EPA-R2-72-066
DECEMBER 1972
ENVIRONMENTAL PROTECTION TECHNOLOGY
Effect of Fuel Additives
A 1 /~~*\ ° T]
on the (Jhemical
and Physical Characteristic:
«/
of Particulate Emissions
in Automotive Exhaust
Office of Research asni Monitoring
U.S. Environmental Protection A
Washington, D.C. 20460
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EPA-R2 72-066
Effect of Fuel Additives
on the Chemical
and Physical Characteristics
of Participate Emissions
in Automotive Exhaust
by
The Dow Chemical Company
Midland, Michigan 48640
Contract No. CPA 22-69-145
Program element No. A11010
Project Officers: Dr. Jack Vfagman, John E. Sigsby, Jr.
Division of Chemistry and Physics
National Environmental Research Center
Research Triangle Park, N.C. 27711
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
December 1972
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
u
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FINAL REPORT June 1972
EFFECT OF FUEL ADDITIVES ON THE CHEMICAL AND
PHYSICAL CHARACTERISTICS OF PARTICULATE
EMISSIONS IN AUTOMOTIVE EXHAUST
By: John B. Moran, Michael J. Baldwin, Otto J. Manary
and Joseph C. Valenta
Organic Chemicals Department
The Dow Chemical Company
Midland, Michigan 48640
Prepared for:
Division of Chemistry and Physics
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Attention: Dr. Jack Wagman
Project Officer
Contract CPA-22-69-145
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CPA--22-69-145
EFFECT OF FUEL ADDITIVES ON THE CHEMICAL AND
PHYSICAL CHARACTERISTICS OF PARTICULATE
EMISSIONS IN AUTOMOTIVE EXHAUST
John B. Moran
Michael J. Baldwin
Otto J. Manary
Joseph C. Valenta
Contributors
R. A. Bredeweg
W. B. Crummett
H. L. Garrett
L. P. Schloemann
L. A. Settlemeyer
J. C. Tou
V. A. Stenger
F. W. Neumann
W. B. Tower
P. A. Traylor
J. C. Valenta
C. E. Van Hall
L. B. Westover
D. F. Wisniewski
C. K. Niemi
H. W. Rinn
The Dow Chemical Company
Midland, Michigan 48640
FINAL TECHNICAL REPORT
July 1969 to May 1972
for
Division of Chemistry and Physics
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Attention: Dr. Jack Wagman, Project Officer
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FOREWORD
This report was prepared by the Transportation Research Group,
Ag-Organic Chemicals Department, The Dow Chemical Company, Midland,
Michigan, as fulfillment of Contract CPA-22-69-145 and extensions
thereto. This work was administered under the direction of the
Division of Chemistry and Physics, Environmental Protection Agency,
with Dr. Jack Wagman as Project Officer.
This report covers work performed from July 30, 1969, to
May 1, 1972. This report was submitted by the authors;
John B. Moran, Michael J. Baldwin, Otto J. Manary, and
Joseph C. Valenta, in July 1972.
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11
ABSTRACT
This report describes work carried out on a research study to
develop methods of generating, collecting, and analyzing particle
emissions from automotive power plants by means sufficiently
accurate and reproducible to allow the determination of the effect
of fuel additives, fuel composition, engine and vehicle operating
mode, and advanced emissions control hardware (limited in scope)
on exhaust particle size, concentration, and composition. An
interim report covering the first year's work was submitted on
July 30, 1970.
In this study, we have examined particle emissions from several
different engines, loaded by an engine dynamometer, and several
different vehicles operated under cruise conditions, the FTP
(California) cycle, and the LA-4 cycle. Particle mass measurement
techniques have included tailpipe measurement methods and air
dilution sampling methods using impaction separators, filters, a
Beta-gauge technique, and piezoelectric crystal techniques.
Several different fuel compositions and fuel additions have been
examined for their effect on particle emissions. Catalytic exhaust
gas reactors have also been evaluated for such effects on a limited
basis.
The data gathered substantiates the applicability and validity of
the techniques developed and, in addition, suggest a very
significant effect of fuel additives, primarily TEL, and to a
limited extent exhaust catalytic reactors on exhaust particle size,
concentration, and composition. The applicability of the techniques
to cycled vehicle studies has been shown.
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i i i
For clarity of presentation, the above studies which represent
the first two year effort in this program are detailed in Part 1
of this report. Part 2 of the report covers the work accomplished
in the last half year of the effort and includes an investigation
of selected dilution tube variables on the physical and chemical
characteristics of particulate exhaust emissions, an evaluation
of the particulate collection capabilities of a second Beta-gauge
instrument, and detailed analyses of some thirty commercial
gasoline samples procured from three different geographical
regions of the United States.
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IV
TABLE OF CONTENTS
Page
FOREWORD ". i
ABSTRACT i i
I. INTRODUCTION 1
II. CONCLUSIONS 4
PART I
III. EXPERIMENTAL PROCEDURES 11
A. Particle Generation 11
1. Engine Dynamometer Studies 11
2. Chassis Dynamometer Procedures 13
B. Particle Collection 16
1. Proportional Sampling Systems '. 21
2. Andersen Sampler/Filter 22
3. Total Dilute Filter 22
4. Piezoelectric Crystal 23
5. Beta-Gauge 25
C. Analysis 25
1. Fuels 25
2. Oils 25
3. Diluent Air 27
4. Exhaust Gases 27
5. Combustion Chamber Deposits 31
6. Exhaust Particles 31
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D. Analytical Methods i 32
1. Optical Microscopy 32
2. Transmission Electron Microscopy (TEM) 32
3. Scanning Electron Microscopy (SEM) and
X-ray Fluorescence 33
4. X-ray Diffraction 35
5. Mass Spectrometry 35
6. High Resolution Mass Spectrometric Analysis .. 39
7. Neutron Activation 40
8. Atomic Absorption 44
9. Emission Spectrometry 46
10. Polarography 52
11. Organic Separation 60
a. Determination of Benzene Solubles
and Ultraviolet Absorptivity 61
b. Determination of Phenolic Content 66
c. Determination of Acidity 71
d. Ultraviolet Fluorescence 79
IV. EXPERIMENTAL RESULTS 84
A. Introduction 84
B. Engines and Vehicles 84
C. Dilution Tube 87
1. Dilution Ratios 87
2. Dilution Tube Profile - Sampling Zone 87
D. Test Fuels and Oil 105
1. Physical Properties 105
E. Combustion Chamber Deposits 108
F. Exhaust Gases 108
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VI
G. Particulate 113
1. Mass Emission Rates 113
2. Mass Distribution 113
3. Major Element Distribution 120
4. HC1, NH3, and H20 120
5. Trace Metal Analysis . 120
6. Crystalline Species 129
7. Particle Morpheus 131
8. Organics 165
V. DISCUSSION OF RESULTS 182
VI. FUTURE 208
REFERENCES 209
PART II
I. CONCLUSIONS 211
II. EXPERIMENTAL PROCEDURE 213
A. Fuel Characterization 213
B. Evaluation of Dilution Tube Variables on the
Collection of Exhaust Particulate Matter 213
1. Variation of Dilution Tube Flow Rate 216
2. Effect of Dilution Air Cooling 216
C. Evaluation of Beta-Gauge,Particulate Mass
Measuring Device 220
III. EXPERIMENT RESULTS 223
A. Fuel Characterization 223
B. Evaluation of Dilution Tube Variables on the
Collection of Exhaust Particulate Matter 223
C. Evaluation of Beta-Gauge 234
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vii
IV. DISCUSSION OF RESULTS 238
A. Evaluation of Dilution Tube Variables on the
Collection of Exhaust Particulate Matter 238
B. Evaluation of Beta-Gauge Particulate
Mass Measuring Device 242
APPENDIX A 244
APPENDIX B • 278
APPENDIX C 300
APPENDIX D 314
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VI 1 1
LIST OF TABLES
Page
1. New Engine Break-in Procedure 11
2. Test Engine Conditioning Sequence 13
3. Vehicle Test Procedure - Chassis Dynamometer 14
4. Exhaust Particle Sample Sources 19
5. Proportional Sampling System for Air-Diluted
Exhaust 21
6. Dr.,. Value - Andersen Model 0203 22
ou
7. Preparation of Standard Solutions 49
8. Analytical Line Pairs 49
9. Representative Precision and Accuracy 53
10. Run Number Designation 85
11. Test Engines and Vehicles 86
12. Dilution Tube Air-Exhaust Ratios and Flow Rates 88
13. Dilution Tube Sampling Zone Temperature 91
14. Dilution Tube Flow Profile - Chassis Dynamometer 95
15. Dilution Tube Flow Profile - Run 44 95
16. Dilution Tube Mass Profile at Sampling Zone 96
17. Particulate Mass Collected by Andersen Samplers 97
18. Particulate Mass Collected by 4 cfm Filters 98
19. Physical Analysis of Test Fuels 106
20. Test Fuel Trace Metals Content 107
21. Engine Oil Physical properties 105
22. Trace Metal Analysis of New Engine Oil 108
23. Used Engine Oil Trace Metal Analysis 109
24. Combustion Chamber Deposits 110
25. Combustion Chamber Deposits Analysis Ill
26. Engine Combustion Chamber Deposits - Trace Metals 112
27. Exhaust Gas Condensate Aldehydes 113
28. Engine Stand Runs - Particulate Mass Emissions 117
29. Emissions Grams Per Mile Chassis Dynamometer 118
30. Mass Medium Equivalent Diameter Exhaust Particulate ... 119
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31. Elemental Mass Medium Equivalent Diameter - Engine
Stand 121
32. Fractions of HC1, NhU, and H90 Present in Exhaust
Particles f 7 1.22
33. Exhaust Particulate - Trace Metals 127
34. X-ray Fluorescence Analysis 120
35. X-ray Diffraction Analysis of Exhaust Particles 129
36. Relative Organic Level by Size Fraction 166
37. Hydrocarbon Type Analysis 168
38. Percent of Total Ion Content 169
39. Organic Analysis of Collected Exhaust Particulates 175
40. Relative Amounts of UV Absorbing Materials 176
41. Relative Amounts of Fluorescent Material 178
42. Analysis of Benzene Soluble Fraction 179
43. Benzene Extracts of Exhaust Particulates 180
44. Analysis of Particulate Benzene Solubles 181
45. Comparison of Particulate Collected 184
46. Filter Temperature During Sampling Run 185
47. Mass Emission Rates 185
48. Emitted Particulate Mass on 4 cfm Filter 186
49. Total Mass Emission Rates 188
50. Mass Emission Rates for Selected Vehicles 189
51. Mass Emission Rates for Selected Vehicles - Cyclic
Operation 190
52. Particulate Mass Emission Rates - Vehicle Cycle 191
53. Effect of Exhaust Catalytic Reactors on Particulate .... 193
54. Effect of Engine Make on Particulate Emissions 194
55. Engine Run and Analytical Method Reproducibi1ity 197
56. Analyses of Runs 21 and 22 204
57. Gasoline Sample Identification .; 214
58. Physical Analyses of Gasoline Samples 224
59. Physical Analyses of Gasoline Samples 225
60. Physical Analyses of Gasoline Samples 226
61. Chemical Analyses of Gasoline Samples 227
62. Effect of Dilution Variable on Particulate Mass
Emission Rates - Non-Leaded Fuel 228
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63. Effect of Dilution Variable on Participate Mass
Emission Rates - 0.5 Leaded Fuel 229
•'64. Lead and Benzo-a-Pyrene Analysis - 0.5 Leaded Fuel .... 230
65. Benzo-a-Pyrene Analysis - Non-Leaded Fuel 231
66. Particulate Trace Metal Analysis - Leaded Fuel 232
67. Particulate Trace Metal Analysis - Non-Leaded Fuel .... 233
68. Evaluation of Industrial Nucleonics Beta Gauge
Using 2.66 cc TEL/Gallon 235
69. Evaluation of Industrial Nucleonics Beta Gauge
Using 0.5 cc TEL/Gallon 236
70. Evaluation of Industrial Nucleonics Beta Gauge
Using Indolene 0 (No Lead) 237
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xi
TABLE OF FIGURES
Page
Figure
1 Particulate Sampling Tube 1
2 Flow Diagram for Engine Exhaust Particulate
Collection 20
3 Crystal Monitor 24
4 Beta-gauge and Tape Sampler System 26
5 Computer Print-out 30
6 Polarographic Determination of Aldehydes 54
7 Polarographic Determination of Aldehydes 56
8 Polarographic Determination of Aldehydes 56
9 Absorptivity Curve 57
10 Polarographic Determination 58
11 Polarographic Determination 59
12 Difference Spectra of 4-Nitrophenate Solutions 75
13 Spectra Obtained Using Benzene Solubles 75
14 Difference Absorbance of Sodium 4-Nitrophenate in
Presence of Benzoic Acid in Methanol 76
15 Difference Absorbance of Sodium 4-Nitrophenate in
Presence of Benzoic Acid in Methanol 78
16 Dilution Tube Temperature Profile - Engine
Dynamometer 91
17 Dilution Tube Flow Profile - Engine Dynamometer 92
18 Dilution Tube Flow Profile - Chassis Dynamometer 93
19 Dilution Tube Profile - Engine Stand Steady-State
Operation 94
20 Tube Temperature Monitor at Sampling Zone -
California 7-Mode Cycle - Cold Start 99
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XI 1
