was within  +15% of the quantity added to the filter.  An ashless
Millipore filter was used because of its high filtering efficiency,
and negligible metals background.

          Sample electrodes are prepared using the following reagents:

(1)  Glycerol - U.S.P.

(2)  Alcoholic Mg(N03)2'6H20


                ?cA5 8m™^!!0?)2l6!!2n     Per liter of 95% Ethanol
                150 mg CO(N03)2-6 H20     v

(3)  Aviation mix carbon

                54 gm graphite
                 6 gm lithium carbonate


The electrode is prepared as follows:
                          2
          The spiked 44 cm  Millipore filter is put into a 100 ml beaker,
to which is added 1 ml of glycerol, 0.5 ml of magnesium nitrate solution,
and 1 ml of concentrated sulfuric acid.  The mixture is heated until
the dense white fumes of 803 cease evolving.  The sample is placed
into a muffle furnace at 1000°F  for one hour.  This procedure is
repeated if ashing was not complete the first time.

          The ash is mixed with  400 ml of a 10% lithium carbonate, 90%
carbon blend in a Wig L-Bug mixer, until a homogeneous mixture is obtained.
This mixture is pressed into a 0.25 inch diameter electrode at 8000 PSI
using an ARL power driven hydraulic briquet ting press with a carbide
lined mold assembly.

          The finished pellet is inserted  into a brace electrode holder
in the quantometer, the counter  electrode a 2-inch x 0.25-inch diameter,
high purity graphite rod with a  flat  tip.  The spectrometer used was
a direct reading ARL Quantometer(10).  The excitation source is a voltage
spark of the ARL multi-source unit, Model No. 4700.  High voltage
excitation having the following  parameters is used:

-------
                                     - 139 -
           Primary Voltage              150
           Discharges per cycle           4
           Capacitance, iff.                0.007
           Inductance, /,h               360

The exposure conditions are as follows;

           Slit Width - primary          20/f
                        secondary       150//
           Prespark                      10 seconds
           Exposure                      50 seconds

The 50-second exposure is controlled by a constant amount of  energy  from
the internal standards.

          The following analytical  lines (AO), were used.

                 _ Element _           AQ

                 Li  (Internal Standard)          6102
                 Ca                              4303
                 Pb                              2833
                 Cu                              3274
                 Al                              3944
                 Zn                              3345
                 Cr                              4254
                 Ni                              3415
                 Fe                              3021

         Calibration curves are constructed by exciting  the electrodes
prepared from the calibration standards (described above) by  plotting
the spectral intensity versus concentration using linear coordinates.
The low standard and high standard  are used to set the instrument
curve, and the curvature is established by the intermediate standards.
Figures A-7 to A-15 show the calibration curves.

         The spectral intensity obtained from the excitation  of  the
electrodes from the samples are compared to those of the standards,
and the equivalent /fgm/cm2 obtained from the calibration curves.   The
emission rate (ER) in gms/km of a given metal is obtained as  follows:
                                  O     _£
         .,„ .      i.   _   Cfgms/cm  ) x 10   gms^/gm x Filter  Area
         ER in gms/km -   -*-* -         -
where Akm is the distance in kilometers accumulated on  the  test  and  F
is the probe volume fraction sampling rate.

-------
                                     - 140 -
                                  Figure A-7



                          Calibration  Curve  for Nickel




                      150 Volts, ~45 Second  Burning Time
    100
     80
t>o
c
•H
•O
(0

-------
                                - 141 -
                               Figure A-8




                     Calibration Curve for Aluminum





                     150 Volts, ~/45 Second Burn Time
100 -
                                                                 5.0
                                    Aluminum

-------
                                      - 142 -
                                     Figure A-9



                           Calibration Curve for Calcium




                          150  Volts, ~45 Second Burn Time
    100
     80
oo
e
•H
•a
n
0)
4-1

-------
                                      - 143 -
                                   Figure A-10
                          Calibration Curve  for  Copper
                         150 Volts, ^45 Second Burn  Time
    100
     80
oo

•H
•O
CO

a

M
0)
60
§
Or
     40
     20
                   1.0
                            2.0
3.0
4.0
5.0
                                         y

                                 y^gms/cm  , Copper

-------
                                       - 144  -
                                    Figure A-ll


                          Calibration Curve  for  Chromium


                         150 Volts,-^_45 Second Burn Time
    100
     80
00
•H
-o
14
0)
4J

-------
                                     - 145 -
                                  Figure  A-12


                          Calibration Curve  for  Zinc



                        150 Volts, *-45 Second Burn Time
   100
     80
 oo
 C
i-l
TJ
 CO
    60
§
o-
    40
    20
                    1.0
2.0          3.0

Vgms/cm , Zinc
4.0
5.0

-------
                                    - 146 -
                                  Figure A-13


                          Calibration Curve for Lead


                        150  Volts, ~-45 Second Burn Time
   100
    80
00
c


"S  60
(-1
0)
0)
3
o-
   40
   20
                  1.0
2.0
 3.0


Lead
4.0
5.0

-------
                                      - 147 -
                                  Figure  A-14



                          Calibration  Curve for Iron



                        150 Volts, -^45 Second Burn Time
   100
oo
•a
CO
0)
4J
    80
    60
§
o-
    40
    20
                  1.0
2.0
3.0
4.0
5.0
                               /Cgms/ctn , Iron

-------
                                    -  148  -
                                   Figure  A-15




                         Calibration Curve for Platinum





                        150  Volts, -^45 Second Burn Time
   100  -
    80  -
oo
c
CO

«S   60
(U
u

0)
c
CO


o-
40  -
    20
                                                                      5.0
                                      2
                                    cm ,  Platinum

-------
                                 - 149 -
          A. 5. 1.2  Assessment of Interaction. Effects on
          _ Metal Determinations _

         Since filters from vehicle  test runs would invariably  have
a combination of various metals or metal derived particulate matter,
it was necessary to determine if there were any interactions which
produced interference which invalidated the 0.45 to 4.5 /Vgm/cm2
calibration curves for any or all of  the metal containing  components.

         Measurements were made with  filters spiked with salts  of Ca,
Pb, Fe, Cu, Al, Zn, Cu, Ni , and Ft to ascertain if major interferences
exist.  The results (excluding Pt)are shown below in Table A-7.  In
some of the mixtures several of the  components were present at  levels
below the minimum detection limit, and above the upper calibration
limit.

         This test matrix had a two-fold purpose:

(1) To determine if spurious results  for some metals would be obtained
    because of high levels of other metal components.

(2) To determine if the presence of other metals would produce
    interactions such that metals which were present at levels  above
    and/or below the calibration limits would appear to be at levels
    within the calibration limits.

         Table A-7 shows that there are no major interferences  so that
each of the metals or their salts may be determined in the presence
of the others without a major error.  The average recovery for  each
metal within the calibration limits is about 86%.

         Regression analysis for each of the metals showed:
Ca (found) = 0.88
                              Clfl
                                   Ca (present) + 0.08 /^gins/cm

Al (gound) = 0.97


Fe (found) = 0.83
                                   Al (present) - 0.07 /jgms/cm
                                   Fe  (present) - 0.35 ftgms/cm'
(4)
Cu (found) = 0.93
                         Cu (present) + 0.09/fgms/cm
          Pb (found) = 1.01 /(     Pb (present) - 0.039 y/gms/cn/
                              cn\£                       »*•

-------
                                 - 150 -
                                                                 2
(6) 482|  Zn (found) = 0.93 x*82!   Zn (present) + 0.129 -*gms/ cm
      cm                       cm                        A1


                                                                 2
(7) #     Cr (found) = 0.89 4      Cr (present) - 0. 120 *gms/cm
      CD/                      Cmt                       /V


(8)  £B2f  Ni (found) = 0.85  ^f   Ni (present) + 0.05 *gms/cm2
      cm^                      cm^                       *
  cm'
         Regression analysis for the eight metals showed:


      (any metal found) = 0.91-4^-  (any metal present) + 0.07,482^
                                cm^                              cm^
          A. 5. 1.3  Effect of Presence of Chromium
          _ on Platinum Determination _

         It was shown however, that although platinum could be determined
by emission spectroscopy to the same sensitivity levels as the other
metals (Figure A-15), the presence of chromium causes appreciable positive
deviations for platinum.  Table A-8 summarizes the experimental matrix
which demonstrates the interference for platinum by chromium.

         Even though the sample contains no platinum, the quantometer
indicates that platinum would be present.  Table A-8 shows that it is
the chromium which is responsible for the spurious platinum readings.
The platinum readings on the quantometer were essentially constant
for the same quantity of chromium despite a four- fold change in the
nickel level and a ten-fold change in the copper level.  Figure A-16
shows that the false quantometer readings for platinum vary linearly
with the quantity of chromium present, but is not a function of other
metals such as nickel and copper.  Platinum therefore was not determined
by emission spectroscopy, but by X-ray fluorescence.  This method
is discussed in Section  A. 5. 2 of this Appendix.

          A. 5. 1.4 Calibrations for High Levels of
          _ Iron, Zinc and Lead _

         In the course  of carrying out the program it was found that
iron, zinc, and lead, were frequently found at levels above 4.
cm2.  Additional calibrations for these three metals were made at
filter loadings up to 11.25 /^gms/cm2.   The higher loading calibration
curves for these metals are shown in Figures A-17 to  A-19.

     A. 5. 2  Platinum Analysis  by X-ray Fluorescence

         Platinum analysis on the glass fiber filters was performed
by X-ray fluorescence ,  since  it was found that  chromium Interfered with the
determination of platinum when using emission spectroscopy.

-------
                                     - 151 -
   200
   150
0)
4J
   100
    50
                                Figure A-16


                  False  Platinum Response of Quantometer
                 	Due  to Presence of Chromium	


                      150  Volts, -2/45 Second Burn Time
     0
                       I
50             100


  False Pt Reading
                                                    150

-------
                                         Figure A-17
                                 Calibration Curve for Lead

                                   (4.5 to 11.25 ygms /cm2)


                               150 Volts, ~45 Second Burn Time
   100
    80
•H
•o
a)

a

M
01
§
o-
60
    AO
    20   .
       4.5   5.0
                     6.0
7.0
8.0
9.0
10.0
11.0
                                        //gins/cm , Lead

-------
                                         Figure A- 18
                                Calibration Curve for Iron

                                  (4.5  to 11.25/fems/cm2)


                             150  Volts,  ~-45 Second Burn Time
  100
   80
60
T>
CO

A

t-i

                                                                           10.0
                                                                                        11.0
                                               , Iron

-------
                                        Figure A-19

                                 Calibration Curve for Zinc
                                  (4.5  to  11.25 yfems/cm2)
150 Volts,
                                             Second Burn Time
   100  _
oo
c
•H
•8
H

-------
                                     - 155 -

                                     TABLE A-7
                    EFFECTS OF PRESENCE OF OTHER METALS ON
    DETERMINATION OF A SELECTED METAL  (0.45  to 4.5  'tgm/cm?  CALIBRATION  CURVE)
Metals Determined