21 Tube Temperature Monitor at Sampling Zone -
California 7-Mode Cycle - Hot Start 100
22 Tube Temperature Monitor at Sampling Zone -
Federal Cycle - Hot Start 101
23 Dilution Tube Flow Monitor at Sampling Zone -
California 7-Mode Cycle - Hot Start 102
24 Dilution Tube Flow Monitor at Sampling Zone -
California 7-Mode Cycle - Cold Start 103
25 Dilution Tube Flow Monitor at Sampling Zone -
Federal Cycle - Hot Start 104
26 Percent Change in Total and Saturated Hydrocarbon
Emissions from 0 to 75 Hours 114
27 Percent Change in Nitric Oxide Emissions from
0 to 75 Hours 115
28 Percent Change in Carbon Monoxide Emissions
from 0 to 75 Hours 116
Exhaust Particulate on Andersen Plates by
29 OM From Run #9 135
30 OM From Run #8 136
31 OM From Run #15 137
32 OM From Run # 11 138
33 TEM From Run # 13 139
34 TEM From Run #2, Plate #1 ..." 140
35 TEM From Run #2, Plate #6 141
36 TEM From Run #2 142
37 SEM From Run #1 143
38 SEM From Run #2 144
39 SEM From Run #2, Plate #6 145
40 SEM From Run #2, Plate #1 146
41 SEM From Run #1, Plate #1 147
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XI 1 1
42 SEM From Run #1 , Plate #1 148
43 SEM From Run #21, Plate #1 149
44 SEM From Run #21, Plate #1 150
45 SEM From Run #42, Plates 1, 4, and 7 151
46 X-Ray Spectrum, Run 21 152
47 X-Ray Spectrum, Run 21, Plate 1 152
48 X-Ray Spectrum, Run 21, Plate 1 153
49 X-Ray Spectrum, Run 21, Plate 7 153
50 X-Ray Spectrum, Run 21, Final Filter 154
51 X-Ray Spectrum, Filter Blank 154
52 X-Ray Spectrum, Run 24, Plate 1 155
53 X-Ray Spectrum, Run #24, Plate #4 155
54 X-Ray Spectrum, Run #25, Plate #1 156
55 X-Ray Spectrum, Run #25, Plate #4 156
56 X-Ray Spectrum, Run #25, Plate #7 157
57 X-Ray Spectrum, Run #25, Filter 1 ; . 157
58 X-Ray Spectrum, Run #25, Filter 2 158
59 X-Ray Spectrum, Run #25, Filter 3 158
60 X-Ray Spectrum, Run #39, Plate #3 159
61 X-Ray Spectrum, Run #39, Plate #6 159
62 X-Ray Spectrum, Run #41, Plate #4 160
63 X-Ray Spectrum, Run #41, Plate #7 160
64 X-Ray Spectrum, Run #42, Plate #1 161
65 X-Ray Spectrum, Run #42, Plate #4 161
66 X-Ray Spectrum, Run #42, Plate #7 162
67 X-Ray Spectrum, Run #42, Individual Particle of
Figure 49A 162
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XI V
68 X-Ray Spectrum, Run #42, Individual Particle of
Figure 49B 163
69 X-Ray Spectrum, Run #42, Individual Particle of
Figure 49C 163
70 X-Ray Spectrum, Run #42, Individual Particle of
Figure 49D 164
71 Mass Spectral Profile - Cycle 3 Manifold 171
72 Mass Spectral Profile - Cycle 3 Manifold Repeat 171
73 Mass Spectral Profile - Pipe, in Cycle 3 172
74 Mass Spectral Profile - Pipe, in Cycle 3 Repeat 172
75 Mass Spectral Profi.le - Pipe, in Cycle 4 173
76 Mass Spectral Profile - Pipe, in Cycle 4 Repeat 173
77 Mass Spectral Profile - Pipe, in Cycle 5 174
78 Mass Spectral Profile - Pipe, in Cycle 5 Repeat 174
79 Ratio RU/RF As Function of A255, Run #20,
Extracts of Andersen Plate Filters 200
80 Ratio RU/RF as Function of A255, Run #19,
Extracts of Andersen Plate Filters 201
81 Ratio RU/RF as Function of A255, Run #21,
Extracts of Andersen Plate Filters 203
82 Ratio RU/RF as Function of A255, Run #22,
Extracts of Andersen Plate Filters 203
83 Dilution Tube Cooling Baffle 218
84 Cut-Away View of Cooling Baffle Sleeve 219
85 Test Matrix for the Study of Diluent Air
Temperatures on Particulate Matter 221
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XV
ACKNOWLEDGMENTS
The authors wish to acknowledge the generous support provided by
the following in the pursuit of this contract.
Mr. Ken Valentine and Mr. Doug McCullough of Pontiac
Motor Division, General Motors.
Messrs. Robert Herling, William Karches , and Bob Griffin
of the Division of Chemistry and Physics, Environmental
Protection Agency, Research Triangle Park, North Carolina.
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I. INTRODUCTION
This is a final report detailing two and one-half years of effort
to develop a fundamental understanding of the nature of particle
emissions from automotive power plants. In general terms, we
have developed reproducible and repeatable generation, collection,
and analysis techniques which allow detailed characterization
of particle emissions. The effect of fuel composition, fuel
additives, cyclic operation, and exhaust catalytic reactors thereon
have been determined.
This report covers work performed from July 1969 to May 1972. An
interim report covering the period July 1969 to July 1970 has been
published.
In Part 1 of this report, the scope of the study has involved
several related steps which provide the basis for the evolution
of the program employed. Specific steps, in order of their
occurrence, are as follows:
1. Engine dynamometer study.
a. Develop methods to generate representative, repeatable,
and reproducible exhaust particles.
b. Develop methods to collect and classify emitted particles
c. Develop methods to analyze emitted particles.
d. Ascertain effect of fuel additives and fuel composition
on emitted particles.
2. Chassis dynamometer study (vehicles).
a. Same as l.(a.b.c.d.) above.
b. Relate vehicle exhaust particles to engine study (1.).
c. Determine effect of hot cyclic operation on exhaust
particles.
d. Determine effect of cold start cyclic operation on
exhaust particles.
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e. Determine effect of exhaust catalytic reactor on
exhaust particles.
f. Determine particle emission rates from several
uncontrolled typical vehicles.
3. Exhaust particle mass measurement sampling system development,
a. Evaluate several mass measurement methods.
1) Tailpipe
2) Air-diluted
a) Beta-gauge
b) Piezoelectric crystal
c) Proportional filter
b. Determine critical sampling factors for exhaust
particles.
In order to accomplish the objectives of the program, it was found
necessary to begin each specific test run with an essentially new,
clean engine and exhaust system; and, that the engine be conditioned
with the specific test fuel using mild cyclic conditions for the
equivalent of 3000 miles before the particle sampling procedures
began. Direct tailpipe sampling of particles was found to be
unsatisfactory. As a result, an air dilution system, similar to
that employed by Habibv ', was designed. When a 350 CID engine is
operating under 60 mph road load conditions, the dilution tube
assembly provides a 12:1 dilution ratio (air:exhaust using one-half
the engine exhaust). The dilution tube was designed so that all
emitted particles can be collected and classified.
Part 1 of this report, then, covers the procedures employed in
the generation, collection, and analysis of exhaust particles
from automotive power plants under cruise and cyclic conditions
from engines and vehicles. It details the effects of engine
make, fuel composition, fuel additives, and catalytic reactors
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on emitted particles. The results of several particle mass
measurement techniques are presented and the reasons for the large
differences in apparent particle mass determined are discussed.
Part 2 of the report presents the results obtained when a further
particle mass measurement technique (Beta-gauge) was evaluated. It
further covers the evaluation of selected dilution tube variables
on the physical and chemical character of collected exhaust
particulate matter. These variables included temperature of diluent
air with cooling ahead of and within the dilution tube after mixing
with the exhaust, and diluent air flow rate. A detailed chemical
and physical characterization of thirty commercially available
gasolines is also presented.
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II. CONCLUSIONS
The report covers the results of a diverse program spanning two
and one-half years directed toward the objective of developing
methods of generating, collecting, and analyzing exhaust particulate
from automotive engines. Further, the project has examined the
effect of fuel composition, fuel additives, generation factors, and
collection systems on particulate emissions. The first year's
program was directed toward development of repeatable and repro-
ducible methods of generation, collection, and analysis utilizing
dynamometer controlled engines. The remaining time was directed
toward expansion of the research effort toward investigation of
vehicle variables, cycle effects, collection parameters, particulate
mass measurement systems, and to a limited degree, an examination
of exhaust catalyst effects.
Many of the conclusions are based upon actual comparisons of data
generated in this program. However, these data comparisons are
interpreted as trends only and not as quantitative changes. A
precise quantitative comparison of the effect of the many variables
studied is impractical since:
a) Only limited data points could be generated within the
time available consistent with the scope of the contract.
b) Subsequent work has revealed other sampling parameters,
consideration of which is necessary in the generation
of more exact values. These parameters, discussed in
Part II of this report, are of particular significance
in the collection of exhaust particulate generated by
power sources running on lead-free or low-lead fuels.
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The conclusions based on this study follow. The page numbers
shown after many of the conclusions refer to the location of
data tables upon which they were based.
Particle Generation and Collection
1. A generation, collection, and analysis system has been
developed which allowed the assessment of the effect of
several fuel factors, fuel additives, driving cycles and
exhaust catalysts on emitted exhaust particulated mass
and composition. (Page 182)
2. From the standpoint of reproducibi1ity the various approaches
for the collection and measurement of exhaust particulate
matter can be rated in the following decreasing order of
confidence:
a) Andersen sampler/filter. (Pages 22, 97, 194)
b) 4 cfm fiber glass-fiber filter. (Pages 98, 195)
c) Millipore membrane filters - sensitive to atmospheric
changes in humidity. (Page 198)
d) Beta-gauge - good for leaded fuel studies; however, its
sensitivity was too low for particulate emissions from
non-leaded fuels. (Pages 25, 194, 195)
e) The piezoelectric crystal monitor gave consistently
lower mass emission rates when compared to the Andersen-
filter collection technique during cruise mode sampling,
and was unreliable during cycling mode operation.
(Pages 23, 194, 195)
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3. Comparison of the particulate matter collected after air
dilution to that collected on a total hot filter at the
exhaust pipe shows that the latter technique afforded
lower particulate mass emission rates than did the collection
of air-diluted particulate matter. Analysis of this collected
particulate matter showed that air-diluted exhaust contained
significantly higher percentages of organic matter for both
non-leaded and leaded gasoline. (Pages 117, 118, 184, 194, 195)
Effects of Test Mode and Engine vs. Vehicle Testing
1. A comparison, across similar engine and fuel types, of engine
(on dynamometer stand) and vehicle testing shows:
a) Engine and vehicle data are similar for particulate
mass emission rates using low lead and non-leaded fuel.
Vehicle particulate mass emission rates are higher
for 3 cc/gal leaded gasoline. (Pages 117, 118, 118a)
b) Vehicle testing afforded higher particulate organics
using leaded fuels but lower levels with non-leaded
fuels. (Page 121)
c) Particulate mass-size distributions were similar for
engine and vehicle tests using leaded or non-leaded
fuels. (Page 119)
2. The California 7-mode cycle and Federal LA-4 23 minute
cycle (FTP) gave higher particulate mass emission rates than
did 60 mph steady state (SS) operation, particularly for
non-leaded and low lead fuels. A comparison of cold to hot
start operation in the California cycle shows that the former
resulted in higher particulate mass emission rate than did
the latter. (Pages 118, 118a, 191)
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Effect of Mileage Accumulation
1. Successive vehicle testing under steady state operating
conditions using low lead and non-leaded fuels showed a
decrease in the mass of emitted particulate matter as mileage
was accumulated over the range of 2,500 miles to 10,000
miles. The vehicle using fully leaded fuel showed an
increase in particulate emissions as mileage increased.