2
fgms/cm. added
"gms/cm found
Percent Recovery
fgms/cm_ added
/,gms/cm found
Percent Recovery
'gms/cnu added
"gins /cm found
Percent Recovery
'fgms/cm» added
'rgms/cm found
Percent Recovery
•gms/cnu added
' gms/cm found
Percent Recovery
2
/(gms/cm_ added
/'gms/cm found
Percent Recovery
«gms/cnu added
//gms/cm found
Percent Recovery
2
•Vgms/cnu added
/^gms/cm found
Percent Recovery
2
/(gms/cnu added
X'gms/cm found
Percent Recovery
2
,Vgms / cm_ added
/'gms /cm f o un d
Percent Recovery
Ca
0.25
<0.45
(a)*
1.01
1.00
99
1.52
1.65
109
2.02
1.65
82
2.53
2.35
93
3.04
2.60
84
3.54
3.15
89
4.05
3.90
96
4.55
3.85
85
0.51
0.50
98
Pb
0.51
0.45
88
1.01
1.20
119
2.02
2.30
114
2.53
2.35
93
3.54
3.60
102
5.06
>4.50
(a)
7.59
>4.50
(a)
8.60
>4.50*
(a)
10.63
>4.50
(a)
13.16
>4.50
(a)
Fe
0.51
0.70
137
2.02
2.10
104
4.05
4.00
99
5.06
4.25
84
6.58
>4.50
(a)
7.59
>4.50
(a)
9.11
>4.50
(a)
10.12
>4.50
(a)
11.64
>4.50
(a)
13.16
>4.50
(a)
Cu
0.25
^0.45
(a)
1.01
1.05
104
1.52
1.60
105
2.02
1.80
89
2.53
2.45
97
3.04
2.80
92
3.54
3.40
96
4.05
3.90
96
4.55
4.25
93
0.25
^0.45
(a)
Al
0.25
<0.45
(a)
1.01
1.05
104
1.52
1.65
109
2.02
1.80
89
2.53
2.50
99
3.04
2.80
92
3.54
3.35
95
4.05
3.95
98
4.55
3.90
86
0.51
0.45
88
Zn
0.25
<0.45
(a)
1.01
1.15
114
4.05
4.40
109
2.02
J.90
94
3.04
2.95
97
5.06
4.30
85
7.59
>4.50
(a)
10.63
>4.50
(a)
11.64
>4.50
(a)
13.16
> 4.50
(a)
Cr
0.25
<0.45
(a)
1.01
1.05
104
1.52
1.65
109
2.02
1.85
92
2.53
2.45
97
3.04
2.75
90
3.54
3.30
93
4.05
3.90
96
4.55
3.95
87
0.51
<0.45
~-88
Ni
0.25
<0.45
(a)
1.01
1.05
104
1.52
1.45
95
2.02
1.65
82
2.53
2.20
87
3.04
2.45
81
3.54
3.05
86
4.05
3.65
90
4.55
3.85
85
0.51
<0.45
88
*(a)  The metal loading was either above the upper calibration  limit  (4.5>^gTns/
      cm2) or below the detection limit (0.45 ,
-------
                                      TABLE A-8
                          PLATINUM-CHROMIUM INTERFERENCE
     Micrograms of
    Indicated Metal
	in Sample	    	Quantometer Readings for Indicated Metal
Pt     Ni     Cr     Cu

  0000
 50      0      0     0
200      0      00
  0      0     50     0
  0      0    200     0
  0    200     50    50
  0     50     50     5
Pt
0
25.5
100.0
17.0
71.0
19.5
17.5
Pb
__
—
—
—
—
0.0
0.0
Cu

—
— —
—
—
40.5
4.0
Al

—
«
—
—
-3.0
-4.0
Zn

—
—
—
—
0
0
Cr

—
—
32.0
95.5
35.0
32.5
Ni

—
—
—
—
89.5
27.0
Ca

—
—
—
—
5.5
4.0
                                                                                                   In

-------
                                   - 157 -
          The X-ray procedure involves exposing circular sections
of the exhaust particulate filter in the X-ray beam of a Phillips
Number 1220 X-ray spectrometer.  An internal standard is made by
spiking one of these filters with 40 /rgm of platinum as an aqueous
solution.  The platinum X-ray peak intensity of the two filters is
then compared and the platinum content of the sample filter determined.
Blank filters are run in every determination.  The minimum detectable
level of platinum by this technique is about 0.35
          The maximum possible emission rates based on this sensitivity
limit is:

              5.6 x 10~5 gms/km for the 1975 FTP

 and          1.55 x 10   gms/km for the 64.36 km/hr, one-hour cruise

-------
                                 - 158 -

                                APPENDIX B


                        MODIFIED ANDERSEN IMPACTOR
          A model 0203 Anderson Impactor was modified and adapted for
use withdrawing samples from the dilution tunnel.  Sampling of the usual
1 CFM however meant that  the opening of the sampling probe coupled to the
impactor would be only 5mm when sized to the flow development tunnel.  A
probe opening this small  is conducive to material sampling losses in the
probe.  The recommended minimum probe diameter to prevent these losses
is 6.4mm(ll).  Increasing the volumetric flow rate through the impactor
would allow longer probe  openings to be used.  However, the high pressure
drop through the impactor limits the volumetric flow rates and, therefore,
the probe dimensions that can be used in the flow development tunnel.

          As a compromise, the flow rate used for sampling with the im-
pactor is 1.5 CFM corresponding to a probe opening consistent with isokinetic
sampling of 6.4MM.  The probe was flared up to one inch ID, a half inch
beyond the probe opening.  This probe was bent at right angles in the
tunnel so that it emerged from the tunnel bottom.  It was necessary to do
this because there was insufficient space for the impactor to fit in with.
the filter housings at the tunnel end.

          To obtain size distributions by weight, one mil thick stainless
steel shimstocks replaced the particulate collection plates normally used
in the Andersen Impactor.  The standard collection plates weigh about 20
grams, which exceeds the 10 gram capacity of the Mettler microbalance used
for weighing.  The shimstock was washed progressively in cyclohexane-toluene
mixture, alcohol, acetone, and then cleaned ultrasonically in an aqueous
detergent solution.  The shimstock was then rinsed with distilled water to
remove the detergent, successively washed in alcohol and acetone and then
dried.

          The cleaned shimstocks were kept in Fetri dishes in a constant
temperature - constant humidity room and weighed daily for four days.  Ex-
pensive testing indicated that the weight change that would be incurred by
a shimstock during a vehicle run should be a reliable measure of the
weight of material deposited of a given particle size range.  The average
weight variation of a clean unused shimstock over a four day interval was
only + Sugms.

          Several tests were carried out under 64.km/hr and 96.km/hr cruises
using an oxidation catalyst equipped vehicle operating on a 0.046 wt %
sulfur fuel.  These test conditions were chosen to determine the feasi-
bility of the modified impactor.  Steady state cruises with a catalyst
equipped vehicle should allow sufficient material to be collected on the
Impactor stages to obtain a size distribution by weight.  The total parti-
culate emission rates obtained with the impactor should be in agreement

-------
                                   - 159 -
with those obtained from the parallel total filters.  Lack of agree-
ment between the total particulate emissions obtained with the Impactor
and the total filters would mean that the Impactor modifications inter-
ferred with its functioning properly.

          All seven stages of the Impactor were used for these test
runs, as was the absolute filter.  This filter is from the same batch
as the 15CFM filters (Gelman Type A Glass Fiber Filter).  The results
for each of the runs in terms of total particulate emissions and sulfuric
acid emissions is shown in Tables B-l and B-2.

                                TABLE B-l
                 Comparison of Impactor and Total Filters

                 64 km/hr, (40mph), one hour cruise vehicle
                 equipped with PTX-IIB oxidation catalyst
                 Fuel Sulfur, 0.046 wt. %

                        Farticulate Emission Rate
                        	gins/km

       Particulate
          Type

          Total

          Sulfate

The agreement between the Impactor and the total filters is within 5%
for both total particulate and sulfate emissions.  About 90% of the parti-
culate and all of the sulfate was less than one micron as shown below.

                                TABLE B-2
                      Distribution of Particulate in
                        Modified Anderson Impactor
                                  gms/km

Particulate             Sum of             Absolute         Shims plus
   Type              Shims (1-7)            Filter            Filter

  Total                 0.009               0.071             0.080

 Sulfate            (not detected)          0.034             0.034

          As shown in Figure B-l, the partlculates above one micron were
log normally distributed.   Similar results were obtained with the 96 km/hr
(60 mph) one hour cruise as shown in Table B-3.
Modified
Impactor
0.080
0.034
Total Filters
-ill ill
0.087 0.087
0.034 0.033

-------
                                  - 160 -
                               FIGURE B-l





                           OXIDATION CATALYST

                            EQUIPPED VEHICLE





                              0.046% S FUEL
     10.0
o

o
I-H
      i.o   _
Q




|


M
     0.1
               0    =64 kn/hr cruise, one hour, cold start



               O    =96 km/hr cruise, one hour, hot start
          50  60  70   80     90    95    98  99  99.5    99.9




                   CUMULATIVE % MASS <" PARTICLE DIAMETER
99.99

-------
Modified
Impactor
0.128
0.060
Total Filters
(1) (2)
0.130 0.131
0.055 0.053
                                      - 161 -
                                TABLE B-3
                  Comparison  of  Impactor  and Total Filters

                      96 km/hr  (40mph) one hour  cruise
                      vehicle equipped with PTX-IIB
                      oxidation  catalyst  - Fuel  Sulfur,
                      0.046 wt.  %

                        Particulate Emission Rate
                        	gins/km

        Particulate
           Type

           Total

          Sulfate

Again good agreement between the Impactor and total filters is obtained
with respect to total particulate and sulfate emissions is obtained.

          Over 95% of the total particulate and effectively all of the
sulfate is less than one micron in diameter as shown in Table B-4.

                                TABLE B-4
                      Distribution of Particulate in
                        Modified Andersen Impactor
                           (96.54 km/hr  cruise)
                                  gins/km

Particulate             Sum of             Absolute         Shims plus
   Type              Shims (1-7)            Filter            Filter

  Total                 0.004               0.124             0.128

 Sulfate           (not detected)           0.060             0.060

As in the previous case, the particulates greater than one micron in dia-
meter were log normally distributed, Figure B-l.  Thus, it appears that at
least for type of steady state cruises in which the particulate emissions
are high, the data obtained with the modified Impactor are reliable.  It
was found that the particulate matter on the shimstocks was difficult to
remove.   Accordingly, new shimstocks were used for each run.

-------
                                  - 162 -
                                APPENDIX C
                             EXHAUST SPLITTER
          An exhaust splitter was designed and tested to determine if ex-
haust particulate could be collected at 32°C (90°F) under high speed
cruise conditions (96 to 113 km/hr).  If only 25% of the raw exhaust from
a 350 CID, V-8 vehicle operating at 113 km/hr for example, this volume of
exhaust would be approximately equivalent to the average output of the
same vehicle under FTP conditions.  In order to accurately measure the ex-
haust particulate emission rates, the ratio of the exhaust volume intro-
duced into the tunnel to that rejected must be constant and accurately
known.

          The basic approach was to split the exhaust so that the ratio of
the volume flow rates of rejected or vented exhaust to that of exhaust
introduced into the tunnel would be 3 to 1 at all times on high speed cruise.
Figure C-l shows a schematic of the exhaust splitter system.

          The raw exhaust as it emerges from the finned tube enters con-
centric pipes designed so that the peripheral laminar area (shaded cross
section in the schematic) is three times the area of the smaller central
pipe.  That is the ID of the smaller central pipe designated as (CD) in
the schematic is 2 inches.  The ID of the larger pipe, designated as AB
in the schematic is 4 inches.

          To accommodate the hot wire anenometer probes, the larger pipe
turns away from the smaller concentric one and its diameter is reduced to
2-f3"inches, so that the area ratio of the pipes no longer concentrically
situated is still 3 to 1.  Hot wire anenometers are placed in the middle
of the large pipe at the point where the diameter is 2"f3~ inches, and into
the middle of the two-inch pipe.  The two probes, although in separate
pipes, are as close to each other as is physically possible so that both
would be operating in split raw exhaust streams having the same temperature.
Under these conditions, if the linear velocities of the sample streams in
each pipe are equal, the volume flow rate ratio in the pipes is 3 to 1.

          Initial work using lab air rather than raw exhaust showed that
this concept was valid.  Laboratory air was pulled into the dilution tunnel
by the CVS at total flows of 150 and 225CFM.  The lab air entered the
tunnel via the diluent air treatment system (dehumidifier, filter and
chiller) and the injection leg of the exhaust splitter.  No attempts were
made to dehumidify the air.  Direct reading flowmeters capable of handling
large flows were inserted in each leg downstream to the anenometers.
The anenometers used were connected to a Datametrics Model 700-6 Anenometer
circuit(13).