(Pages 188, 189, 190)
2. Successive testing of the same vehicles using the FTP and
California 7-mode testing sequences resulted in a decrease
in particulate emissions with increased mileage accumulation
(700 to 10,000 miles) for both the cold and hot start test
modes except for the vehicle running on fully leaded fuel.
The vehicle using the fully leaded fuel under the same
testing sequence showed a small decrease in emitted particulate
matter with mileage accumulation under the cold start FTP
mode. However, a small increase was observed under the hot
start FTP conditions as the vehicle mileage increased.
(Pages 190, 191)
Particle Analysis
1. In general, as evidenced by transmission scanning electron
microscopic examination, the percentage of organics associated
with exhaust particulates increased with decreasing particle
size. (Page 166)
2. In general, 50 percent of the mass of exhaust particles were
smaller than 0.1 micron (MMED). (Page 119)
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3. There is no apparent correlation between the aromaticity
or saturated hydrocarbon content of the various test fuels
studied with the concentration of benzene soluble material
in the exhaust particulate matter collected. However, in
general the use of non-leaded fuels afforded exhaust
particulate containing the highest percentages of benzene
solubles. (Pages 175, 179, 180, 181)
Effect of Tetraethyl Lead
1. Increased concentrations of tetraethyl lead (TEL) from trace
levels to 3.0 ml/gal resulted in increased particle emissions,
increased combustion chamber deposits, and increased hydrocarbon
emissions. (Pages 108, 110, 113, 114, 117, 118, 118a)
2. Increased concentrations of TEL from trace levels to
1.5 ml/gal resulted in disproportionate increase in
combustion chamber deposits^ but an increase in particulate
emissions. (Pages 108, 110, 113, 117)
3. A comparison of 91 RON non-leaded and low (0.5 cc/gal) lead
fuel indicated that the leaded gasoline afforded higher
particulate mass emission rates and combustion chamber deposits.
The particulate matter in the case of the low lead fuel con-
tained higher concentrations of trace metals and had a lower
MMED than the non-leaded fuel. (Pages 108, 110, 113, 120)
A similar comparison of 100 RON non-leaded to 100 RON
1.5 cc/gal leaded gasoline showed that the latter fuel
afforded higher engine combustion chamber deposits,
particulate mass emission rates, and particle MMED. Of the
variables studied, TEL had the most pronounced effect on
particle size. (Pages 108, 113, 119)
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4. Microscopic particle examination indicated that the
percentage of organic material associated with exhaust
particles increased with decreasing TEL concentration.
(Page 166)
Effect of Other Fuel Additives and Engine Oil
1. Lead scavengers had a pronounced effect on exhaust, particulate
and gaseous emissions, and on combustion chamber deposits.
The more effective the scavenger, the lower were the hydro-
carbon emission levels and the greater the particulate
emission levels (motor mix, EDB, and EDC had been evaluated).
EDB appeared the most efficient scavenger. (Pages 108, 113, 117)
2. The use of the amine salt of mixed alkyl phosphates as a
detergent additive in 3.0 ml/gal TEL motor mix base fuel,
decreased hydrocarbon emission levels, but increased particulate
emissions when compared to the base fuel. (Pages 108, 113, 117)
3. The use of N-r[-butyl-£-aminophenol (antifouling agent) as a
fuel additive increased both combustion chamber deposits and
particulate emissions. This additive resulted in a reduced
level of particulate organics. (Pages 108, 113, 117, 165)
4. The use of 2,6-di -;t-butyl-£-cresol (oxidation inhibitor) as
a fuel additive afforded a reduced level of combustion
chamber deposits and little change in particulate mass
emission levels. Particulate organic content was significantly
reduced. (Pages 108, 113, 117, 165)
5. The use of Amoco 200 heavy duty motor oil afforded little
change in either combustion chamber deposits or particulate
emissions. (Pages 110, 113, 117, 118)
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6. The use of non-leaded fuels containing no additives afforded
particulate matter containing the highest percent concentra-
tions of trace elements. However, on an absolute weight
basis, the levels of trace metals associated with exhaust
particulate showed an increase with the presence of the
various fuel additives studied. Analysis of combustion
chamber deposits indicated that their trace metal concentra-
tion or mass was affected to only a minor extent by variations
in the types of fuel additive studied. (Pages 127, 128)
Effect of a Catalytic Converter
1. The use of a single catalytic exhaust converter resulted in
a reduction in the mass of emitted particulate matter during
the FTP cold start test sequence. However, an increase in
the particuate mass generally resulted during the hot start
testing sequences. (Pages 192, 193)
The use of this control device showed an insignificant effect
on particle size. (Page 194)
2. Trace metal levels were found to be higher than in similar
runs made without the catalytic exhaust converter.
(Pages 127, 128)
3. Total unburned hydrocarbons were significantly reduced in
the presence of this oxidation catalyst. No differences in
NO emissions were observed. (Page 114)
}\
Effect of Fuel Octane Rating
No significant trend in either particulate mass emission rate
or combustion chamber deposits was evident from a comparison
of 91 RON to 100 RON non-leaded fuel. (Pages 113, 117, 118)
-------
PART 1
-------
-11-
III. EXPERIMENTAL PROCEDURES
A. PARTICLE GENERATION
1. Engine Dynamometer Studies
The test engine was completely disassembled, cleaned, and
reassembled according to manufacturer's specifications. It was
then mounted on the dynamometer bed plate and. attached to a
fully instrumented Eaton Dynamatic dynamometer. Appropriate
control and sensing devices were attached to the engine. The
following procedure (Table 1) was then employed to run-in the
new engine, using Indolene HO 30 fuel.
TABLE I
NEW ENGINE BREAK-IN PROCEDURE
(28 hours)
1) Warm up engine to 180°F coolant outlet temperature at
1000 rpm, no load. Set spark advance, timing, and idle
according to manufacturer's specifications.
2) Run one hour at 1500 rpm, no load, automatic spark
advance and fuel flow. Shut down, retorque cylinder
heads, drain and change lubricating oil.
3) Run Cycle 1
RPM Man. Vac. (In. Hg) Time (Hr)
1500
2000
2400
2600
2000
5.0
4) Run Cycle 2
RPM Man. Vac. (In. Hg) Time (Hr)
1500 7.0 0.2
2000 7.0 0.6
2500 7.0 1.0
3000 7.0 1.0
2000 7.0 0.2
3.0
15.0
14.0
14.0
14.0
11.0
1.0
1.0
1.0
1.0
1.0
-------
-12-
5) Repeat Cycle 2.
6) Run Cycle 3
RPM Man. Vac. (In. Hg) Time (Hr)
2000 WOT* 1.0
2500 WOT 1.0
3000 WOT 1.0
3500 WOT 0.5
2800 WOT 0.5
4.0 x 4 cycles
= 16 hours
*WOT - wide open throttle
7) While engine is hot, run motoring compression and conduct
leak-down check.
The engine was removed from the dynamometer, drained, partially
dismantled, cleaned, reassembled, and placed back on the dynamo-
meter stand. A typical vehicle exhaust system for the specific
test engine was attached to one bank of cylinders. The other
bank of cylinders was attached to the dynamometer cell exhaust
system. Suitable engine monitors were attached to the engine in
order to provide continuous monitoring of oil pressure and
temperature, coolant temperature, carburetor air flow rate (using
a Meriam Laminar Flow Element 50MC-2-45F) and temperature, etc.
The engine was then run for 75 hours continuously using the
following "conditioning" sequence (Table 2) employing the
specific test fuel designated for that run. During the
conditioning sequence, total unburned hydrocarbons, oxygen,
nitrogen, carbon monoxide, carbon dioxide, and oxides of nitrogen
were measured at frequent intervals by FID, gas chromatography,
chemical absorption, and a Scott NO/NOp analyzer, respectively.
Air/fuel ratios were also calculated based upon exhaust gas
composition.
-------
-13-
TABLE 2
TEST ENGINE CONDITIONING SEQUENCE
Cycle RPM Time (Min.) Vac. (In. Hg) Decay
1 800 2 18.8
2 1070 13 16.4 1/2 min.
3 1615 20 17.2 1/2 min.
4 2125 13 14.3 1/2 min.
5 1070 12 16.4 1/2 min.
Sequence repeats after each five cycles.
Following the conditioning sequence, the engine exhaust system
was attached to the dilution tube inlet pipe and a 48-hour
continuous particle sampling run was begun with the engine
operating at 2250 rpm and 17" Hg manifold vacuum (equivalent
to 60 mph road-load).
At the termination of the test run, the engine was removed from
the dynamometer stand, dismantled, and samples for analysis were
removed. The samples included engine oil, and combustion chamber
and piston head deposits which were carefully removed, weighed,
and stored in glass vials. The engine was completely cleaned,
reassembled, and reinstalled on the dynamometer stand.
Subsequent tests did not require the break-in procedure noted
in Table 1 unless a new engine was used. If the same engine was
used again, the next test series began with the conditioning
sequence noted in Table 2 after attachment of a new exhaust
system.
2. Chassis Dynamometer Procedures
A Clayton CT-200-0 chassis dynamometer with a variable inertia
flywheel assembly was used in all tests conducted under this
program. A Chelsa direct-drive Model PLDUP-300A fan was
-------
-14-
located in front of the test vehicle, and operated at 1750 rpm
providing 18,750 scfm air flow. In these tests, the vehicle was
operated under approximately 60 mph road-load cruise conditions
(2250 rpm - 17" Hg manifold vacuum) and under cyclic conditions
of the Federal Test Procedure (old California cycle) and LA-4
procedure driven by a vehicle operator following the cycle on a
strip-chart recorder driver aid.
Table 3 indicates specific procedures employed to prepare
each vehicle for test run.
TABLE 3
VEHICLE TEST PROCEDURE - CHASSIS DYNAMOMETER
1) General Vehicle Inspection
Exhaust System:
a) Inspect for holes or cracks, dents, and collapse
b) Inspect for leaking joints
Engine, check
a) All fluid levels
b) All coolant hoses
c) Air pump fan, power steering, and belts
d) Check heat riser (if applicable) for fullness of operation
e) Check automatic choke operation and adjustment
2) Engine Analysis and Tune-up
Leak Down Test
a) Remove all spark plugs
b) Determine percent leak down of each cylinder
c) Install recommended, new, and gapped spark plugs,
points, and condenser
Scope Check
a) Start engine and allow to warm up for at least 15 minutes
-------
-15-
TABLE 3 (contd.)
b) With engine running at fast idle, check
•Spark plugs
•Spark plug wires
•Distributor cap and rotor
•Coil output
•Points
c) With engine running at idle, check
•Dwell
•Timing
d) With engine running at 1500 and 2400 rpm, check
timing advance
e) Carburetor Adjustment
•Tighten intake manifold and carburetor
•Install new air cleaner element
•With engine running at specified idle
speed, adjust air to fuel ratio to
speci fications
•Make final adjustment on idle speed
f) Recheck all scope patterns for normal appearance
3) Instrumentation and Equipment Installation
Thermocouples - install thermocouples in
a") engine oil - dipstick
b) coolant - upper radiator hose - engine out
c) carb air - air filter element
Vacuum and RPM monitors
F)attachtachometer to ignition coil
b) connect "U" tube monometer to intake manifold
c) install throttle cable (if running under cruise mode)
Wheels
a") remove rear wheels
b) Install test tires and wheel assemblies to insure
safe operation
4) Procedure for Cold, Hot Starts, and Engine Temperature
Stabi1i zati on
Cold Start
a) Place vehicle on the dynamometer rolls, set inertia
weights for specific vehicle, and go through the
preparation for test as well as the tune-up procedure.
b) Allow at least a 12-hour soak period
c) Connect vehicle tailpipe to dilution tube.
d) Start the vehicle and proceed with the individual test
-------
-16-
Hot Start
Continuation of the cold start only after the engine
temperature has stabilized.
Engine Temperature Stabilization
Upon completion of the tune-up procedure the vehicle is
started cold and driven a total of 32 highway miles at
60 mph to allow the engine temperature to stabilize. The
vehicle is then driven on to the dynamometer rolls and
prepared for the test during which time the engine idles for
approximately five minutes. When preparation has been
completed, the vehicle is placed in gear and the speed is
increased to 2250 rpm and the intake manifold vacuum is
set at 17.0" Hg by controlling the amount of load imposed
on the drive wheels. At the time, when the load and the
speed become stabilized, the tailpipe is connected to the
dilution tube inlet pipe and sampling is started.
B. PARTICLE COLLECTION
Exhaust particles were collected by two basic techniques,
one from each of the two exhaust systems attached to the engine.
One exhaust system was sampled with a total exhaust hot filter
attached to the tailpipe during two test runs. Normally, the exhaust
from this side of the engine was exhausted through the dynamometer
cell exhaust system. The other exhaust system particulates were
collected after air dilution in a large dilution tube described
below.
The total exhaust hot filter consisted of a stainless steel filter
holder, capable of holding four 8" x 10" filter papers fitted with
nine strip heaters totalling 8720 watts to preheat the holder
to 150°F to avoid condensate on the filter media during engine
start-up. The filter assembly was attached directly to the exhaust
tailpipe by a short connector. The exhaust was pulled through
the filtering area of 1.75 sq ft by a Sutorbuilt positive displacement
pump capable of 800 cfm at 8" Hg, which was exhausted to the test
cell exhaust system.
-------
-17-
Air dilution and cooling of the exhaust from the other side of
the engine was accomplished by a dilution tube 16 inches in
diameter and 27 feet in length, with a 90 degree bend section,
constructed of extruded polyvinyl chloride (PVC) pipe in several
sections with butt joints which were taped during assembly prior
to each run (Figure 1). The dilution tube was in a temperature
and humidity controlled instrument room with the engine test cell
on one side and the chassis test cell on the other so that a simple
180 degree rotation of the inlet section allowed operation of the
same tube from either exhaust source.
Air was pulled from the dynamometer cell or chassis dynamometer
room through a Dri-Pak Series 1100 Class II PIN 114-110-020
untreated cotton filter by a pump at the exit end of the tube
at a rate of about 500 cfm. Exhaust was delivered to the tube
via a tailpipe extension which was brought into the bottom of
the tube downstream of the filter assembly. The extension was
bent 90 degrees inside the tube, thus allowing the introduction
of the exhaust stream parallel to the tube axis. Within the
dilution tube, along the perpendicular plane of the end of the
exhaust extension was a mixing baffle which has an 8-inch center
hole and was attached to the inside diameter of the tube. The
baffle presented a restriction to the incoming dilution air in
the same plane as the end of the exhaust extension and performed
three essential functions.
a) Provided a turbulent mixing zone of exhaust gas and
dilution air.
b) Eliminated engine exhaust pulsations in the tube.
c) Caused the tube to perform as a constant volume device
over a wide range of engine exhaust output volumes.
Particle.sampling with the dilution tube system was accomplished by
two basic methods.
-------
Scale = 5 Feet = 2"
\
Figure 1
00
I
7'0"
PARTICULATE SAMPLING TUBE
O
-------
-19-
a) Gravitational fall-out in the tube.
b) Proportional sampling at the extreme end (exit) of the
tube.
A schematic of the collection system using the dilution tube is
shown in Figure 2.
The gravitational fall-out in the tube provided several discrete
samples. First, seven small slits 3/8" x 3" were cut in the
bottom of the tube. Special cover glasses were attached to the
outside of the tube to collect the material that fell through the
slit. The tube was constructed of several sections taped together
Thus, removal of particle samples from each section provided
additional discrete samples as a function of distance from the
exhaust inlet.
At the extreme end of the tube, a proportional sampling zone was
employed to collect particle samples which were still in the air-
exhaust stream. Several proportional techniques were employed.
These are discussed below. Figure 2 shows the Andersen Impact
Sampler (Model 0203) with back-up 142 mm filters. Table 4
summarizes the sample sources.
TABLE 4
EXHAUST PARTICLE SAMPLE SOURCES
Tailpipe: Total hot exhaust filter
Air Diluted: Dilution tube
-slit samples
-tube sections
Sampling zone
-proportional samples
-------
Figure 2
Flow Diogrom for Engine Exhoust
Particulote Collection
f
Air
out
Fliter
I
Instrument
r r^\ ana>
JEn9ID.?. J* ° oj" N Control Room
Mix ing ^-
Air
in,
Eng ine
Dynamometer
Eng ine
Part iculate
Gravimetric Fallout
Flow —
Control
/
1
1
1
f
\
\
\
^A
1
1
*-•*
.-••
1 1
1 >
-«
*-
s
s
s
*\
\
111 in, ' //7///y///// \s/7s///7///
1
5
1
X-
N,
X.
V
•«.
S.
X
>s
V
=•;
t
\ t /
Sampling Slits
Tail Pipe
— -^^^.
i ^^
Ai
| Pu
, ,
Anderson ^_
Seoorotor
Standard Muffler
^ °cott Research ins, Millipore
NQ nnri NOo — r ,
IMU ana wu2 f ilter
Analysis
* risner bas rartiTioner
CO, C02, N2, 02 Flow Meter— >
. ^. RA/\t/*mMK\ 1HOA
T^ DeCKmon luyA
Total Hydrocarbon
*
4
1 Ma
v^y
t
Analyzer ^
t
Exhaust P ipe
Pump
I
ro
o
i
Manometei
-------
-21-
1. Proportional Sampling Systems
Several proportional sampling systems have been used to determine
particle mass and mass-size distribution in the sampling zone of
the dilution tube. Each system employed sample pick-up probes of
appropriate diameter to provide isokinetic samples from the
air-exhaust stream. Pick-up probes entered the tube at right
angles, bend inside the tube 90 degrees so that the opening was
perpendicular to the tube axis and pointing directly upstream
toward the exhaust inle;t section. The specific systems used are
summarized in Table 5.
TABLE 5
PROPORTIONAL SAMPLING SYSTEMS FOR AIR-DILUTED EXHAUST
System
Sample
Flow Rate
1) Andersen Model 0203 1 cfm
with 142 mm back-up
filter
Remarks
Provides mass-size distribution
Glass collection plates used.
(Used for full run.)
2) Total diluted
filter
4 cfm Total mass only. (Used for
full run.) Higher operating
temperature than 1.
3) Piezoelectric
crystal
1 1/min Thermo-Systems, Inc. Prototype
instrument. (Real time
measurements.)
4) Beta-gauge
1 cfm Tape sampler operated to get
total sample. Mass read with
Beta-gauge. 20-minute sample.
-------
-22-
2. Andersen Sampler/Filter
Andersen Samplers Model 0203 with back-up 142 mm filters were
used as the basic particle collection device in these
studies. Sample probes sized to deliver an isokinetic sample
from the dilution tube were connected to the Andersen Sampler
through which a proportional sample was drawn at 1 cfm. The
DJ-Q cut-off values for the Andersen stages are listed in
Table 6.
TABLE 6
D (2) VALUE - ANDERSEN MODEL 0203
bU
Stage 1 D5Q 9y
Stage 2 D5Q 5.45y
Stage 3 DSQ 2.95y
Stage 4 D5Q 1.55y
Stage 5 D5Q 0.95y
Stage 6 D5Q 0.54y
Preweighed glass or stainless steel collection plates were used
in this study. Back-up filters were either Millipore type AAWP
0.8y or Gelman 0.3y Type A 142 mm diameter. Millipore filters
were routinely used while the Gelman filters were used for
special analytical applications.
3. Single Proportional Filter
A total mass emission rate at the sampling zone of the diluted
exhaust was obtained by pulling an isokinetic proportional
sample at 4 cfm through a single 142 mm filter of the types
mentioned above. This technique was found necessary in order
to obtain relatively large sample mass for analytical purposes.
This sampling system operated in the same zone as the Andersen
Samplers.
-------
-23-
4. Piezoelectric Crystal
All piezoelectric crystal mass monitors are based on the same
principle. A piezoelectric crystal, such as quartz, is placed
in an oscillating electric field, the latter oscillating at a
frequency close to the crystal's natural frequency of
(3)
vibrationv . If small particles attach themselves to the
surface of the crystal, the natural frequency of the crystal
decreases. The change in natural frequency is detected and is
proportional to the mass of the attached particles. The
sensitivity of these devices is exceptional, easily detecting
mass changes of tenths of micrograms.
Two commercial versions; have been developed utilizing different
techniques to collect the particles on the crystal. The
(4}
instrument developed by Atlantic Researchv ' uses impaction
as the collection technique. Particles larger than a specified
size are accelerated through an orifice and impact on the
surface of the crystal which is coated with an adhesive. Particles
smaller than the cutoff size follow the air stream past the
crystal. Because of the theoretical limitations of this collection
technique, particles less than 0.3y diameter cannot be satis-
factorily collected on the crystal with the Atlantic Research
instrument. Thermo-Systems, Inc.' ' with funding by EPA have
also developed a piezoelectric crystal monitor, which was
used in this program. A schematic is shown in Figure 3. This
instrument uses a point to plane electrostatic precipitator
to deposit the particles onto the crystal. An external vacuum
source draws a 1 liter/min sample stream through an intense
corona discharge near the needle point negatively charging
the particles. The air flow and electric field carry the
particles to the surface of the crystal. A second crystal,
the one on the left in Figure 3, is used as a reference
crystal to correct for environmental changes.
-------
-24-
Figure 3
Crystrl Monitor
FREQUENCY
COUNTER
PIEZOELECTRIC
MICROJJALANCE
ELECTRONIC
PRECIPITA
TOR POv.'E
SUPPL
VACUUM SUPPLY
AEROSOL III
-------
-25-
5. Beta-Gauge
A prototype Beta-gauge and tape sampler systenr ' was also
evaluated (Figure 4). The tape sampler collects the particulate
sample on a filter and the mass collected on the tape is deter-
mined from the Beta gauging technique. With this technique,
14
the tape is placed between a beta source, in this case C , and
a beta radiation detector. A fraction of the radiation from
the source passes through the filter tape and the particulate
deposit to the detector. The greater the mass of the particulate
deposits on the tape, the less is the amount of radiation reaching
the detector. After correcting for the mass of the tape medium
and the background radiation, the mass loadings on the tape
can be calculated.
C. ANALYSIS
Collected exhaust particles have been analyzed for both physical
and chemical character. Many analytical techniques have been
employed, some of which provide very similar data in the interest
of correlating trends observed. This section reviews the basic
analytical concepts applied to each of the many test components
from fuels to exhaust particles. Detailed descriptions of the
specific analytical procedures employed are then presented.
1. Fuels
Each test fuel was analyzed to verify concentrations of
additives under study. Additionally, complete physical
(distillation, octane numbers, fluorescence indicating
analysis [FIA] composition, and Reid vapor pressure [RVP])
and trace metal analysis was determined.
2. Oils
Engine oils were examined for trace metals both before and
after test runs. Compliance of physical properties with
specifications was verified.
-------
B Gauge & Tape Sampler System
V
ro
CT>
Figure 4
-------
-27-
3. Diluent Air
Mass and composition of the filtered diluent air participate
was determined with the engine or vehicle operating in the air
pick-up zone as during a test run. This data was necessary to
provide a correction factor applicable to the mass emission
rates determined during a test run.
4. Exhaust Gases
Engine exhaust gases were analyzed routinely several times
during the conditioning sequence and during sampling runs.
Schematically, exhaust gas sample points are as shown earlier
in Figure 2 (page 20). The engine exhaust gas was analyzed
for oxygen, nitrogen, carbon monoxide, carbon dioxide, and
total hydrocarbons. The hydrocarbons were broken down into
saturates and unsaturates. These analyses were done by gas
chromatography, chemical absorption, and a total hydrocarbon
analyzer. Data reduction was via an IBM 1800 computer through
a Bell Telephone ASR 33 Teletype interface.
a) Analytical Equipment
A Fisher Gas Partitioner was used for the analysis of
oxygen, nitrogen, carbon monoxide, and carbon dioxide.
The partition column consisted of a 6-foot section
containing hexamethyl phosphoramide and a 6-1/2 foot
section containing 13x molecular sieves in series.