-------
                                      FIGURE C-l
                             SCHEMATIC OF EXHAUST SPLITTER
                               Dilution
                                Tunnel
                       Diluted
                       Exhaust
*   c
->
         IDEp = 3.46"
Vented Exhaust
to Variable
Speed Pump
                                              Exhaust
                                              Injector
                                                                         To  CVS  and
                                                                         Particulate
                                                                         Filters
                                   Hot  Wire Anenometers
                                          to
                                   Da tametries  Linear
                                    Velocity Readout
                                                2"  ID

                                             Raw Exhaust

                                             =T  Finned Tube 2" ID
                                                                       U)
                                                                        I
                                     Tail Pipe

-------
                                  - 164 -
          The experimental test was carried out oppositely to how the
splitter would be used in practice.  For a given total volume flow rate,
the flow in the vent leg was adjusted with a variable speed pumps until
the volumetric flow rate ratio was 3 to 1.  The linear velocities in
each leg were indicated on the Datametrics Readout.  Table C-l below
shows that the linear velocity results agreed to within about 4%.

                                TABLE C-l
                         Performance of Exhaust
                           Splitter on Lab Air

                                              Corresponding Linear
                    Measured                   Velocities (ft/rain)
                    Flow Rate               Datametrics
  CVS                 (CFM)	            Readout
Setting          Vent       Inlet      (Arbitrary Units)     Actual ft/min
 (CFM)            Leg        Leg           Vent   Inlet       Vent   Inlet

  150             72.7      24.5           0.89   0.95        1111   1125

  225            132.7      44.0           1.52   1.65        2029   2018

          The procedure in an actual run would be to adjust the variable
speed pump until the linear velocities in the vent and inlet legs were equal.
No volumetric flow rate measurement would be made because it is doubtful
that any flow meter would function properly after exposure to hot corrosive
exhaust, and any flowmeter in the inlet leg could alter the quantity of
particulate matter entering the dilution tunnel.  Table C-l shows that it
should not be necessary to measure the volumetric flow rates.  All that
would be necessary would be to maintain equal linear velocities in leg.

          Although Table C-l shows that this approach is promising, this
method has not been successful in actual runs with catalyst equipped vehi-
cles.  Several anemometer probes have failed when exposed to hot raw ex-
haust from oxidation catalyst equipped vehicles.  It is probable that
corrosion of the sensing wires due to exposure to hot sulfuric acid aerosol
is the cause.  In several vehicle tests, the sensing wires were missing
after the run, or else was attached to only one binding post.

          Another approach along the same basic idea was to measure the
linear velocities using Pitot tubes, and equalizing the velocities by ad-
justing the pressure drop in the vent leg using a variable speed pump.
The pressure drops were small and subject to rapid oscillations, making
equalization extremely difficult.  Attempts to damp these oscillations were
not successful.

-------
                                  - 165 -


                                APPENDIX D
               BASIS OF  SELECTION  OF THE  SULFUR AND NITROGEN
                 CONTAINING ORGANIC COMPOUNDS WHICH MIGHT
               	APPEAR  IN AN AUTO  EXHAUST
          The  rationale for selecting  classes of nitrogenous  and non-
sulfate  sulfur compounds as possible exhaust components  is based on known
chemical reactions which produce  these compounds.  Only  those components
known  to exist in vehicular exhaust, which  can  function  as precursors
to  compound  types or as reactants involved  in their production, are consi-
dered.   Several examples will be  considered in  some detail.

          Schuchmann and Laidler  (14)  have  shown the existence of alkyl
nitriles in  automobile exhaust, which  are the products of reaction between
nitric oxide and alkyl radicals,  i.e.,
                RCH2'  +   NO  	^  RCN    +    H20


Based on the above reaction, alkyl nitrites could also be a logical ex-
haust product as a result of reaction between nitric oxide and alkaxy
radical as shown below:
                      RO-    +     NO    	RONO
          Scizinger and Dimitriades (15), have shown that nitroalkanes are
components of automobile exhaust.  Nitroalkanes could conceivably be made
by reaction of alkyl radicals and N0_.  However, it is not necessary to
invoke this reaction to account for nitroalkanes.  Levy (16), has shown that
in the presence of nitric oxide,alkyl nitriles are convented to nitro-
alkanes .

          Ter Hoar, et. al.(17), have reported the presence of nitrates in
exhaust particulates.   Organic nitrates could be formed by reaction of
alkyl nitrites with peroxides as shown below(18):


            RCH2ONO      +      R'OOH  	^  R'OH    +    RCH ONO

-------
                                   - 166  -
          The absence of peroxides in end gas condensate as demonstrated
by Alperstein and Bradow(19) and the presence of alcohols (15) and nitrates (17)
in automobile exhaust may be the result of the above type of reaction.
Although the formation of the aromatic analogues of the nitrogenous com-
pounds listed is less likely than their aliphatic counterparts, tests for
the nitrogenous aromatic compounds were also carried out.

          Arguments applied to the possible formation of nitrogenous exhaust
matter are applicable to the non-sulfate sulfur compounds.  For example,
sulfinic acids could be produced by reaction of SO, and an aromatic species
as shown below (2):
Aromatic sulfonic acids  could result  from reaction  of  SO-  and an aromatic
species as shown below (21):
          There are  several factors  operating  against  the  formation  of
aromatic sulfonic  acids  in  auto  exhaust:  The  low  concentration  of SO-  in
conventional vehicle exhaust,  and  the  greatly  reduced  level  of aromatic species
(organics in general)  in the exhaust of an  oxidation catalyst equipped
vehicle.  However, if  one grants the possibility of aromatic sulfonic acids,
the presence of sulfones is also possible by virtue of the following re-
action^):

            R(£-S03H      +    R'^-H

Another possible mechanism  by which  sulfones may be formed is by the re-
action of SO- with a conjugated  di-olefin as shown below(23):

                 R H  H
           Sulfur  compounds such as thiocarbonyls,  sulfides,  and mercaptans
 are  possible  only under reducing conditions.   Should operating conditions,
 over an  oxidation catalyst become  net rich,  a number of S02 reduction pro-
 ducts including H_S are then possible.  This  condition is unlikely unless
 engine or  system  malfunctions occur.   Should  these malfunctions occur, H^S
 could react with  various reactive exhaust components such as ketones,
 aldehydes, and olefins to produce thiocarbonyls and mercaptans as shown
 below: (14)       R,                 Rl
                 RC=fO  +  H-S	> RC=S       and possible polymers

                 RC=0  +  H2S 	^ RC=S

                    C—PU   .A-  U  C        ^  /PU  ^ PQH
                    —\stlty  T  rind        w  \\ti\r..) -L»on
                  ^     fc      ^               j  j

-------
                                   - 167 -
          Mercaptans could also possibly be formed by the reaction be-
tween alcohols present in exhaust and H.S as shown below (25):

              ROH   +   H2S  - ^ RSH and H20, although this is a
less likely route to mercaptans.

          In situations where H.S is produced alkyl  isothiocyanates may
be produced if notroalkanes are also present by virtue of the following
possible pathway (26,27).
                                   RC-NHOH
                 RC-NHOH - ^ RNCO  +  H_0

                 RNCO + H2S -- 7> RNCS  +  H20

          The occurrence of many of the organic sulfur compounds , parti-
cularly the thiocarbonyls , sulfides, and mercaptans, in auto exhaust how-
ever, is extremely unlikely for  the following reasons.  The operating con-
ditions favoring H_S formation (high catalyst temperature and oxygen de-
ficiency) do not normally occur  in oxidation catalyst emission control
systems, so that H.S formation over the catalyst is unlikely unless engine
or system malfunctions occur (28).  Even if H.S were produced, the formation
of a mercaptan by reaction of H.S with an alcohol becomes more unfavorable
with increasing temperature, precisely the conditions assuming oxygen de-
ficiency favorable for H.S formation.   Thermodynamic calculations based on
Free Energy of Formation data obtained from Stull, et. al(29) show that in
the temperature range of 800 to  1200 F, mercaptans should not form.

          The occurrence of nitrogenous and sulfur compounds in automobiles
would expected to be at most at  trace levels.  That they should be present
in automotive exhaust particulate is even more remote.  For example, if
all of the nitrogenous additive was convented to all or any of the nitro-
genous compounds discussed, it can readily be shown that there is not
sufficient nitrogen containing additive to produce enough of these compounds
to co-exist as two phases (vapor plus liquid) at the particulate collection
temperature.  Only the liquid form could be trapped as particulate, and
it cannot exist as a liquid under the test conditions.

          Assume that an alkyl nitrile such as valeronitrile (CH_)_ -CH-
(CH2)_CN was an exhaust component.  At the particulate collection temper-
ature 90F, the vapor pressure of this compound is 12mmHg.  At a tunnel flow
rate of 450CFM (12,600 liters/min) , the minimum production rate of valero-
nitrile required to maintain the equilibrium vapor pressure calculated from
the ideal gas law is :

                 (12/760) atm (12600)  lit/min
                 (365"K) 82x10-3 litatm mole-1 deg-1

               =  6.65 moles /min

               =  645 gms/min

-------
                                 - 168 -
          This production rate is many orders of magnitude greater than
that of a nitrogenous exhaust product derived from a nitrogenous additive
could possibly be.  This applies to all the nitrogenous compounds tested
for.  Therefore, if nitrogenous additives result in nitrogenous organic
compounds as exhaust components, they must exist as gaseous components
if they exist at all.  The only ways nitrogenous particulate exhaust
compounds could exist would be if they were strongly chemadsorbed on
particulate matter, or if they survived as high molecular weight nitro-
genous components.  It is unlikely therefore, that there is an effect of
nitrogenous additives on exhaust particulate emissions.

          Using a similar argument, it can be shown that it is highly
unlikely that non-sulfate sulfur compounds would show up as exhaust parti-
culate.  The negative tests obtained for the nitrogenous and non-sulfate
sulfur compounds in exhaust particulate substantiates the above discussion.

          Coupling this discussion with the negative test results, it may
be concluded that there is no exhaust particulate derived from the ashless
nitrogenous additives used.  It may also be concluded that regarding
sulfur containing particulate, sulfate is the overwhelmingly predominant
species and most likely only one capable of existing as particulate.

          Although the previous discussion pertained to nitrogenous and
non-sulfate sulfur containing particulate matter, similar conclusions can
be drawn regarding the presence of many of these compounds as gaseous com-
ponents of exhaust.  This would particularly apply to the non-sulfate
sulfur compounds, especially the divalent sulfur compounds.  For example,
consider the formation of COS produced by the following reaction:


          C02  +  H2S  	-)  COS  +  H20

In raw, undiluted automotive exhaust, the C02 and H20 partial pressure
are comparable, greatly exceeding any H2S present.  Consequently, the
equilibrium constant for COS formation is the ratio of

              Pcos PH20  _  Pcos
         K =  PH2S PC02  "  PR2S

        The value of K at temperatures ranging from 800°F to 1160°F
ranges from 2.1 x 10~6 to 1.1 x 10"7.  Thus, the COS concentration can
only be a negligible fraction of the H2S concentration.  Since H2S
formation is unlikely, and at most would exist at low levels for small
time intervals, COS could not be a component of automotive exhaust.  Similar
types of arguments could be extended to other organic compounds containing.
di-valent sulfur.