Total hydrocarbons were obtained from a Beckman Model
109A Total Hydrocarbon Analyzer. The concentration
of unsaturated hydrocarbons was determined by passing
the sample through an absorption tube (1/2" x 8") filled
with 30-60 mesh pink Chromosorb impregnated with 50 percent
mercuric perchlorate.
-------
-28-
The output of the gas chromatograph was coupled with
a Hewlett-Packard Model 3370A Digital Intergrator which
has an ASCII coded output to drive an ASR 33 Teletype
and punch paper tape.
b) Samp!ing
A Neptune Dyna-Pump was used to pull the sample from
the exhaust pipe sampling point through 1/4" OD stainless
steel tubing and transfer it to the total hydrocarbon
analyzer and the gas sampling valve of the gas chromatograph
through 1/8" OD stainless steel tubing. A manifold system
was provided to allow the operator to calibrate the
equipment with the appropriate standards.
c) Standardization
A gas mixture containing known concentrations of oxygen,
nitrogen, argon, carbon monoxide, carbon dioxide, and
n-hexane was used as a reference standard for the total
hydrocarbon analyzer and the Fisher Gas Partitioner.
d) Operation
The operator typed the proper computer code and program
number on the teletypewriter, injected the reference
standard, and pressed the integrator start button.
As the peaks emerged, the time and area information
was encoded and stored on punched paper tape. Each
succeeding exhaust gas was identified along with the
N
total hydrocarbon level, and run in the same manner
as the standard. When the series was finished, the
punched tape was sent to the computer by teletype over
regular telephone lines.
-------
-29-
e) Data Reduction
A typical output format for the gas analysis is shown
in Figure 5. Identification of the components in the
standard was based upon each peak size in descending
order. Estimated retention time was the updated time
of each peak in the standard. Retention time windows
are 4 seconds plus 2 percent of the retention time.
Actual percent is a direct ratio of the area counts
in the unknown sample to the area counts in the standard
times the volume percent in the standard. The total
percent actual will normally be 97-98 percent since
water is removed from the saturated sample after the
sampling valve.
A correction for the unresolved argon in oxygen was
made based upon response factors and the amount of
argon found in a number of exhaust gas samples by mass
spectroscopy.
The actual percent was normalized to 100 percent in the
next column on a moisture free basis, and an Exhaust
Gas Analysis report was issued (Figure 5). The air-
to-fuel ratio was calculated from this analysis, the
total hydrocarbon content, and the percent carbon in
the fuel.
b. Oxides of Nitrogen
1) Equi pment
Beckman Ultraviolet Analyzer
Beckman Infrared Analyzer
Recorder - Texas Instrument Company
The above pieces of equipment were in a single, self-
contained unit built by Scotts Research Labs Inc.,
San Bernardino, California.
-------
-30-
Figure 5
G. C. ANALYSIS - TECHNICAL DATA -
CSV RUN 23 GCT 16
CYCLE 2 72.9 K0URS
KG 620.
10-16-70
PEAK
N0.
1
2
3
A
5
ACT
22
59
83
104
187
TIME
o EST*
21.
59.
• 83.
107.
•' IBS.
«
PCT. VSL.
ACTUAL N0RM.
0
12
1
0
81
1
97
2
2
.000
.003
.493
.900
.033
.626
.060
.940
.940
0.
12.
1*
0.
83.
1.
1 00.
000
366
530
927
492
675
000
COMPOUND
IDENTIFICATI0N
C0MP0SITE
CARBON DIOXIDE
0XYGEN
ARG0N
NITR0GEN
CARBON M0N0XIDE
TOTALS
BALANCE BY DIFFERENCE
T0TAL CONTAMINATION LEVEL
EXHAUST GAS
GGV RUM
CYCLE 2
KC 620 «
23
72
0CT 16
o9 H0URS
ANALYSIS
10-16-70
TIME PERCENT IDENTIFICATION
83.
107.
83.
186.
59.
0.9 ARC3N
83«5 NITROGEN
1.5 eXYGl'M
1.68 CARO'JN K9NOXIDE
12.4 CARDON DIOXIDE
100.0 T0TAL
FRACTION CARBON IN FUEL 0.8625
T0TAL HYDR3CARBCN CONTENT 620. PPM.
AIR/FUEL RATI0 14.S
-------
-31-
2) Calibrating Gases
Nitric oxide (3545 ppm in nitrogen)
Nitrogen dioxide (862 ppm in nitrogen)
These standard gases were purchased from Scotts
Research Labs, Inc.
Nitrogen was used as zero calibrating gas.
3) Procedure
Before making NO, NCL measurements, the paper filters
(Whatman #3) to each analyzer were changed and the
Drierite dryer in the exhaust sample line was replaced.
Both analyzers were standardized using the appropriate
calibrating gas at a constant flow. The zero standardizing
was done using nitrogen as the calibrating gas and using
the same flow rate.
After the instrument was standardized, the exhaust gas was
passed through the analyzer using the same flow rate
as in the standardization step. The NO, N02 values were
recorded by the dual pen Servo-riter recorder. Figure 2
indicates the source of the exhaust gas sample.
5. Combustion Chamber Deposits
Combustion chamber deposits were carefully removed from valve faces,
heads, and piston tops; weighed, and analyzed for major elements
and, in some cases, for trace metals.
6. Exhaust Particles
The collection and classification techniques employed allow
the calculation of mass emission rates in grams/mile of
exhaust particulate. Additionally, cumulative mass distribution
data can be calculated. Several collection methods were used,
-------
-32-
all of which allowed determination of mass emission rates
but not cumulative profiles. Additionally, a fairly complex
analytical scheme was used to determine chemical composition,
trace metals, organic fractionation, crystalline species, Nhk,
HC1, HpO, major elements, and physical character.
D. ANALYTICAL METHODS
1. Optical Microscopy
Optical microscopy was used to provide two basic evaluations
of collected particles. First, low magnification documentation
of particle character and distribution on collection surfaces
and devices (electron microscope grids, etc.) was obtained and,
second, documentation of particle size, character, and crystalline
morphology at 400x under polarized light. Although several
crystalline species were identified by X-ray diffraction,
it was not been possible to reliably identify these particles
by polarized light alone because of the similar morphology of
the different crystalline species.
2. Transmission Electron Microscopy (TEM)
The transmission electron microscope (TEM) was used to characterize
and photographically document those exhaust particles which are
smaller than one micron and to obtain crystallographic analysis
of them by means of electron diffraction. Sampling for this
work was done by attaching transmission electron microscope
grids, which had been previously given a carbon reinforced
collodion substrate, directly onto the Andersen Sampler collection
plates and on the Millipore filter following the Sampler. After
sampling, the grids were removed and stored in a desiccator to
await analysis.
The TEM used was the Phillips EM300 where standard instrumental
operating conditions were employed, including a 100 kV operating
potential to give the best penetration of the electron dense
-------
-33-
particles. The particles under consideration here were those
o
ranging in size from 100 to 1000 A. Photomicrographic documentation
was carried out recording similarities and differences as these
were observed.
3. Scanning Electron Microscopy (SEM) and X-ray Fluorescence
The Scanning Electron Microscope (SEM) was used to identify
(X-ray spectrometer) the collected exhaust particles from the
Andersen Sampler and the Millipore backup filter.
a. Instrumentation
Cambridge Stereoscan Mark 2A
Ortec Non-dispersive X-ray Detector
Nuclear Data Analyzer
Varian Vacuum Evaporator
Kinney Vacuum Evaporator
b. Work Outline
1) Particle characterization (SEM) on plates of
Andersen Sampler
2) Particle identification (X-ray).
3) Single element X-ray scan.
4) X-ray spectra on impingement area of Andersen
plates and spectra on backup filter.
c. Techniques and Methods
1) Substrates for sample collection: The most satis-
factory substrates for photomicrography were micro
cover glasses, while where X-ray analysis was employed,
ultra pure carbon strips proved best. Silica interference
from micro cover glasses, halogens in epoxy, and thermal
instability in mylar film reduced the desirability
for using these materials as substrates where X-ray
analysis was to be carried out.
2) Storage and sample preparation: All samples were
maintained in a dry atmosphere from collection to
-------
-34-
examination. Both the glass cover slip and the carbon
strip substratum were attached to SEM sample stubs with
conducting silver paint. Samples for SEM characterization
o
were made conductive with a thin layer (^200 A) of gold
or gold-palladium evaporated. Graphite carbon was
sputtered on the samples used for X-ray diffraction.
3) Normal operation for the Stereoscan:
a) Gun potential - 20 to 30 kV (depending on
sample degradation and resolution needed).
b) Vacuum - ^10" Torr.
c) Sample angle - 20°
d) Working distance - 11 mm
e) Polaroid P/N Type 55 film with 100 sec exposure
4) Normal operations for X-ray Spectrometer (warranted
215 ev FWHM resolution):
a) Gun potential - 30 kV
b) 1024 channel - Series 2100 Nuclear Data Multichannel
Analyzer
c) Collection time - 200 sec
d) Count rate - ^60 c.p.s.
e) Spectra recorded on Moseley 7035B X-Y Recorder
f) Single channel recording
g) Polaroid P/N Type 55 film
400 sec or 800 sec exposure depending on
concentration
d. Analysi s
1) Particle characterization and photomicrographical
documentation was done with the scanning electron
microscope employing standard operational procedures.
2) Particle identification involved elemental analysis
using the X-ray spectrometer on the scanning electron
microscope. This included, for multiple particles, full
-------
-35-
spectrum elemental scan, and single element scan. Spot
scans were carried out on single particles or in specific
regions of particles.
4. X-ray Diffraction
Crystalline components in the collected exhaust particles were
determined using a 143,6 mm diameter DeBye-Scherrer powder camera
with Cu or Fe radiation and a 114.6 mm diameter Guinier-type
focusing powder camera with Cu radiation. Diffraction pattern
analysis was conducted using the published ASTM Powder Diffraction
Standards and our own file of 12,000 standard patterns. The lower
limit for detection of a component in a mixture is generally
about 5 percent.
5. Mass Spectrometry
Mass spectrometry was used in this project for the semi-
quantitative and qualitative comparison of the levels of NH~,
HpO, HC1, and organics associated with auto exhaust particulates.
Different mass spectrometric techniques were tried and their
advantages and disadvantages evaluated.
The mass spectra were obtained at 70 ev using a standard
90 degree magnetic sector mass spectrometer. The sample was
scraped from the trays of the Andersen Sampler, weighed and
devolati1ized in a 500 cc reservoir. The vapors were introduced
into the ion source of the mass spectrometer through a 2 mil
diameter molecular leak while the inlet system was held at
200°C. In an attempt to avoid changes in composition during
sampling, the scans were delayed one minute to assure complete
volatilization of organics. Both the masses and the intensities
of peaks were digitized automatically during scanning of the
mass spectrum. A low energy (^10 ev) mass spectrum of one
sample showed the presence of intense peaks at m/e=17, 18
and 36 which could be due to NH3, HpO, and HC1. These tentative
identifications were extended to other samples.
-------
-36-
Assuming that the average instrumental sensitivity for the
components in the sample remained approximately constant
between samples, the following quantities were calculated as
a measure of the relative amounts of NH-, H20, HC1 and organics
respectively.
Iiy - 0.21 I,
W x S,
NH3,
HC1 and
I
W
200
E
i = 40
W x S
^
1 8
x S.
••^
i.
i
t
H20
Organics
where I. is the intensity of the peaks at m/e = i, W the
weight in mg of sample loaded, and S. the toluene sensitivity
of the mass spectrometer on the day when the samples were
run.
The term 0.21 I18 in the case of NH_ was introduced to correct
for the contribution of the fragment ion H0+ from H^O to
the intensity of the peak at m/e = 17. The mass spectral
profile of organics in the auto exhaust particulates was
plotted using a B-5500 computer by connecting the mass to
charge peak tops after the intensities of the peaks had been
normalized by the computer according to the following formula:
!i
250
£
J = 25
28, 32, 44, 36, 38
Plots were made of the data for those spectra with enough
intensity to be judged significant. The plotted profiles
allow one to make a direct comparison of the relative changes
in organic composition for the samples obtained at different
engine conditions.
-------
-37-
The direct probe sample introduction technique was also
used in the characterization of the particulates. This
technique allows the sample to be heated up to 600°C in a
miniature oven located a few millimeters away from the electron
beam in the mass spectrometer. The mass spectra were taken
at different temperatures of the oven and show the presence
of PbClBr, PbBr2, and organic components giving peaks at
m/e = 43, 55, 57, 69, 71, et al. However, the technique
did not allow one to observe the quantitative differences
between samples.
A combination technique of direct probe and field ionization
mass spectrometry was also tried. Field ionization mass
spectrometry is a technique for ionizing molecules with
O
a high electric field in the order of O.lv/A. This is a
much milder means of ionization than electron impact. Hence,
the fragmentation of a molecular ion is very much reduced in
the field ionization mass spectrum and thus the spectral features
are simplified. The field ionization mass spectra of only one
sample were obtained using a CH4B mass spectrometer. These
were weak and complex. However, peaks 14 masses apart are
clearly shown in some of the spectra. Two series of peaks were
observed: a) m/e = 92 + 14xn, where n = 0-6 or higher,
b) m/e = 94 + 14xm, where m = 0-4 or higher, which might be due
to the molecular ions of:
OH
^^"
CH2CnH2N+l and f -H-CmH,MXl (or
respectively.
High resolution mass spectrometry was also used in this study
to find the accurate masses of the ions observed in the mass
spectrum within an accuracy of 5 millimass units. The accurate
-------
-38-
masses were used for the calculation of the elementary
compositions of the ions which should reflect the composition
of the sample to some extent. The high resolution mass spectrum
was recorded on a photo plate by using a CEC HOB high resolution
mass spectrometer. The data were processed with use of a
Grand-Datex photo plate reader and a B-5500 computer. It was
found that the data obtained were extremely complex and difficult
to interpret. However, the hydrocarbon ions were clearly shown
in the high resolution mass spectrometric data.
In an attempt to determine the applicability of a small mass
spectrometer to direct monitoring of the engine exhaust components
and to follow the compositions changes in the exhausts at
different engine conditions, a portable cycloidal mass spectrometer
was used on line. Gaseous components in the exhaust manifold and
in the exhaust pipe after the muffler were sampled. The exhaust
sample was introduced into the mass spectrometer through a needle
valve with the high pressure end packed with quartz wool to avoid
plugging of the valve by the combustion particles in the
exhaust stream. Because of the high concentration of H20,
air, CO, and C02 in the exhaust, the mass spectral peaks
detected were normalized according to !,•/£,• c-,1 , where I.
I 1 ^ 0 *T 1
is the intensity of the peak at mass i. The normalized mass
spectral patterns were plotted employing an IBM 1130 computer
by connecting the tops of the normalized peaks at the adjacent
masses with a straight line for convenient comparisons between
spectra.
For the samples trapped on the glass fiber filter papers, it
was extremely difficult, if not impossible, to remove the
trapped samples from the filter papers and to obtain their
mass spectra in the previously described ways. A special
technique was therefore required. Since the filter papers
used always absorb moisture, a background spectrum of ^3 mg
of water in a 500 cc reservoir at 200°C was obtained before
the samples spectrum. The sample spectra were corrected for
-------
-39-
peaks shown in the water background which were due to the
compounds desorbed from the walls of the spectrometer by the
water. The reservoir was then disconnected from the spectrometer
and flushed with argon. The filter paper was cut into small
pieces and packed on the bottom of the reservoir which was
then connected to the spectrometer. The reservoir was chilled
with liquid nitrogen for two minutes, pumped to a desired
vacuum and then heated to 200°C in about three minutes. The
mass spectrum was scanned one minute after the leak valve
to the spectrometer had been opened. The mass spectral pattern
was then calculated and plotted in the usual manner. No
significant peaks, except those due to water, were detected
for the unused clean filter paper.
6. High Resolution Mass Spectrometric Analysis
High resolution mass spectra of dilution tube and Andersen
samples from run No. 27 (Type A fuel commercial 3 cc TEL)
were obtained using a direct introduction probe system and
recording spectra as a function of increasing probe tempera-
ture and amount of sample evolved. The spectra were recorded
on photographic plates and these data were reduced using Shell
Oil Company HIRES programs. The sample was introduced at room
temperature and allowed to warm up to the ion source temperature
by radiation. When no more sample evolved, the sample was removed
and placed immediately in the heated probe and spectra were
continuously recorded as the probe temperature increased to
approximately 400°C. The recording period for each spector
was controlled as a function of the integrated ion current.
The resulting information was combined after data processing
to give a single composite spectrum for each sample. The
spectra were recorded on the Ilford Q-2 type plate.
-------
-40-
7. Neutron Activation
This method is applicable to the determination of total chlorine
and bromine in samples containing 100 to 20,000 yg of chlorine
and 1-10,000 yg of bromine. Both bromine and chlorine can be
quantitatively and nondestructively determined in the same
sample by taking advantage of the large difference in gamma ray
energy between the isotopes of bromine and of chlorine.
To further eliminate any possible interference, one can measure
the chlorine gamma radiation through a lead absorber which will
reduce the bromine radiation to a much larger extent than the
chlorine radiation.
Interferences
High levels of sodium may cause a change in sensitivity
limits but would not normally prevent analysis. Manganese
would also interfere, but is easily detected and if found,
the samples can be measured with the high resolution detector
with some loss in sensitivity.
Apparatus
a) Automatic sample changer-gamma spectrometer, Nuclear
Model 1085 using a 3-inch well Nal(Tl) crystal
b) A solid 3" Nal(Tl) detector with input to sample changer
c) lonization chamber, 1-2500 mr/hr range
d) TRIGA reactor with maximum flux in the lazy susan of
11 2
5 x 10 neutrons/cm /sec
e) Computer-teletype hook-up for calculations
f) Lead "pig" with wall thickness 1/2" and hole diameter
of 0.662"
g) Ge(Li) detector and Nuclear Data Model 2200 multichannel
analyzer
-------
-41-
Reagents
a) Chloride standard solution of 1 mg/ml. Weigh out 0.7546 g
NH4C1 and dilute to 500 ml.
b) Bromide standard solution 1 mg/ml. Weigh out 0.6129 g
NH4Br and dilute to 500 ml.
c) Sodium standard solution 1 mg/ml. Weigh out 1.479 g
HCOONa and dilute to 500 ml.
Procedure
a) Sample Preparation - Samples were received in 2 dram
polyethylene vials and were heat sealed for irradiation.
Standard solutions of chloride, bromide, and sodium
were placed in 2 dram polyethylene vials at the same
height as the samples and the vials were heat sealed.
b) Irradiation - Samples and standards were initially
10 2
irradiated at a neutron flux of 5 x 10 neutrons/cm /sec
(nv) for 10 minutes. The flux could be increased by a
factor of 10 to 5 x 10 if the initial irradiation
produced too little radioactivity. In such a case, one
would need standards at a ten-fold dilution.
c) Counting for Chlorine - A 1 ml aliquote of each standard
was transferred into a clean 2 dram polyethylene vial
and diluted to the volume of the samples. Several types
of counting systems may be used depending on the radiation
being emitted from the sample. With only chlorine, bromine
and sodium present in the sample, the sample should be
counted by the 3-inch solid detector (item b under
Apparatus) through the lead "pig" (item f under Apparatus)
if large amounts of bromine are present. Because of
the variation of absorption coefficient with energy
of gamma rays passing through lead, this permits a much
greater reduction in bromine gamma rays than chloride
gamma rays and reduces the interference from bromine.
-------
-42-
In this case the output of the 3-inch detector is used
as an input to the amplifiers of the sample changer.
One of the single channel analyzers in this instrument
is sent to cover the chlorine-38 gamma ray at 2.16 Mev,
the secone single channel analyzer is set to cover the
sodium-24 gamma ray at 2.75 Mev.
Two or four minute counts can be taken at the discretion
of the analyst.
The sample changer was used as a timing device and to
record the counts observed, but the samples were changed
by hand each time the printer prints a set of data. All
samples and standards were counted twice.
If manganese is found to be present in the samples,
the samples must be counted with the Ge(Li) detector.
The information which is stored in the memory of the
analyzer must be read out on paper tape after each
measurement. The peak areas are then integrated by
summing the counts in each channel over the region of
interest. Samples which show very low amounts of
radioactivity can be counted in the well type Nal(Tl)
detector in the sample changer. Again, the single
channel analyzers were set to cover the chlorine and
sodium gamma rays.
Bromine standards were counted any time a Nal(Tl)
detector was used so that the contribution to the
chlorine can be subtracted once the amount of bromine
is determined.
d) Counting Bromine - After the chlorine and sodium have
decayed away, the bromine-82 can be measured either
with the solid Nal(Tl) detector or with the well
-------
-43-
detector depending on the radiation intensities. A
single channel analyzer was set to cover the bromine-82
gamma ray region from 0.554-0.777 Mev.
Calculations for Use of Nal(Tl) Detector
Calculations were made for bromine first.
a) (Std bromine counts-background) x decay corr. _ counts _ R
yg of Br yg Br
(counts for sample-background) x decay corr. _ hrom'ne
Calculations for chlorine proceeded as follows:
The bromine contribution to the chlorine measurement was
subtracted as follows:
yg Br in sample x count in Br std. during Cl measurement =
Bromine count to be subtracted from chlorine count (A)
Chlorine count - A = true chlorine count
If sodium were present then the bromine conbribution to the
sodium must also be subtracted.
Dual channel cross-interference calculations for the sodium
contribution to the; chlorine were made by computer.
Since there was a very broad range in the amounts of
bromine and chlorine in the samples investigated, it was
necessary to be thoroughly familiar with all possible
counting techniques;.
Immediate decisions; had to be made on the proper counting
device to be used because of the short half life of
chlorine-38 (37.3 min.).
-------
-44-
Since the whole procedure is nondestructive, samples could
be returned after a sufficient decay period for the deter-
mination of lead by other techniques^?'.
8. Atomic Absorption
a. Method for Lead Determination
Following nitric acid digestion, particulate samples were
washed into 50-ml volumetric flasks and diluted to mark.
This normally put the concentration of lead in the flasks
between 20 and 200 jag Pb/ml . If the concentration was
higher than 200 yg Pb/ml, the sample required redilution.
The samples were analyzed on an atomic absorption spectro-
photometer (Perkin-Elmer Model 303) using a hollow cathode
lamp with a lead cathode filament. Operating conditions
were as follows: 10 milliamps tube current, light path
slit opening - 4, ultraviolet light range, acetylene-
air oxidizing flame, one-slot burner head, wavelength -
2170 angstroms. The sample solution is aspirated into
the flame where lead atoms present absorb the light from
the lead cathode filament. The amount of absorbed light
is proportional to the concentration of lead. The samples
were analyzed in conjunction with the following series
of lead standards: 10, 20, 40, 60, 80, 100, 150, and 200 yg
Pb/ml. The concentration of the standards was plotted
versus their absorbance values giving a standard curve.
With the absorbance values for the samples and the standard
curve, it was possible to determine the concentration of
lead in the samples. The sensitivity for the lead deter-
mination in an air-acetylene flame is about 0.25 yg Pb/ml
at 1 percent absorption. The detection limit is 0.1 yg
Pb/ml.
-------
-45-
b. Determination of Lead and Iron in Engine Combustion
Chamber Deposits
These samples were thoroughly ground in a mortar prior to
analysis to obtain uniform samples. The ground sample was
dissolved in nitric acid and lead determined by atomic
absorption. A portion of the sample solution was also used
in the determination of iron. Iron is reduced with
hydroxylamine to the ferrous state, and reacted with
1,10-phenanthroline in an acetate buffered solution (pH 5)
to form an orange-red complex. Photometric measurements
were made using a Beckman DU-2 spectrophotometer. Operating
conditions were as follows: sensitivity setting - 2,
slit opening - 0.10 mm, wavelength - 510 nm, 40 mm optical
cells. The concentration of iron was determined from a
standard curve. For a one gram sample diluted to 100 ml,
the detection limit is about 1 ppm and the sensitivity
- 1 ppm.
c. Gravimetric Method for Lead Determination in Millipore
'Filters
Following nitric acid digestion, concentrated sulfuric
acid was added to the sample to precipitate lead sulfate.
The solution was filtered, and the precipitate dried and
weighed to determine the amount of lead percent. In
addition, the filtrate was analyzed by atomic absorption
for trace amounts of lead. This analysis is included in
the total amount of lead reported for the sample.
d. Determination of Lead and Other Metals in Fiberglass
Fi 1 ters"
The fiberglass filters cannot be digested completely with
nitric acid. They were cooked with concentrated nitric
acid for two hours to leach out the metals. The pulp was
filtered and washed and the filtrate analyzed by atomic
absorption for lead, and- by emission spectroscopy for other
metals.