-------
                               - 169 -


                              APPENDIX E

                               RAW DATA
E.I  List of Raw Data Tables
                                Title
Table

 E-l     Gaseous Emissions - Unequipped Mileage Accumulation Vehicle
 E-2             |          - Unequipped Test Vehicle
 E-3             [          - Engelhard Monolithic Oxidation Catalyst
 E-4                       - Engelhard Pelletized Oxidation Catalyst
 E-5                       - UOP (1) Monolithic Oxidation Catalyst
 E-6                       - Matthey-Bishop Monolithic Oxidation Catalyst
 E-7                       - Grace NOX Reduction Catalyst
 E-8                       - Gould NOX Reduction Catalyst
 E-9                       - Grace Pelleted Oxidation Catalyst
 E-10                      - UOP (2) Monolithic Oxidation Catalyst
 E-ll                      - Air Products Pelletized Oxidation Catalyst
 E-12                      - Sulfate Storage Experiment
 E-13           \f          ~ Engelhard Monolithic Oxidation Catalyst
                             After Misfire
 E-14    Metal Derived Particulate Emissions - Unequipped Mileage Accumulation
                                               Vehicle Runs (1-15) and Unequipped
                                               Test Vehicle Runs (16-30)
 E-15                                        - Engelhard Monolithic Oxidation
                                               Catalyst
 E-16                                        - Engelhard Pelletized Oxidation
                                               Catalyst
 E-17                                        - UOP (1) Monolithic Oxidation
                                               Catalyst
 E-18                                        - Matthey-Bishop Monolithic
                                               Oxidation Catalyst
 E-19                                        - Grace Reduction Catalyst
 E-20                                        - Gould NOX Reduction Catalyst
 E-21                                        - Grace Pelletized Oxidation
                                               Catalyst
 E-22                                        - UOP (2) Monolithic Oxidation
                                               Catalyst
 E-23                                        - Air Products Pelletized
                \|/                              Oxidation Catalyst
 E-24                                        - Sulfate Storage Experiment
 E-25    Sulfate Emissions - Unequipped Mileage Accumulation Vehicle
 E-26                      - Unequipped Test Vehicle
 E-27                      - Engelhard Monolithic Oxidation Catalyst
 E-28                      - Engelhard Pelletized Oxidation Catalyst
 E-29                      - UOP (1) Monolithic Oxidation Catalyst
 E-30                      - Matthey-Bishop Monolithic Oxidation Catalyst
 E-31                      - Grace NOX Reduction Catalyst
 E-32                      - Gould NOX Reduction Catalyst
 E-33                      - Grace Pelletized Oxidation Catalyst
 E-34                      - UOP (2) Monolithic Oxidation Catalyst
 E-35           \/          - Air Products Pelletized Oxidation Catalyst
 E-36                      - Sulfur Storage Experiment

-------
                                     - 170 -
                                    TABIE E-l
GASEOUS EMISSIONS
UNEQUIPPED MILEAGE ACCUMULATION VEHICLE
Test No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
70 (2)
" 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
0.091 75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
Gaseous Emissions, gms/km
CO
8.76
[170.38]
7.54
5.90
8.58
9.09
[ 	 ]
	
2.63
8.59
9.49
[169.92]
4.23
2.62
8.24
HC
1.23
[9.24]
0.417
0.05
1.57
1.38
[ 	 ]
	
0.06
1.21
1.62
[24.43]
2.60
0.010
1.80
NO
A
0.86
[19.12]
0.61
1.76
0.97
1.02
[ 	 ]
	
0.73
1.00
1.38
[2.93]
0.34
0.60
1.17
SO.
z
	
	
	
	
0.239
	
	
0.181
0.301
0.363
[4.47]
0.154
0.154
0.347
0.019% S = EPA furnished reference fuel
0.110% S = EPA reference fuel plus additive package
0.090%   = High aromatic fuel plus additive package

75 FTP   = 1975 Federal test procedure
Idle (1) = One hour idle
40 (1)   = 40 mph (64 km/hr) cruise for one hour
70 (2)   = 70 mph (112 km/hr) cruise for two hours
(Idle gaseous emissions, brackets, are in gms/hr)*

-------
                                     -  171 -
                                    TABLE E-2
GASEOUS EMISSIONS
UNEQUIPPED TEST VEHICLE
Test No.
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
0.110 75 FTP
Idle (1)
40 (1)
70 (2)
11 75 FTP
0.091 75 FTP
Idle (1)
40 (1)
70 (2)
" 75 FTP
Gaseous Emissions, gms/km
CO
6.33
[21.69]
3.15
2.32
6.84
6.23
[29.4]
3.09
1.72
6.28
7.13
[35.14]
1.92
00.61
6.61
HC
0.78
[10.85]
0.18
0.04
3.70
0.71
[7.06]
0.17
0.05
0.99
0.75
[8.56]
0.17
0.05
0.74
NO
0.97
[3.05]
0.28
0.86
0.78
0.77
[2.20]
0.29
0.86
0.85
0.84
[6.30]
0.43
0.54
0.84
SO,
	 2 	
0.048
[1.260]
[0.025]
[0.035]
0.076
0.284
[3.262]
0.202
• 0.167
0.295
0.318
[5.26]
0.160
0.136
0.301
0.019% S  = EPA furnished reference fuel
0.110% S  = EPA reference fuel plus additive package
0.090%    = High aromatic fuel plus additive package

75 FTP    = 1975 Federal test procedure
Idle (1)  = One hour idle
40 (1)    = 40 mph (64 km/hr) cruise for one hour
70 (2)    = 70 mph (112 km/hr) cruise for two hours
(Idle gaseous emissions, brackets, are in gms/hr)*

-------
                                     - 172 -
                                    TABLE E-3
             % Fuel
Test No.     Sulfur
   36        0.019
   37
   38
   39
   40
   41        0.110
   42
   43
    44
    45
    46        0.091
    47
    48
    49
    50
CASEOUS EMISSIONS
ENGELHARD MONOLITHIC OXIDATION
CATALYST EQUIPPED VEHICLE
Caseous Emissions, gms/km
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
CO
3.26
[7.70]
0.05
	
1.18
1.45
[5.32]
0.20
0.024
2.03
1.40
[7.26]
0.28
	
2.01
HC
0.29
[4.45]
0.04
	
0.63
0.80
[5.62]
0.08
0.003
0.42
0.28
[6.10]
0.08
	
0.28
NO
	 x
0.91
[8.66]
0.15
	
0.74
1.20
[3.91]
0.52
0.19
0.88
1.33
[3.91]
1.04
	
1.31
so,,
-x-0
0
0
0
0
0.134
[2.55]
0.057
0.009
0.139
0.080
[2.14]
0.050
	
0.098
0.019% S  = EPA furnished reference fuel
0.110% S  = EPA reference fuel plus additive package
0.090%    = High aromatic fuel plus additive package

75 FTP    = 1975 Federal test procedure
Idle (1)  = One hour idle
40 (1)    = 40 mph (64 km/hr) cruise for one hour
70 (2)    = 70 mph (112 km/hr) cruise for two hours
(Idle gaseous emissions, brackets, are in gms/hr)*

-------
                                      - 173  -
                                    TABLE E-4
GASEOUS EMISSIONS
ENGELHASD PELLETIZED OXIDATION
CATALYST EQUIPPED VEHICLE
Test No.
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
70 (2)
" 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
0.091 75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
Gaseous Emissions, ems/km
CO
2.528
[0.81 ]
0.019
	
2.501
1.528
[7.506]
0.154
0.086
1.327
2.162
[4.676]
0.218
0.044
2.808
HC
0.217
[1.458]
0.016
	
0.224
0.349
[3.964]
0.075
0.029
0.176
0.324
[2.333]
0.089
0.008
0.219
NOX
1.370
[0.54 ]
0.008
	
1.318
1.229
[8.73 ]
0.601
1.581
1.013
1.194
[8.932]
0.740
3.111
1.171
SO 2
0.015
[0.0 ]
0.0
	
0.093
0.043
[0.544]
0.0
0.0
0.058
0.061
0.0
0.022
0.129
0.066
0.019% S  = EPA furnished reference fuel
0.110% S  = EPA reference fuel plus additive package
0.090%    = High aromatic fuel plus additive package

75 FTP    = 1975 Federal test procedure
Idle (1)  = One hour idle
40 (1)    = 40 mph (64 km/hr) cruise for one hour
70 (2)    = 70 mph (112 km/hr) cruise for two hours
(Idle gaseous emissions, brackets, are in gms/hr)*

-------
                                      - 174 -
                                     TABLE E-5
Test No.
   66
   67
   68
   69
   70
   71
   72
   73
   74
   75
   76
   77
   78
   79
   80
% Fuel
Sulfur
 0.019
 0.110
 0.091
GASEOUS EMISSIONS
UOP(l) MONOLITHIC OXIDATION
EQUIPPED TEST VEHICLE
CATALYST


Gaseous Emissions, gins/km
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
CO
2.652
[22.766]
0.129
0.174
1.770
1.742
[ 4.946]
0.119
0.121
2.124
1.800
[ 4.136]
0.132
0.147
1.863
HC
0.274
L11.416]
0.042
0.018
0.191
0.250
[ A. 277]
0.048
0.014
0.264
0.191
[ 4.158]
0.033
0.013
0.150
NOX
1.091
16.728]
0.694
1.955
0.927
1.079
[5.098]
0.505
0.118
0.622
1.277
[6.836]
0.706
3.570
1.305
S02
0.061
[0.0 ]
0.0
0.031
0.029
0.190
[o.o ]
0.031
0.117
0.186
0.074
[0.0 ]
0.043
0.107
0.004
 0.019% S   = EPA furnished reference fuel
 0.110% S   = EPA reference fuel plus additive package
 0.090%     = High aromatic fuel plus additive package
 75 FTP     = 1975  Federal  test procedure
 Idle  (1)   = One hour idle
 40 (1)     = 40 mph  (64 km/hr)   cruise  for one hour
 70 (2)     = 70 mph  (112 km/hr)  cruise  for two hours
 (Idle gaseous emissions, brackets,  are  in gms/hr)*

-------
                                     - 175 -
                                    TABLE E-6
GASEOUS EMISSIONS
MATTHEY BISHOP MONOLITHIC OXIDATION
CATALYST EQUIPPED TEST VEHICLE
Test No.
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
0.019% S
0.110% S
0.090%
75 FTP
Idle (1)
40 (1)
60 (2)
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)**
11 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
0.091 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
Gaseous Emissions,, gms/km
CO
1.373
[ 8.834]
0.200
0.427
0.959
1.035
[ 8.067]
0.267
0.555
2.663
1.040
[5.430]
0.288
0.549
2.087
HC
0.232
[ 5.584]
0.047
0.033
0.146
0.241
[ 6.361]
0.058
0.033
0.323
0.244
[4.061]
0.049
0.030
0.253
NOX
1.083
[11.524]
0.598
2.208
0.578
1.116
[ 7.020]
0.648
2.430
1.136
1.313
[8.381]
30.890
2.938
2.112
S02*
0.031
[ 0.961]
0.037
0.022
0.023
0.245
[ 3.694]
0.197
0.213
0.275
0.233
[2.960]
0.160
0.194
0.388
= EPA furnished reference fuel
= EPA reference fuel
= High aromatic fuel
= 1975 Federal test
= One hour idle
= 40 mph (64 km/hr)
= 60 mph (96 km/hr)
plus additive
plus additive
procedure

cruise for one
cruise for two
package
package


hour
hours












(Idle gaseous emissions, brackets, are in gms/hr)*
*   S02 calibrated from S02 in air calibration curve (no correction factor was  used)
**  60 mph (96.54 km/hr) supplants the former 70 mph cruise test runs

-------
                                     -  176  -
                                    TABLE E-7
GASEOUS EMISSIONS
GRACE NOX REDUCTION
CATALYST EQUIPPED VEHICLE
Test No.
96
97
98
99
100
101
102
103
10 A
105
106
107
108
109
110
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)
11 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
0.091 75 FTP
Idle (1)
40 (1)
60 (2)
•• 75 FTp
Caseous Emissions, gms/km
CO
10.177
[42.206]
0.350
1.913
7.298
10.657
[98.550]
0.603
0.208
]0.439
10.828
[41.926]
0.474
0.350
14.262
HC
0.375
[4.19]
0.055
0.057
0.498
0.446
[11.804]
0.099
0.024
0.455
0.454
[13.640]
0.077
0.057
0.531
NO
2.006
[8.906]
1.469
3.175
.1.907
2.138
[10.530]
1.976
1.682
1.860
2.529
[7.873]
1.842
4.783
2.705
so,.