-------
-46-
9- Emission Spectrometry
a. Principle
Organic matter in the sample is destroyed by wet ashing in
sulfuric, nitric and perchloric acids. The resulting
solution is taken to dryness and the residue is taken
up in a spectroscopic buffer solution containing the internal
reference element, palladium. A portion of the solution
is dried on pure graphite electrodes. The electrodes thus
prepared are excited in an a.c. arc discharge and the spectrum
is photographed. The intensity ratios of selected lines
are determined photometrically and the concentration of
each element is read from an analytical curve relating
intensity ratio to concentration.
b. Apparatus
1) Excitation. Excitation is obtained by the use
of a 2400 volt a.c. arc discharge - Jarrel-Ash Custom
Varisource, or equivalent.
2) Spectrograph - Baird 3 meter grating spectrograph.
Reciprocal dispersion is 5.55 A/mm in the first order.
3) Developing equipment - Jarrel-Ash Company. Plates
are developed in a thermostatically controlled developing
machine, washed and dried over heat in a stream of air.
4) Densitometer. Spectral lines are measured with
a non-recording projection type densitometer. Densitometer
Comparator, Baird Associates Inc., or equivalent.
5) Calculating equipment. A calculating board is
employed to covert densitometer readings to log intensity
ratios. Jarrel-Ash Co.
6) Wet ashing equipment. A micro Kjeldahl digestion
rack is used for wet ashing the organic solvents.
-------
-47-
Reagents and Materials
1) Distilled nitric and perchloric acids. Perchloric
acid is an intense oxidizing agent. Organic matter
should not be heated in perchloric acid unless in the
presence of sulfuric or nitric acid.
2) Sodium nitrate, reagent grade (NaN03).
3) Palladium diamine nitrite, Pd(NH3)2(N02)2.
4) Water soluble salts of the elements Al , Ca, Cu,
Fe, Mg, Mn, Ni, Pb, Sn, and Zn.
5) Electrodes, high purity graphite, 1/4" diameter
by 3/4" length. Ultra Carbon Corporation.
6) Photographic plates - Eastman Spectrum Analysis
No. 3.
7) Kjeldahl flasks, 10 ml.
Calibration
1) 0.2182 gm of palladium diammine nitrite Pd(NH3)2N02)
were dissolved in water. 10 ml of concentrated reagent
grade nitric acid were added and the mixture diluted to
volume with water in a 100 ml volumetric flask. This
solution contains 1 mg Pd per ml.
2) A buffer solution was prepared by dissolving 20
gm of sodium nitrate in water. 5.0 ml of the palladium
solution above and 7.5 ml of concentrated reagent grade
nitric acid were added and the whole diluted to 100
ml .
3) A stock solution containing 0.01% (0.1 mg/ml)
each of the elements Al, Ca, Cu, Fe, Mg, Mn, Ni, Pb, Sn,
and Zn was prepared. Two aliquots of this solution were
diluted ten-fold and one hundred-fold to provide 0.001%
and 0.0001% solutions.
-------
-48-
4) Standard additions of the impurity elements were
made to Kjeldahl flasks as shown in Table 7.
5) 0.5 ml of concentrated reagent grade sulfuric acid
was added to the Kjeldahl flasks and the solution
evaporated to dryness. After cooling, 1 ml of concen-
trated nitric acid was added and the mixture was
evaporated to dryness again. The residue was taken up
in 5 ml of buffer solution, warming, if necessary,
to put the salts into solution.
6) The end of the 3/4" graphite electrodes was polished
on filter paper and placed in a stainless steel drying
tray. A drop of kerosene was placed on the top of
each electrode to seal the porosity and the electrode
allowed to dry. One pair of electrodes was prepared
for each of the standard addition solutions by pipetting
0.03 ml of the solution onto the end of each electrode.
The electrodes were dried slowly over micro burners
in a gas drying oven and stored in a desiccator until
run.
7) The samples were excited in water cooled electrode
holders using the following conditions:
(1) Current, 4.0 amps, a.c. arc.
(2) Spectral region, 2150-3550 A.
(3) Slit width, 50y.
(4) Electrode gap, 2 mm.
(5) Pre-burn period, 10 seconds.
(6) Exposure period, 90 seconds.
8) The emulsion was calibrated by use of a stepped filter
or by other recommended methods described in the
"Recommended Practice of Photographic Photometry in
-------
-49-
Conccntration
Table 7
ml. of Ht£nc!a.rd addition impurity solution
Blank
O.CO001%
0. 0000251-
O.CGOo5%
0.0001%
o.ooor:5%
0. GOO •*?•';>
0.00075%
0.001%
O.O025%
0.005%
0.01 %
O.5 E! .
1.25 Eil.
o.r.s ni.
O.5 ol.
1.25 nl.
2.5 r.d.
O.375 al.
0.5 til.
1.25 nl.
2.5 ml.
5.0
0.0001% i
II
Q.CO!%
ii
it
M
0.01%
It
II
II
It
301
"
"
11
II
M
II
II
II
II
II
Element
Analytical
Lino A
Al
Ca
Cu
Fe
Fe
Tj»y
MS
Lin
L'n
Ni
Ni
Pb
Pb
an
Sn
Zn
3092.71
3179.33
3273.03
3021.O7
302O.G4
>{G02.69
2779.83
2S33.C3
27S-i.S2
3414.77
3037-.G-i
2873.32
2033.07
3175.02
2£G3.33
33':.'j .03
Table 8
Analytical Liao Pairs
Internal Standard
LIno A
3027.91 Pd
ii
it
it
it
it
it
:c.V/;round
Concentration
Range %
O.O00025-O.0010
O.OOO25-O.O1O
O.OO001-O.00025
O.OOO1-O.O10
O.OOO025-O.O050
O.OOG025-O.GO10
O.OOO5-O.O10
O.OOO5-0.010
O.OOCO1-O.C010
O.OOC025-O.0010
O.OO05-O.O10
O.OO10-O.O10
O.OO005-0.005O
O.OOO05-O.COGO
O.OOO75-O.O10
O.OOO1-O.O10
-------
-50-
Spectrochemical Analysis" A.S.T.M. Designation:
E116, Methods for Emission Spectrochemical Analysis,
(1964).
9) The emulsion was processed according to the following
conditions:
(1) Developer (D19, 20.5°C), 3 1/2 minutes.
(2) Stop bath (SB-4), 1 minute.
(3) Fixing bath (Kodak Rapid Fixer), 2 minutes.
(4) Washing, 3 minutes.
(5) Drying, in a stream of warm air.
10) The relevant analytical line pairs were selected
from Table 8. The relative transmittances of the
internal standard line and each analytical line were
measured with a densitometer. The transmittance
measurements of the analytical line pairs were converted
to intensity ratios by the use of an emulsion calibration
curve and a calculating board.
11) Analytical curves were constructed by plotting
concentration as a function of intensity ratio on log-
log graph paper. For best results, the average of
at least four determinations recorded on two plates were
plotted.
Procedure
1) The available sample was weighed directly into
a Kjeldahl flask. Sulfuric acid was not used in the
wet ash procedure because test samples usually contained
a large amount of lead which would form the insoluble
sulfate. Wet oxidation was carried out with nitric
and perchloric acid only. Extreme caution was exercised
in the use of this technique. Concentrated nitric
-------
-51-
acid was added dropwise, a few tenths ml at a time,
to the hot mixture to aid in oxidation. A few drops
of concentrated perchloric acid may be added to the
hot solution after most of the free carbon has been
destroyed, to hasten complete oxidation. When the
solution became water clear, it was evaporated to dryness.
After cooling, 0.5 ml of nitric acid was added and the
mixture evaporated to dryness. The addition of 0.5 ml
of nitric acid was repeated and the solution evaporated
to dryness again. The inorganic residue was dissolved
in dilute nitric acid and the volume adjusted to a
known concentration, usually 10 mg/ml. If the original
sample size was below 30 mg, a less concentrated solution
was usually made up. Aliquots of this solution were taken
to dryness and then the buffer solution (d2) added
in an amount to give a dilution factor of lOOx. One
sample was analyzed by the direct reader while a
second was examined photographically. Some samples
had to be run at factors larger than lOOx in order
to get the concentration for some elements to fall
within the range of the analytical curves. By varying
the sample to buffer ratio any number of concentration
or dilution factors could be achieved. A blank of
the acids used was carried through in the same manner
as the sample.
2) Proceed as in d(6), (7), (8), (9), and (10) of the
calibration procedure. Duplicate spectra were recorded
for each sample;.
f. Calculations
The intensity ratios were converted to concentration by
use of the analytical curves.
-------
-52-
g. Precision and Accuracy
Representative precision and accuracy of the method are
given in Table 9. Each of the twelve samples A,, Ap, A3,
B, , Bp, B-, C,, Cp, C3, D, , Dp, D3, was analyzed by means
of duplicate excitation^8'9^.
10. Polarography
The analytical method for the determination of carbonyl compounds
in automotive exhaust emissions employed polarographic techniques.
Samples for analysis were collected from undiluted exhaust effluent
using ice-water cooled cold traps and via a sample probe welded
into the engine or vehicle exhaust system. A Princeton Applied
Research Model 170 Electrochemistry System was used as the monitoring
device. The derivative pulse polarographic mode yielded the
best combination of resolution and sensitivity for the classification
of carbonyl compounds. A dropping mercury electrode with a
Princeton Model 172 Drop Timer was employed as the working electrode.
Hydrazine derivatives (hydrazones) were employed for the deter-
mination of the carbonyl compounds, since hydrazones are easier
to reduce than the free compounds, thus eliminating many possible
i nterferences.
An acetate buffer of approximately pH 4 (an equimolar mixture
of acetic acid and sodium acetate, 0.1M in water) was used to
control pH for hydrazone formation and also acted as supporting
electrolyte. Hydrazine was added as a 2 percent aqueous solution.
In this system formaldehyde gave a peak potential (half-wave
potential) of -0.92v vs. a saturated calomel reference electrode.
A platinum wire was employed as the auxiliary electrode.
With the above system, it is possible to distinguish between
and simultaneously determine aromatic aldehydes, formaldehyde,
higher aliphatic aldehydes, and aliphatic ketones as shown in
Figure 6.
-------
TABLE 9
Representative Precision and Accuracy
0>
•H
p.
a
a*
Al
Jt
A2
A3
Bl
JL
B2
D
"3
C,
i
C2
C3
Dl
A.
D2
D3
% Al
O.OOOO44
O.OOOO52
O.OOOO45
O.OOOO52
O.OOOO4
O.OOOO52
O.OOO12
O.OOOO97
O.OCO097
O.OOOO94
O.OOGO32
O.OO011
O.OO028
O.OO03O
0.00020
O . OCO23
0 COQ24
0.00028
0.00074
O.OOO64
O.OC059
O.OO06S
O.OO059
O.OOO53
% Ca
0.00043
0.00050
O.OOO43
0.00037
O.OOO43
O.OO05O
O.OO105
0.00093
O.O0096
O.OOO68
0 . OGGS5
O.OC074
0.0023
0.0018
0.0-022 a
O.002G3
O.O023
0.00275
O.007O
O.O054
O.OO49
0.0057
0.0048
O.OO6O
% Cu
O.OOO048
O.OOOO54
0.000046
O.OOOO47
O.OOO05O
O.OOOO48
O.OOO12
0.00010
O.OOOO99
O.OOOO95
O.OOOOS5
0.000096
O.OOO23
O.O0028
O.OOO23
O.OOO25
0.00026
O. 00028
....