-------
                                     - 177 -
                                    TABLE E-8
Test No.
  Ill
  112
  113
  115
  116
  117
  118
  119
  120
  121
  112
  123
  124
  125
% Fuel
Sulfur
0.019
0.110
0.091
CASEOUS EMISSIONS
GOULD NO REDUCTION CATALYST
EQUIPPED VEHICLE
Gaseous Emissions, gms/km
Run Type
75 FTP
Idle (1)
40 (!)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
CO
12.560
[75.589]
0.131
0.006
8.102
J1.558
[5.195]
0.1.80
0.014
6.458
6.173
[9.050]
0.140
0.066
6.466
HC
0.582
[7.247]
0.055
0.003
0.285
0.430
[3.424]
0.046
0.005
0.297
0.452
[4.428]
0.038
0.023
0.327
NO
K
1.515
[1.205]
1.721
0.319
1.890
2.032
[6.134]
2.083
0.503
2.967
1.966
[6.588]
2.249
3.865
2.620
SO
0.119
[0.035]
0.024
0.004
0.053
0.290
[1.62]
0.139
0.020
0.271
0.243
[1.577]
0.107
0.125
0.242
0.019% S  = EPA furnished reference fuel
0.110% S  = EPA reference fuel plus additive package
0.090%    = High aromatic fuel plus additive package
75 FTP    = 1975 Federal test procedure
Idle (1)  = One hour idle
40 (1)    = 40 mph (64 km/hr) cruise for one hour
70 (2)    = 70 mph (112 km/hr) cruise for two hours
(Idle gaseous emissions, brackets, are in gms/hr)*
Exhaust gas recycle and air pump disconnected

-------
                                     - 178 -
                                    TABLE E-9
Test No.
  126
  127
  128
  129
  130
  131
  132
  133
  134
  135
  136
  137
  138
  139
  140
             % Fuel
             Sulfur
             0.019
             0.110
               ii
             0.091
CASEOUS EMISSIONS
GRACE PELLETIZED OXIDATION
CATALYST EQUIPPED VEHICLE
Gaseous Emissions, gms/km
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
CO
1.563
[3.000]
0.116
0.051
1.739
1.519
[3.445]
0.103
0.048
0.966
1.274
[6.826]
0.278
0.063
2.053
HC
0.182
[4.212]
0.027
0.015
0.150
0.162
[3.726]
0.028
0.011
0.164
0.154
[4.039]
0.030
0.011
0.134
NO
1.188
[6.005]
0.686
1.788
1.215
1.304
[6.977]
0.016
1.887
1.323
1.332
[7.571]
0.813
2.801
1.412
S00
0.032
[0.000]
0.006
0.022
0.010
0.070
[0.389]
0.076
0.13]
0.131
0.072
[0.972]
0.055
0.005
0.08]
0.019% S  = EPA furnished reference fuel
0.110% S  = EPA reference fuel plus additive nackage
0.090%    = High aromatic fuel plus additive package
75 FTP    = 1975 Federal test procedure
Idle (1)  = One hour idle
40 (1)    = 40 mph  (64 km/hr) cruise for one hour
60 (2)    = 60 mph  (96 km/hr) cruise for two hours
(Idle gaseous emissions, brackets, are in gms/hr)*

-------
                                     - 179 -
                                   TABLE E-10
GASEOUS EMISSIONS
UOP(2) MONOLITHIC OXIDATION CATALYST
EQUIPPED VEHICLE
Test No.
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
0.110 75 FTP
Idle (1)
40 (1)
60 (2)
" 75 FTP
0.091 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
Caseous Emissions, gms/km
CO
0.666
[2.862]
0.105
0.089
1.431
0.768
[4^.471]
0.098
0.070
0.653
0.805
[4.018]
0.103
0.065
1.227
HC
0.101
[3.845]
0.016
0.018
0.127
0.098
[4.439]
0.025
0.021
0.105
0.154
[4.374]
0.023
0.012
0.239
NO
x —
1.231
[8.597]
0.776
2.877
1.150
1.303
[8.921]
0.770
1.946
1.316
1.270
[5.918]
0.829
2.574
1.345
son
0.008
[0.000]
0.000
0.018
0.028
0.046
[0.194]
0.045
0.110
0.146
0.094
[0.389]
0.061
0.005
0.187
0.019% S  = EPA furnished reference fuel
0.110% S  = EPA reference fuel plus additive package
0.090%    = High aromatic fuel plus additive package
75 FTP    = 1975 Federal test procedure
Idle  (1)  = One hour idle
40 (1)    = 40 mph  (64 km/hr) cruise for one hour
70 (2)    = 60 mph  (96 km/hr) cruise for two hours
(Idle gaseous emissions, brackets, are in gms/hr)*

-------
                                     - 180 -

                                    TABLE  E-ll
GASEOUS EMISSIONS
AIR PRODUCTS PELLETIZED
OXIDATION CATALYST EQUIPPED VEHICLE
Test No.
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
0.110 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
0.091 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
Caseous Emissions, gms/km
CO
3.825
[4.838]
0.049
0.027
1.860
4.607
[4.126
0.109
0.041
1.012
1.089
[2.786]
0.160
0.049
1.421
HC
0.268
[3.996]
0.017
0.010
0.115
0.185
[2.754]
0.027
0.015
0.135
0.170
[2.970]
0.016
0.013
0.174
NO
J"t
1.113
[14.515]
0.945
1.211
0.849
0.840
[8.64]
0.352
1.021
0.854
1.241
[8.402]
0.948
2.024
1.172
SO
0.028
[0.000]
0.002
0.016
0.001
0.040
[0.000]
0.030
0.080
0.042
0.082
[0.184]
0.044
0.096
0.076
0.019% S   = EPA furnished reference fuel
0.110% S   = EPA reference fuel plus additive package
0.090%     = High aromatic fuel plus additive package

75 FTP     = 1975 Federal test procedure
Idle (1)   = One hour idle
40 (1)     = 40 mph  (64 km/hr) cruise for one hour
60 (2)     = 60 mph  (96 km/hr) cruise for two hours
(Idle gaseous emissions, brackets, are in gms/hr)*

-------
                                -  181 -
                               TABLE E-12
         GASEOUS EMISSIONS, TEST VEHICLE EQUIPPED WITH ENGELHARD
      PELLETIZED OXIDATION CATALYST AFTER CATALYST WAS CONDITIONED
     ON A 0.091% S FUEL FOR 3200 KM ON THE FEDERAL DURABILITY CYCLE
Test No.
171
172
173
174
175
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)
" 75 FTP
Emission Rates, j>ms/km
CO
1.225
[3.283]
0.137
0.040
1.011
HC
0.192
[5.411]
0.042
0.014
0.193
NO
	 x —
1.201
[10.033]
0.627
2.472
1.092
S00
0.050
[0.983]
0.016
0.088
0.077
                               TABLE E-13
              GASEOUS EMISSIONS, TEST VEHICLE EQUIPPED WITH
                ENGELHARD MONOLITHIC OXIDATION CATALYST*

Test No.

31
32
33
34
35
% Fuel
Sulfur Run Type

0.019 75 FTP
Idle (1)
40 (1)
" 70 (2)
" 75 FTP
Emission Rates, gins /km
CO

0.77
[6.11]
0.22
0.15*
4.84
HC

0.70
[2.08]
0.050
0.010
0.92
NO
X
1.66
[6.98]
0.38
0.18
1.11
SO,
	 2—
0.035
[1.54]
0.045
0.003
0.057
Temperature runaway due to misfire 19 minutes into the run resulting
in catalyst deactivation, compare runs 31 and 35.  The emission rates
for Test No. 34 are presented on normalized basis.

A second catalyst of this type was conditioned and screened (Table E-3)
Runs 36-50.

-------
                                                              TABLE E-14
                                              METAL DERIVED EXHAUST PARTICULATE EMISSIONS
                                BASE CASE RUNS WITH UNEQUIPPED MILEAGE ACCUMULATION VEHICLE RUNS  (1-15)
                                               AND UNEQUIPPED TEST VEHICLE RUNS (16-30)
Test
 No.

  1
  2
  3
  4
  5
  6
  7
  8
  9
 10
 11
 12
 13
 14
 15
 16
 17
 18
 19
 20
 21
 22
 23
 24
 25
 26
 27
 28
 29
 30
  Run
  Type

75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
% Fuel
Sulfur

0.019
0.110
0.091
0.019
0.116
0.091
EMISSION RATE, CMS /KM AS
Ca
0.00025
[<0.0008]
0.00003
0.00011
0.00016
0.00014
[0.0022]
0.00004
0.00001
0.00017
0.00014
[0.0012]
0.00002
0.00001
0.00009
0.00007
[0.0004]
0.00001
<6 x 10-6
0.00002
0.00005
[<0.0004]
0.00002
<6 x 10-6
0.00004
0.00007
[0.0004]
0.00001
<0. 00001
0.00002
Al
<0. 00005
[<0.0008]
<0. 00001
6 x 10-6
0.00006
0.00020
[0.0015]
0.00002
0.00001
0.00006
0.00006
[<0.0004]
<6 x 10-6
<0. 00001
0.00004
0.00007
[<0.0004]
<6 x ID'6
<6 x ID"6
<0. 00002
0.00004
[<0.0004]
<6 x 10-6
<6 x ID"6
<0. 00002
0.00004
[<0.0004]
<6 x 10~6
<6 x lO-6
<0. 00002
Zn
0.00035
[0.0008]
0.00010
0.00009
0.00064
0.00027
[0.0035]
0.00005
0.00003
0.00080
0.00027
[0.0006]
0.00002
0.00003
0.00040
0.00016
[0.0006]
0.00001
0.00001
<0. 00002
0.00007
[0.0004]
0.00001
<0. 00001
0.00006
0.00010
[<0.0004]
<6 x 10-6
< 0.00001
0.00007
INDICATED METAL*
Cr
0.00005
[<0.0008]
0.00003
<0. 00001
0.00005
0.00007
[0.0009]
0.00002
<0. 00001
0.00009
0.00020
[0.0006]
<6 x ID"6
<6 x 1(T6
0.00005
0.00007
[< 0.0004]
< 0.00001
<6 x 10-6
< 0.00002
0.00012
[<0.0004]
<6 x 10~6
<6 x 10-6
< 0.00002
0.00004
[<0.0004]
<6 x 10-6
<6 x ID'6
<0. 00002
Fe
0.00134
[0.00032]
0.00022
0.00015
0.00080
0.00022
0.0080
0.00022
0.00012
0.00132
0.00134
[0.0040]
0.00003
0.00008
0.00052
0.00121
[0.0037]
0.00009
0.00006
0.00004
0.00123
[0.0005]
0.00004
0.00004
0.00028
0.00091
[0.0018]
0.00002
0.00006
0.00031
Cu
0.00012
[<0.0008]
0.00002
<6 x 10-6
0.00016
0.00014
[0.0019]
0.00002
0.00001
0.00031
0.00027
[<0.0004]
<6 x 10-6
0.00002
0.00025
0.00047
[0.0009]
<6 x 10-6
0.00004
0.00002
0.00040
[0.0008]
0.00002
0.00001
0.00037
0.00021
[0.0008]
0.00002
0.00002
0.00039
Ni
<0. 00005
[<0.0008]
0.00001
<0. 00001
0.00004
0.00005
[0.0009]
0.00001
<0. 00001
0.00008
0.00019
[<0.0004]
<6 x 10-6
0.00001
0.00005
0.00008
[<0.0004]
<6 x ID"6
<6 x 10~6
<0. 00002
0.00009
[<0.0004]
<6 x 10-6
<0. 00001
<0. 00002
0.00004
[<0.0004],
<6 x 10~b
<6 x 10"6
<0. 00002
Pb
0.00043
[0.0008]
0.00011
0.00009
0.00042
0.00058
[0.0063]
0.00014
0.00006
0.00006
0.00087
[0.0122]
0.00010
0.00006
0.00049
0.00070
[0.0024]
0.00005
0.00004
<0. 00002
0.00062
[0.0069]
0.00021
0.00010
0.00042
0.00059
[0.0004]
0.00011
0.00009
0.00037
                                                                                                                              oo
                                                                                                                              ro
  75 FTP   = 1975 Federal Test Procedure
  Idle (1) = one hour idle
  40 (1)   " 40 mph (64 km/hr) cruise for one hour
  70 (2)   = 70 mph (112 km/hr) cruise for two hours

  *  Bracketed numbers are idle emission rates of metals  in  gms/hour.

-------
                                                         TABLE E-15


                                         METAL DERIVED EXHAUST PARTICULATE EMISSIONS
Toot*
ico u
No.
31
32
33
34
35
36*
37
38
39
40
41
42
43
44
45
46
47
48
49
50
%Fucl
C UC J-
Run Type Sulfur
75 FTP 0.019
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP 0.019
Idle (1)
40 (1)
70 (2)
75 FTP "
75 FTP 0.110
Idle (1)
40 (1)
70 (2)
75 FTP "
75 FTP 0.091
Idle (1)
40 (1)
70 (2)
75 FTP "
EMISSION RATE, GMS/KM AS INDICATED METAL*
Ca
0.00010
[<0. 00180]
0.00004
0.00021
0.00016
0.00010
[ 0.00180]
<0. 00003
0.00009
0.00013
0.00016
[ 0.00180]
0.00003
<0. 00002
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Al
>0. 00010
[ 0.00180]
<0. 00003
0.00079
0.00051
0.00029
[ 0.00400]
0.00005
0.00016
<0. 00010
0.00021
[<0. 00180]
0.00004
0.00003
<0.00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Zn
>0. 00033
[ 0.00180]
<0. 00003
0.00204
0.00202
>0. 00100
[ 0.01440]
0.00011
0.00027
0.00039
0.00100
[<0. 00180]
0.00016
0.00015
0.00048
0.00043
[ 0.00220]
0.00003
>0. 00024
0.00079
Cr
0.00013
[ 0.00180]
<0.00003
0.00031
0.00025
0.00016
[<0. 00180]
<0. 00003
<0. 00058
<0. 00010
0.00037
[<0. 00180]
0.00003
0.00004
<0. 00010
0.00019
[<0. 00180]
<0. 00003
0.00001
0.00011
Fe
0.00202
[ 0.03600]
0.00010
0.00440
0.00202
>0. 00200
[>0.0018 ]
0.00021
>0. 00058
>0. 00100
>0. 00202
[ 0.00320]
>0. 00028
>0. 00020
>0. 00100
>0. 00100
[ 0.00240]
0.00006
>0. 00012
>0. 00100
Cu
0.00051
[ 0.00920]
<0. 00003
0.00115
0.00092
0.00038
[<0. 00180]
<0. 00003
0.00008
<0. 00010
0.00075
[<0. 00180]
0.00005
0.00006
0.00045
0.00065
[<0. 00180]
<0. 00003
0.00003
0.00072
Ni
0.00010
[ 0.00180]
O.00003
0.00021
0.00022
<0. 00010
[<0.0018 ]
<0. 00003
<0. 00058
<0. 00010
0.00020
[<0. 00180]
0.00004
0.00004
<0. 00010
0.00020
[<0. 00180]
<0. 00003
<0. 00001
0.00015
Pb
0.00100
[ 0.0180 ]
0.00011
0.00440
0.00101
>0. 00100
[ 0.00680]
0.00015
0.00046
0.00056
0.00101
[ 0.00320]
0.00024
>0. 00020
>0. 00100
0.00100
[ 0.00400]
0.00004
>0. 00012
0.00085
                                                                                                                                            oo
                                                                                                                                            LJ
*  Bracketed numbers are  idle emission  rates of metals  in gms/hour.

+  Replacement PTX-IIB  (Runs 36-50)  after  first PTX-IIB deactivated  (Run 34)  due  to  excessive  temperature  rise  resulting  from misfire.

-------
                                                        TABLE  E-16
                                        METAL DERIVED EXHAUST  PARTICULATE EMISSIONS

Test
No.
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65

% Fuel
Run" Type Sulfur
75 FTP 0.019
Idle (1)
40 (1)
70 (2)
75 FTP "
75 FTP 0.110
Idle (1)
40 (1)
70 (2)
75 FTP "
75 FTP 0.091
Idle (1)
40 (1)
70 (2)
75 FTP "


Ca
0.00010
[<0. 00180]
0.00003
0.00004
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00004
<0. 00010
0.00024
[ 0.00380]
0.00006
0.00002
0.00029
EMISSION

Al
0.00026
[<0. 00180]
<0. 00003
>0. 00028
>0. 00100
0.00046
[<0. 00180]
<0. 00003
0.00006
0.00016
0.00020
[ 0.00200]
<0. 00003
0.00001
0.00022
RATE, GMS/KM

Zn
0.00076
[ 0.00260]
0.00004
>0.00057
>0. 00200
0.00037
[<0. 00180]
0.00005
0.00012
0.00019
0.00027
[<0. 00180]
<0. 00003
0.00002
0.00075
AS INDICATED

Cr
0.00021
[<0. 01800]
<0. 00003
>0. 00028
0.00024
0.00028
[<0. 00180]
<0. 00003
0.00005
<0. 00010
0.00018
[<0. 00180]
<0. 00003
<0. 00001
0.00012
METAL*

Fe
>0. 00202
[>0. 01800]
0.00028
>0. 00057
>0. 00200
>0. 00202
[ 0.00760]
0.00018
0.00073
>0. 00100
>0. 00101
[ 0.00620]
0.00023
>0. 00010
>0. 00202


Cu
0.00025
[<0. 01800]
0.00004
>0. 00028
0.00059
0.00048
[<0. 00180]
<0. 00003
0.00010
0.00043
0.00037
[<0. 00180]
<0. 00003
0.00001
0.00078


Ni
0.00019
[<0. 00160]
0.00003
0.00026
0.00019
0.00026
[<0. 00180]
<0. 00003
0.00006
<0. 00010
0.00021
[<0. 00180]
<0. 00003
<0. 00001
0.00015


Pb
>0. 00100
[0.00860]
0.00016
>0.00057
>0. 00100
>0. 00202
[0.00480]
0.00015
>0. 00036
0.00050
0.00076
0.00200
0.00007
0.00003
0.00057
                                                                                                                                               co
                                                                                                                                               I
Bracketed numbers are idle emission  rates  in  gins/hour.

-------
                                                         TABLE E-17


                                         METAL DERIVED EXHAUST FARTICULAXE EMISSIONS
                              TEST VEHICLE EQUIPPED WITH UOP (1) MONOLITHIC OXIDATION CATALYST
EMISSION RATE, CMS /KM AS INDICATED METAL*
Test
No.
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
% Fuel
Sulfur
0.019
11
II
11
11
0.110
11
It
II
II
0.091
ii
11
11

Ca
0.00025
[0.00240]
0.00005
0.00002
0.00015
0.00018
[0.00440]
0.00005
<0. 00010
0 .00020
0.00019
[0.00380]
0.00006
0.00007
0.00022
Al
0.00030
[ 0.00180]
<0. 00003
0.00002
0.00031
0.00032
[ 0.00640]
0.00003
0.00001
0.00018
0.00016
[<0.00180]
<0. 00003
0.00007
0.00021
Zn
0.00035
[<0. 00180]
<0. 00003
0.00008
0.00100
0.00048
[ 0.00280]
0.00004
0.00001
0.00022
0.00025
[<0. 00180]
<0. 00003
0.00016
0.00018
Cr
0.00015
[<0. 00180]
<0. 00003
0.00002
<0. 00010
0.00026
[ 0.00240]
<0.00003
<0. 00001
<0. 00010
0.00012
[<0. 00180]
<0. 00003
0.00008
<0. 00010
Fe
>0. 00101
[ 0.00740]
0.00010
0.00016
> 0.00202
>0. 00202
[>0. 01800]
0.00021
>0. 00008
0.00087
0.00202
[ 0.00280]
0.00016
0.00016
0.00085
Cu
0.00030
[<0.00180]
<0. 00003
0.00003
0.00060
0.00028
[ 0.00260]
<0. 00003
<0. 00001
0.00034
0.00030
[ 0.00180]
<0. 00003
0.00008
0.00038
Ni
0.00017
[<0. 00180]
<0. 00003
<0. 00001
<0 .00010
0.00027
[ 0.00260]
<0. 00003
<0. 00001
<0. 00010
0.00010
[<0. 00180]
<0. 00003
0.00008
<0. 00010
Fb
0.00059
[<0. 00180]
0.00004
0.00008
0.00053
0.00087
[ 0.00780]
0 .00007
0.00002
0.00029
0.00037
[ 0.00200]
0.00014
>0. 00008
0.00039
                                                                                                                                           00
                                                                                                                                           Ul
Bracketed numbers are idle emission rates in gms/hour.

-------
                                                        TABLE E-18



TEST VEHICLE
METAL DERIVED EXHAUST PARTICULATE EMISSIONS
EQUIPPED WITH MATTHEY-BISHOP MONOLITHIC OXIDATION CATALYST
EMISSION RATE, CMS /KM AS INDICATED METAL*
Test
No.
81
82
83
84
85+
86+
87
88
89
90
91
92
93
94
95
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
% Fuel
Sulfur
0.019
II
II
II
11
0.110
II
II
If
II
0.091
II
II
It
It
Ca
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
—
—
[<0. 00180]
0.00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
0.00001
<0. 00010
Al
0.00012
[<0. 00180]
<0.00003
0.00002
—
—
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
0.00001
<0. 00010
Zn
0.00024
[<0. 00180]
<0.00003
>0. 00010
—
—
[<0. 00180]
0.00003
0.00008
0.00018
0.00013
[<0. 00180]
0.00007
>0. 00010
0.00020
Cr
<0. 00010
[<0. 00180]
<0. 00003
0.00001
—
—
[<0. 00180]
<0. 00003
0.00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Fe
>0. 00101
[ 0.01820]
0.00017
>0. 00020
—
—
[ 0.00360]
>0. 00030
>0. 00018
0.00095
>0. 00020
[ 0.00600]
0.00025
>0. 00020
>0. 00101
Cu
<0. 00010
[<0. 00180]
<0.00003
0.00004
—
—
[<0. 00180]
<0. 00003
0.00002
0.00030
0.00039
[<0. 00180]
<0. 00003
0.00003
0.00037
Ni
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
—
—
[<0. 00180]
<0.00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
0.00010
Pb
0.00514
[ 0.00300]
0.00014
>0. 00010
—
—
[ 0.00280]
0.00013
0.00009
0.00034
0.00048
[ 0.00240]
0.00004
>0. 00010
0.00029
                                                                                                                                           I

                                                                                                                                           I--
                                                                                                                                           CO
*  Bracketed numbers are idle emission  rates  in gms/hour

±  Samples 85, 86 Submitted to EPA  for  Platinum Analysis

-------
                                                       TABLE E-19
                                       KETAL DERIVED EXHAUST PARTICULATE EMISSIONS

                                   TEST VEHICLE EQUIPPED WITH GRACE REDUCTION CATALYST
EMISSION RATE, CMS /KM AS
Test
No.
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
% Fuel
Run Type Sulfur
75 FTP 0.019
Idle (1)
40 (1)
60 (2)
75 FTP "
75 FTP 0.110
Idle (1)
40 (1)
60 (2)
75 FTP "
75 FTP 0.091
Idle (1)
40 (1)
60 (2)
75 FTP "

Ca
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00006
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010

Al
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
0.00010
[<0. 00180]
<0. 00006
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010

Zn
0.00025
[<0. 00180]
<0. 00003
0.00008
0.00045
0.00021
[<0. 00180]
<0. 00006
>0. 00010
0.00016
<0. 00010
[<0. 00180]
<0.00003
0.00005
0.00027
INDICATED METAL*

Cr
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00006
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010

Fe
0.00064
[ 0.00580]
0.00014
>0. 00009
>0. 00200
>0. 00100
[<0. 00180]
>0. 00056
>0. 00009
0.00028
0.00020
[ 0.00220]
0.00011
0.00005
0.00062

Cu
0.00016
[<0. 00180]
<0. 00003
<0. 00001
0.00025
0.00017
[<0. 00180]
<0. 00006
0.00002
0.00021
0.00016
[<0. 00180]
<0. 00003
0.00001
0.00037

Ni
<0.00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00006
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010

Pb
0.00016
[0.00200]
0.00005
0.00005
0.00046
0.00045
[0.00240]
0.00010
0.00006
0.00019
0.00025
[0.00300]
0.00007
0.00009
0.00036
                                                                                                                                      I

                                                                                                                                      M
                                                                                                                                      oo


                                                                                                                                      I
*  Bracketed numbers are idle emission rates of metals in gms/hour.

-------
                                                      TABLE E-20
METAL DERIVED EXHAUST PARTICULATE EMISSIONS
TEST VEHICLE EQUIPPED WITH GOULD NOX REDUCTION CATALYST

Test
No.
Ill
112
113
114
115
116
117
118
119
120
121
122
123
124
125

% Fuel
Run Type Sulfur
75 FTP 0.019
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP 0.110
Idle (1)
40 (1)
60 (2)
75 FTP "
75 FTP 0.091
Idle (1) "
40 (1)
60 (2)
75 FTP


Ca
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0 .00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
0.00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
EMISSION

Al
0.00016
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
0.00002
<0. 00010
< 0.00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
RATE, CMS /KM

Zn
0.00012
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
0.00016
[<0. 00180]
<0. 00003
0.00006
0.00010
0.00022
[<0. 00180]
<0. 00003
0.00002
0.00020
AS INDICATED

Cr
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
METAL*

Fe
>0. 00100
[ 0.00400]
0.00006
0.00004
<0. 00010
0.00058
[<0. 00180]
0.00008
>0.00020
0.00038
0.00165
[ 0.00820]
0.00008
0.00040
0.00047


Cu
0.00030
[<0. 00180]
<0.00003
<0. 00001
0.00017
0.00010
[<0. 00180]
<0. 00003
0.00003
0.00024
0.00038
[<0. 00180]
<0. 00003
0.00002
0.00025


Ni
>0. 00202
[ 0.01040]
0.00016
0.00008
>0.00100
0.00047
[ 0.00260]
0.00005
0.00010
0.00103
>0. 00202
I 0.00680]
0.00008
>0. 00009
>0. 00101


Pb
0.00036
[ 0.00200]
0.00003
0.00006
0.00017
0.00026
[<0. 00180]
0.00002
>0. 00010
0.00022
0.00043
[<0. 00180]
<0. 00003
0.00002
0.00054
                                                                                                                                            00
                                                                                                                                            oo
Bracketed numbers are idle emission rates of metals in gms/hour.

-------
                                                           TABLE E-21
Test
 No.
 126
 127
 128
 129
 130
 131
 132
 133
 134
 135
 136
 137
 138
 139
 140
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
% Fuel
Sulfur
0.019
0.110
0.091
METAL DERIVED EXHAUST PARTICULATE EMISSIONS
TEST VEHICLE EQUIPPED WITH GRACE PELLETIZED OXIDATION CATALYST
EMISSION RATE, GMS/KM AS INDICATED METAL*
Ca
0.00011
[<0. 00180]
<0. 00003
0.00003
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00010
<0. 00010
Al
0.00013
[<0. 00180]
<0. 00003
0.00003
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
0.00011
[<0. 00180]
<0.00003
<0. 00010
<0. 00010
Zn
0.00168
[<0. 00180]
0.00014
0.00046
0.00047
0.00018
[ 0.00300]
<0. 00003
0.00003
0.00011
0.00058
[<0. 00180]
0.00009
0.00004
<0. 00010
Cr
<0. 00010
[<0. 00180]
<0.00003
0.00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00010
<0. 00010
Fe
0.00246
[ 0.0026C]
0.00010
>0. 00046
0.00048
0.00172
[ 0.00360]
0.00005
0.00005
0.00076
0.00235
[ 0.01100]
0.00026
0.00006
0.00106
Cu
0.00019
[<0. 00180]
<0. 00003
0.00005
0.00019
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
0.00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00010
<0. 00010
Ni
0.00064
[<0. 00180]
<0. 00003
>0. 00009
0.00017
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00010
<0. 00010
Pb
0.00063
[<0. 00180]
0.00005
>0. 00023
0.00020
0.00021
[<0. 00180]
<0. 00003
0.00003
0.00012
0.00035
[ 0.00240]
0.00009
0.00002
0.00021
                                                                                                                             oo
                                                                                                                             SO
  *  Bracketed numbers are idle emission rates in gms/hour.

-------
                                                            TABLE E-22
Test
 No.
 141
 142
 143
 144
 145
 146
 147
 148
 149
 150
 151
 152
 153
 154*
 155
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
% Fuel
Sulfur
0.019
0.110
0.091
METAL DERIVED EXHAUST PARTICULATE EMISSIONS
TEST VEHICLE EQUIPPED WITH UOP (2) MONOLITHIC OXIDATION CATALYST

Ca
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[ 0.00180]
0.00003
EMISSION RATE, GMS/KM AS INDICATED METAL*
Al
0.00010
[<0. 00180]
<0. 00003
0.00001
<0. 00010
0.00019
[ 0.00220]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
Zn
0.00086
[<0. 00180]
0.00005
0.00023
0.00048
0.00142
[ 0.00200]
0.00022
0.00003
0.00024
0.00024
[<0. 00180]
0.00003
Cr
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
Fe
0.00493
[ 0.00960]
0.00019
0.00046
0.00012
0.00246
[ 0.00920]
0.00027
0.00006
0.00214
>0. 00246
[ 0.01200]
0.00019
Cu
0.00025
[<0. 00180]
<0. 00003
0.00003
0.00036
0.00032
[<0. 00180]
<0. 00003
<0. 00001
0.00020
0.00030
[<0. 00180]
<0. 00003
Ni
0.00019
[<0. 00180]
<0. 00003
0.00004
<0. 00010
0.00017
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
Pb

[ 0.00180]
0.00006
0.00015
0.00040
0.00067
[<0. 00180]
0.00008
0.00002
0.00024
0.00036
[ 0.00300]
0.00005
                                                                                                                            \o
                                                                                                                            o
           <0.00010
<0.00010
                                        0.00013
                            <0.00010
                                                                     0.00236
                                                         0.00026
                                                                                                <0.00010
0.00030
    Bracketed numbers are Idle emission rates in gms/hour.
    Filter badly fragmented.

-------
                                                           TABLE E-23
METAL DERIVED EXHAUST PARTICULATE EMISSION KATES
TEST VEHICLE EQUIPPED WITH AIR PRODUCTS PELLETIZED OXIDATION CATALYST

Test
No.
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170

% Fuel
Run Type Sulfur
75 FTP 0.019
Idle (1) "
40 (1)
60 (2)
75 FTP "
75 FTP 0.110
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP 0.091
Idle (1)
40 (1) "
60 (2)
75 FTP "


Ca
<0. 00010
[<0. 00180]
<0. 00003
< 0.00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
0.00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
0.00001
<0. 00010
EMISSION

Al
0.00028
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
0.00005
0.00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
RATE. CMS /KM AS INDICATED METAL*

Zn
0.00111
[<0. 00180]
<0. 00003
0.00004
0.00024
0.00022
[<0. 00180]
0.00019
0.00001
0.00012
0.00019
[<0. 00180]
<0. 00003
0.00005
0.00012

Cr
<0. 00100
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
0.00003
>0. 00009
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010

Fe
>0. 00246
[ 0.00660]
0.00010
0.00015
0.00116
0.00154
[<0. 00180]
>0. 00068
0.00046
0.00235
0.00493
[ 0.01720]
0.00026
>0. 00023
0.00246

Cu
0.00025
[<0. 00180]
<0. 00003
<0. 00001
0.00017
0.00028
[<0. 00180]
0.00007
<0. 00010
<0. 00010
0.00015
[<0. 00180]
<0. 00003
0.00001
<0. 00010

Ni
<0. 00010
[<0. 00180]
<0. 00003
0.00001
<0. 00010
0.00016
[<0. 00180]
0.00008
>0. 00009
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
0.00001
<0. 00010

Pb
0.00065
[<0. 00180]
<0. 00003
0.00004
0.00026
0.00048
[<0. 00180]
0.00015
0.00001
0.00015
0.00030
[<0. 00180]
<0. 00003
0.00004
0.00032
Bracketed numbers are idle emission rates in gms/hour.

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                                                            TABLE E-24
                                         METAL DERIVED EXHAUST PARTICULATE EMISSION RATES
                                 TEST VEHICLE EQUIPPED WITH ENGELHARD PELLETIZED OXIDATION CATALYST
                     AFTER CONDITIONING ON 0.091% SULFUR FUEL FOR 6400 KILOMETRES ON FEDERAL DURABILITY CYCLE
Test
No.
171
172
173
174
175
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
EMISSION RATE, CMS/KM
% Fuel
Sulfur
0.019
ii
11
II
"
Ca
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Al
0.00017
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Zn
0.00045
[<0. 00180]
<0. 00003
0.00003
< 0.00010
AS INDICATED
Cr
0.00021
[<0. 00180]
< 0.00003
<0. 00001
<0. 00010
METAL*
Fe
>0. 00246
[ 0.00300]
0.00008
0.00009
0.00125
Cu
0.00040
[<0. 00180]
<0. 00003
<0. 00001
0.00016
Ni
0.00029
[<0. 00180]
<0. 00003
< 0.00001
<0. 00010
                                                                                                                                Pb


                                                                                                                              0.00104

                                                                                                                            [<0.00180]

                                                                                                                             <0.00003

                                                                                                                              0.00002

                                                                                                                              0.00016
Bracketed numbers are idle emission rates in gms/hour.

-------
                             - 193 -
                            TABLE E-25
Test No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
SULFATE EMISSIONS
UNEQUIPPED MILEAGE ACCUMULATION
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
70 (2)
" 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
70 (2)
" 75 FTP
0.091 "
Idle (1)
40 (1)
70 (2)
11 75 FTP
VEHICLE
Sulfate
Emission Rate*
gms/km
0.002
[0.005]
0.001
0.002
0.003
0.003
[0.027]
<0.001
0.005
0.002
0.002
[0.028]
<0.001
0.003

-------
                              - 194 -
                            TABLE E-26


Test No.
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
SULFATE EMISSIONS
UNEQUIPPED TEST VEHICLE
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
0.110 75 FTP
Idle (1)
40 (1)
70 (2)
" 75 FTP
0.091 75 FTP
Idle (1)
40 (1)
70 (2)
it 75 FTP
                                                      Sulfate
                                                  Emission Rate*
                                                  	gms/km
                                                       0.001
                                                      [0.021]
                                                     <0.001
                                                       0.001
                                                       0.001
                                                       0.003
                                                      [0.021]
                                                     <0.001
                                                       0.002
                                                       0.002
                                                       0.002
                                                      [0.024]
                                                       0.001
                                                       0.002
                                                       0.002
*  Numbers in brackets are idle emission rates  in gms/hr.

-------
                              - 195 -
                            TABLE E-27
SULFATE EMISSIONS
TEST VEHICLE EQUIPPED WITH ENGELHARD
MONOLITHIC OXIDATION CATALYST
Test No.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
70 (2)
" 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
11 70 (2)
" 75 FTP
0.091 75 FTP
Idle (1)
40 (1)
70 (2)
11 75 FTP
Sulfate
Emission Rate*
gins /km
0.002
[0.103]
0.012
0.010
0.004
0.060
[0.048]
0.101
0.055
0.053
0.087
[0.028]
0.076
0.057
0.050
*  Numbers in brackets are idle emission rates in gms/hr.

-------
                              - 196 -






                            TABLE E-28
SULFATE EMISSIONS
TEST VEHICLE EQUIPPED WITH ENGELHARD
PELLETIZED OXIDATION CATALYST
Test No.
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle
40 (1)
70 (2)
75 FTP
0.110 75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
0.091 75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
Sulfate
Emission Rate*
gms/km
0.003
[0.022]
0.001
0.027
0.002
0.008
[0.052]
0.104
0.103
0.029
0.016
[0.0 ]
0.078
0.046
0.006
*  Numbers in brackets are idle emission rates in gms/hr.

-------
Test No.
   66
   67
   68
   69
   70
   71
   72
   73
   74
   75
   76
   77
   78
   79
   80
                              - 197 -
                            TABLE E-29
SULFATE EMISSIONS
TEST VEHICLE EQUIPPED WITH UOP(l)
MONOLITHIC OXIDATION CATALYST
% Fuel
Sulfur
0.019
11
11
it
11
0.110
11
II
II
It
0.091
n
it
n
it
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
Sulfate
Emission Rate*
gins /km
0.003
[0.021]
0.013
0.011
0.001
0.022
[0.011]
0.183
0.065
0.027
0.033
[0.034]
0.165
0.061
0.008
*  Numbers in brackets are idle emission rates in gms/hr.

-------
                            -  198 -
                           TABLE E-30
SULFATE EMISSIONS
TEST VEHICLE EQUIPPED WITH MATTHEY BISHOP
MONOLITHIC OXIDATION CATALYST
Test No.
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)
" 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
0.091 75 FTP
Idle (1)
40 (1)
" 60 (2)
11 75 FTP
Sulfate
Emission Rate*
gins /km
0.003
[0.0 ]
0.006
0.010
0.003
0.032
[0.0 ]
0.055
0.068
0.016
0.024
[0.0 ]
0.043
0.058
0.015
* Numbers in brackets are idle emission rates in gms/hr.

-------
Test No.
   96
   97
   98
   99
  100
  101
  102
  103
  104
  105
  106
  107
  108
  109
  110
                             -  199  -
                            TABLE E-31
TEST
GRACE
% Fuel
Sulfur
0.019
ii
11
ii
it
0.110
II
II
II
II
0.091
ii
ii
ti
it
SULFATE EMISSIONS
VEHICLE EQUIPPED WITH
NO REDUCTION CATALYST*
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
Sulfate
Emission Rate**
gms/km
0.002
[o.ooo]
0.002
0.001
0.001
0.004
[o.ooo]
0.065
0.027
0.005
0.001
[o.ooo]
0.043
0.024
<0.001
 *  Exhaust gas recycle and air pump disconnected.
**  Numbers in brackets are idle emission rates in gms/hr.

-------
                             - 200 -
                           TABLE E-32


Test No.
Ill
112
113
114
115
116
117
118
119
120
121
122
123
124
125
SULFATE EMISSIONS
TEST VEHICLE EQUIPPED WITH
GOULD NO REDUCTION CATALYST*
J\
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
0.110 75 FTP
Idle (1)
40 (1)
60 (2)
11 75 FTP
0.091 75 FTP
Idle (1)
40 (1)
60 (2)
" 75 FTP
                                                       Sulfate
                                                   Emission Rate**
                                                   	gms/km	
                                                        0.002
                                                       [0.000]
                                                        0.002
                                                        0.006
                                                      <0.001
                                                      <0.001
                                                       [0.000]
                                                        0.044
                                                        0.039
                                                        0.003
                                                        0.001
                                                       [0.000]
                                                        0.034
                                                        0.040
                                                        0.000
 * Exhaust gas recycle and air pump disconnected.
** Numbers in brackets are idle emission rates in gms/hr.

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                             - 201 -

                           TABLE E-33
Test No.
  126
  127
  128
  129
  130
  131
  132
  133
  134
  135
  136
  137
  138
  139
  140
SULFATE EMISSIONS
TEST VEHICLE EQUIPPED WITH GRACE
PELLETIZED OXIDATION CATALYST
% Fuel
Sulfur
0.019
If
11
II
"
0.110
II
II
II
II
0.091
ii
H
ii
it
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
Sulfate
Emission Rate*
gms /km
0.002
0.000
0.006
0.019
0.007
0.009
0.000
0.088
0.146
0.034
0.010
[0.047]
0.067
0.096
0.026
* Numbers in brackets are idle emission rates  in  gms/hr.

-------
                               - 202 -
                           TABLE E-34

                         SULFATE EMISSIONS
                    TEST VEHICLE EQUIPPED WITH
               UOP(2) MONOLITHIC OXIDATION CATALYST


Test No.
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155

% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)
•• 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
60 (2)
•i 75 FTP
0.091 75 FTP
Idle (1)
" 40 (1)
60 (2)
" 75 FTP
Sulfate
Emission Rate*
gms/km
0.006
[0.025]
0.015
0.024
0.008
0.032
	
0.176
0.113
0.090
0.078
[0.022]
0.160
0.110
0.052
*  Numbers in brackets are idle emission rates in gms/hr.

-------
                               - 203 -
                            TABLE  E-35
SULFATE EMISSIONS
TEST VEHICLE EQUIPPED WITH AIR PRODUCTS
PELLETIZED OXIDATION CATALYST
Test No.
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
% Fuel
Sulfur Run Type
0.019 75 FTP
Idle (1)
40 (1)
60 (2)
11 75 FTP
0.110 75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
0.091 75 FTP
Idle (1)
40 (1)
60 (2)
ii 75 FTP
Sulfate
Emission Rate*
gms /km
0.014
[0.030]
0.012
0.017
0.004
0.032
[0.033]
0.096

0.054
0.023
[0.394]

0.103
0.075
*  Numbers in brackets are idle emission rates  in gms/hr.

-------
                               - 204 -
                             TABLE E-36


                    SULFATE EMISSIONS  AFTER STORAGE

                 Test Vehicle Equipped With Engelhard
           Pelletized Oxidation Catalyst  After  Conditioning
           Catalyst for 3200 km on Federal Durability  Cycle
                                                       Sulfate
Test No.





,2
171
172
173
174
175
Precision
% Fuel
Sulfur
0.019
it
ii
ii
ti
of Total
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
Particulate Emission
Emission Rate
gms/km
0.044
	
0.119
0.103
0.100
Measurements
          As previously discussed in Section II. 2. 2. 4, two parallel
probes coupled to appropriate filters are required to serve as internal
checks on the particulate sampling system.  Reliable, accurate exhaust
particulate emission rates can be obtained only if close agreement
between parallel filter increases are consistently obtained.

          Regression of 172 of the program runs showed the following
filter correspondence:

          AW  =0.98 AWfi where
           W^ and AWg are the weight gains of parallel filters
           A and B respectively.

-------
                                     - 205 -
                                   APPENDIX F


                        REFERENCES USED IN THE APPENDICES


 (1)  Standard Method of Test for Water Soluble Sulfates in Paper
      and Paperboard, ASTM D-1099.

 (2)  B. Budesinsky and L. Krumlova,  Analytica Chimica Acta, 39, 375
      (1967).

 (3)  Sulfur Dioxide Pulsed Fluorescent Gas Analyzer Model 40, Thermo
      Electron Corporation, Valtham,  Massachusetts.

 (4)  Instruction and Operation Manual PD 101, Perma Pure Dryer, Perma
      Pure Products, Inc., Oceanport, New Jersey.

 (5)  M. Beltzer, R. J. Campion, J. Harlan, and A. M.  Hochhauser, "The
      Conversion of SO  Over Automotive Oxidation Catalysts," SAE Paper
      No. 750095, Automotive Engineering Exposition, Detroit, Michigan,
      February 24-28, 1975.

 (6)  Standard Method of test for Water Using Karl Fisher Reagent,
      ASTM D203.

 (7)  Aquatest II Coulometer, Photovolt Corporation, New York, New York.

 (8)  F. Feigl, Spot Tests in Organic Analysis, 7th Edition, Elsevier
      Publishing Company,  1966.

 (9)  M. Beltzer, R. J. Campion, and  W. L.  Petersen, "Measurement
      of Vehicular Particulate Emissions,"  SAE Paper No. 740286,
      February 25-March 1, 1974.

(10)  Applied Research Labs, Sunland, California.

(11)  R. L. Dunn, Plant Engineering,  15, 91 (1971).

(12)  PVC Varea-Meter, Cat. File 520.210,  Wallace and Tiernan Division,
      Pennwalt Corp., Belleville, N.J.

(13)  Model 700-6 Anemometer, Bulletin No.  537-700-6-P Datametrics,
      Subsidiary of I.T.E. Imperial Corporation, Wilmington, Mass.

(14)  H. P. Schucmann and K. J. Laidler, J. Air Poll. Control Assoc.,
      22., 52 (1972).

(15)  D. E. Seizinger and B. Dimitriades,  ibid, 22_, 47  (1972).

(16)  J. B. Levy, Tnd. and Eng. Chem., 48.  762 (1956)

-------
                                      - 206 -
(17)   G.  L.  Ter Haar, £t al. , J. Air Poll. Control Assoc., Z2, 39  (1972).

(18)   N.  V.  Sidgwick, The Organic Chemistry of Nitrogen, p. 5, New Edition,
      Revised and Rewritten by T. W. J. Taylor and W. Barker, Oxford
      University Press, 1942.
(19)  M. Alperstein and R. Bradow, Trans. SAE, J75.. 7*7  (1967).

(20)  R. M. Hann, J. Am. Chem. Soc., 57, 2166  (1935).

(21)  L. Lieserson, e_t _al. , Ind. and Eng. Chem., 40,  508  (1948).

(22)  G. Fouque and J. Lacroix, Bull. Soc. Chim. France,  33.  180  (1923).

(23)  0. Grummit, A. E. Ardis , and J. Pick, J. Am. Chem.  Soc., ^70,  5167  (1950),

(24)  Kirk-Othmer, Encyclopedia of Chem. Technology,  2nd  edition, V.  19,
      p. 378 (1969).

(25)  A. Binz and L. H. Pence, J. Am. Chem. Soc., 61,  3134  (1939).

(26)  H. B. Hass and E. F. Riley, Chem. Rev.,  32, 395  (1943).

(27)  H. L. Yale, Chem. Rev., _33, 209  (1943).

(28)  G. J. Barnes and J.  C.  Summers, "Hydrogen  Sulfide Formation Over
      Automotive Oxidation Catalysts," Presentation  to The  Society  of
      Automotive Engineers, February 24-28,11974, Detroit,  Michigan.

(29)  D. R. Stull, E. F. Westrum, Jr., and G.  C. Sinke, "The  Chemical
      Thermodynamics of Organic Compounds, John  Wiley and Sons,  Inc., 1967.

-------
                                             207
                                    TECHNICAL REPORT DATA
                             (Please read Jiiilnirtioiiit on the rci etsc before completing]
 1  REPORT NO.
    EPA-650/2-75-054
              3 RECIPIENT'S ACCESSION-NO
 4 TITLE ANDSUBTITLE
   Particulate Emissions From  Prototype Catalyst Cars
              5 REPORT DATE
               May  1975
                                                            6. PERFORMING ORGANIZATION CODE
 7. AUTHOR
-------