__
__
__
„_
--
% Fe
0.00043
O.OOO55
O.OOO44
O.OOO43
O.OOO46
O.OOO46
0.0010
O.OOQ04
0.00090
O.OO105
O.OOiO
O.OOIO
O.OO25
O.OQ30
0.0023
O.OO235
O.OO275
O.OO285
O.OOS5
O.O053
O.OO57
O.OO39
O.QOSO
0.0085
% Mg
0.00049
O.OO052
0.0(X>47
O.OOO50
O.OO053
O.OOO49
O. 00105
O.OOO95
0.00092
0.00091
O.OOIO
O.OO09O
O.OO23
0.0023
0.0023
0.0024
O.0023
O.O024
0.0057
O.O051
0.0048
O.OO47
0.0045
O.O055
% Mn
O.OOO46
O.OO057
0.00051
O.OO050
O.OOO49
O.OOO46
O.OOIO
0.0012
0.0011
O.OOO66
0.00086
O.OOO92
O.OO265
O.OO195
O.OO265
0.00275
O.OO245
O.0023
O.OO59
O.O058
O.OO45
O.OO48
O.OO47
O.OO54
"; Ni
O.OO047
0.00055
O.OOO45
O.OOO51
O.OOO47
O.OOO48
O.OOIO
O.O0096
O.OOIO
O.OO105'
O.OOIO
O.OO1O5
O.OO245
0.00265
0.0023
0.00245
O.O026
0.00255
O.OO65
O.OO58
O.O056
O.0057
0.0050
O.O055
% Pb
O.OOO56
O.OOO59
O.OO050
O.O0051
O.OOO52
O.OOO53
O.O0105
O.OO098
O.OOIO
O.OO105
O.OOIO
O.OOIO
O.OO235
0.00255
0.00245
0.0026
O.OO25
O.OO245
O.OOS6
O.OO45
O.OO45
O.OO48
O.OO43
O.OO49
% Sn
0.00052
O.OOO59
O.OO053
O.OOO50
O.OOO50
O.OO04G
0.0011
O.OO094
O.O0105
O.OO105
O.OOO99
O.OOIO
0.00255
O.O027
O. 00215
0.0023
O.0025
O.OO265
0.0064
O.OO59
0.0053
O.OO57
0.0054
O.OO49
%Zn
0.00040
O.OOO45
O.OO054
O.OOO4O
O.OOO52
0. OOO-12
O.OOO94
O.OO12
O.O0125
O.OOIO
O.OOO96
0.00115
O.OO14
O.OO215
O.OO225
0.0030
O.OO3O
O.OO2O
0.0058
O.OO5O
0.0050
O.OO6O
O.O037
O.OC41
co
i
AJ( A2, and A3 contain. O.OOO05% of Al aa
-------
-54-
±fffl±H
! I . T I i '• '
j-j-rrHrPolarographic Determination of Aldehydesj-
.__].. u-t-u...—_^._M_—,—.-T^., _t_^—TiiiTti I"! 1! M~r!i
•TTTTTZn
MHn
I i : I . .
rTTTi ! i |T
1 ' i -r
±t±t±t±t±
l_^..J_l_l..k
!~ftl-H-
-et4--t-r--
-------
-55-
Since aromatic ketones, e.g. benzophenone, give polarographic
response in pH 4 buffer without hydrazine, it is also possible
to detect aromatic ketones. Lead and zinc could also be determined
from the samples under these conditions.
Since formaldehyde was the main carbonyl component of the
condensate samples, all results were calibrated against and
reported as formaldehyde. The upper curve in Figure 7 shows an
actual sample without hydrazine present and demonstrates the
lack of interference in the carbonyl region. The lower curve
shows the same sample after the addition of hydrazine. Figure 8
shows the same solution after the addition of a formaldehyde
standard. These two figures clearly establish the presence
of formaldehyde in the exhaust samples.
Experimental
The absorptivity at 255 nm of benzene soluble particulate residues
can be used as a measure of aromaticity. As shown in Figure 9,
PbBr2 has an absorptivity of 16.6 at 255 nm. Thus the presence
of lead compounds can alter the absorptivity and produce an
erroneous measure of aromaticity. Measurement of the absorptivity
at 300 rather than 255 nm minimizes the interference of lead
compounds in measuring aromaticity.
Lead can be polarographically determined as Pb in pH 4
acetate buffer. The peak potential is -0.42v vs. SCE. Figure 10
demonstrates the presence of lead in an actual run and Figure 11
shows the recovery of added Pb (added as PbClp)-
A description for the polarographic examination of these samples
fol1ows .
-------
——'"I : •
"Wrff
i_u;. -i. i
Figure 8
Polarographic Determination of Aldehydes
•'.-•. Figure 7
;;.-_-_ Polarographic Determination of Aldehydes^±i
r.- .no.hy3i}a2iuft-ij
ill
—as -abov«-:with-hyd
t
en
crv
-------
-57-
Figure 9
0/7
WAV GLEN 6rfH
* ' 90,01
-------
•r--rrrrt"T"t"
-i-'t-rt- rrf - -
-58-
Figure 10
Polarographic Determination
, -i •-?•• .•»-*. t—t r- —i- —^—
t.i..; }.: l.i_t- _L__E
> T I I T . i i
0.5 ml Run #40
pH 4 Acetate Buffer
No Hydrazine
b±;±rj±
i i i T i 1
o.ov
-O'HV
-uv
-------
Figure 11
Polarographic Determination
0.5 ml Run #40
pH 4 Acetate Buffer
No Hydrazine
40 mg Pb (as PbCl2)
~;]4-H-H-H-
i-H-rt-Ht
H"n n-h
l-t H-H-r-r-
-H-rh-H--h
t—t-T
-TEJ13-:
±1±PT
! ' I !
0*0 V
-------
-60-
Procedure
Pipet 2 ml of methanol sample into a 25-ml volumetric flask.
Add 10 ml of pH 4 acetate buffer and dilute to volume with
water. Transfer this solution to a polarographic cell and
deaerate with oxygen-free nitrogen for ten minutes. Record a
derivative pulse polarogram from 0 to -1.6 V vs. SCE. Add
2 ml of hydrazine reagent to the polarographic cell and
deaerate for 5 minutes. Again, record the polarogram from
0 to 1.6 V vs.. SCE.
Lead and aromatic ketones are determined from the waves obtained
without hydrazine at the peak potentials listed above. Formaldehyde,
higher aliphatic aldehydes, aromatic aldehydes, and aliphatic
ketones can be determined from the second polarogram with
hydrazine present.
All responses should be calibrated by addition of known amounts
of standard compounds to actual runs. Peak heights are linear
with concentration.
In this system, zinc has a peak potential of -1.00 V vs. SCE,
but it can be differentiated from benzophenone by the fact
that it possesses only one polarographic wave.
11. Organic Separation
Micro methods have been developed for the determination of the
following in automotive exhaust particulate samples.
a) Benzene solubles and ultraviolet absorptivity
b) Phenolics
c) Total acidity
d) Ultraviolet fluorescence
-------
-61-
Determination of Benzene Solubles and Ultraviolet
Absorptivity
1) Scope
Samples obtained as scrapings from Andersen impingement
plates or on sheets of fiberglass filters were used
to quantitatively collect auto exhaust particulates.
The following method can apply to particulate matter
from industrial or urban air and exhausts whenever the
filter can be physically extracted and does not produce
an appreciable blank of benzene solubles.
The weight percent and relative ultraviolet absorbance
of the benzene solubles were obtained, both based on
total particulate collected. The weight percents were
related to the total organic content, and the absorbance
values related to the aromatic moieties present.
2) Principle
The samples are extracted with benzene and the residue
weighed after evaporation of the filtered extract. The
residue is dissolved in methanol and the absorbance
quantitatively measured.
3) Interferences
Trace solvent impurities and equipment trace contamination
could be the main sources of interferences. Detection
and correction is accomplished by processing blanks
and controls along with the samples. Organics present
as metal salts; are not accounted if insoluble in benzene.
Any lead compounds soluble in benzene would give high
results because the lead cation has appreciable absorbance
in the ultraviolet region. Highly conjugated aliphatic
compounds are not expected, but their presence would
lead to higher absorbance values.
-------
-62-
4) Apparatus
a) Spectrophotometer, Gary Model 14 or equivalent,
and matched 1-cm cells.
b) Vacuum oven set at 45-55°C and storage desiccator
to maintain vials at constant weight.
c) Balance, sensitivity ±0.02 mg.
d) Mechanical shaker.
e) Small mouth bottles and vials (2x7 cm) with
Teflon-lined screw lids. The glass lips are ground
flat with emery cloth to assure leak-proof seals.
f) Sintered glass, filter funnels (medium),
volumetric flasks and pipets.
g) Steam heated bath and a nitrogen supply terminated
with medicine dropper nozzles for evaporation under a
stream of flowing nitrogen gas.
5) Reagents
a) Benzene, spectrophotometric grade. The UV-cutoff
(absorbance of 1) should be less than 280 nm in a
1-cm cell; evaporation of 100 ml should produce less
than 0.1 mg residue.
b) Methanol , spectroscopic grade. The UV-cutoff
should be less than 210 nm in a 1-cm cell, and
the evaporation of 100 ml should produce less than
0.1 mg residue.
6) Procedure
a) Weigh by difference to ±0.1 mg the collected
particulates. Remove the particulates by scraping
with a razor blade when Andersen plates are used,
weigh to ±0.1 mg, transfer to an extraction bottle
and extract using 10 to 50 ml of benzene for amounts
0.2 to 25 mg. When a sample on a glass-fiber filter
is analyzed, cut the filter into small sections
-------
-63-
and transfer to an extraction bottle; extract using
50 to 600 ml of benzene for 0.01 to 0.7 g of collected
participate. Shake for a minimum of 4 hours. Tape
the lids to prevent unscrewing and leakage.
b) Collect the extracts by filtration using
sintered glass funnels. Transfer all filter segments
to the funnel. Rinse several times with benzene,
using a glass tamper to press dry the filter cake.
c) Evaporate most of the benzene in the filter flask
by heating on the steam cone with a stream of nitrogen
directed to the surface. Quantitatively transfer to
vial, predried to constant weight of ±0.04 mg using
benzene rinses. Complete the evaporation of the
benzene as described. Do not let the benzene tempera-
ture exceed 60°C, and do not let the vial remain on
the steam cone when evaporation is complete (Note 9b).
Remove the last benzene trace by storing 5 minutes
in a vacuum oven at 10 mm pressure and 45-55°C.
Store in a desiccator containing barium oxide for
at least 10 minutes to equilibrate, and weigh by
difference the residue to ±0.04 mg.
d) Dissolve in approximately 1 ml/mg of methanol or
a minimum of 5.00 ml. This dilution was used for
various determinations (Note 9d).
e) Scan the base line characteristics of the spectro-
photometer and cells from 460 to 220 nm with methanol
in the sample and reference 1-cm cells. Then scan
the appropriate, quantitative dilution of a small
aliquot of (d) to have a net absorbance between
0.2 to 1.2 at 255 nm without changing the balance
(Note 9c). Methanol is used in the reference cell.
Record the net absorbance at 255 nm, the dilution,
and the wavelength of prominent spectral features.
-------
-64-
f) Repeat steps (a) through (e) using an unused
porous glass filter as blank.
i
7) Calculati ons
a) Relative UV absorbance/mg particulate sample
Ral uv/mg - =p. x 1520
where
A = net absorbance of benzene solubles at
255 nm of the dilution analyzed after
correction for base line and blank
mgs = particulate analyzed, mg
V = absorbance dilution volume, ml
T = volume containing all benzene solubles, ml
B = aliquot of T used in absorbance dilution, ml
b) Absorptivity (a)
AVT
B (mgR - mgB)
where
mgR and mgB are mg of benzene solubles from
sample and blank respectively.
c) Relative UV absorbance of total particulate (x 10" )
AVT mgp
Rel UV particulate = —g— x —-
where
= mg total particulate on filter
-------
-65-
d) Percent benzene soluble (%„)
(mgR- mgR)
of __ i\ D v "1 fl O
°B mg^
8) Precision and Accuracy
Precision and accuracy cannot be calculated because
known or duplicate samples were not analyzed. Results
are most meaningful when 3 mg or more of benzene
solubles is collected.
9) Notes
a) All equipment and containers must be cleaned
using dichromate sulfuric acid, rinsed thoroughly
and dried at 110°C to minimize trace contamination.
b) Valori (Reference 10) has shown that the loss
of polynuclear aromatics during evaporation is low.
c) From 0.3 to 0.07 mg benzene solubles per ml of
methanol is usually required to produce a net
absorbance in the range indicated.
d) If insoluble material is present, transfer the
contents to a preweighed centrifuge tube and
centrifuge. Remove the clear liquor with a medicine
dropper and return to the initial vial. Rinse the
insolubles and inner surface of the tube with
methanol several times. Remove the residual
solvent and determine the weight of this residue
as described in 6(c).
-------
-66-
b. Determination of Phenolic Content
The weight percent phenolics in the benzene soluble fraction
of the participate have been obtained.
1) Principle
Phenolic materials produce a 20-30 nm shifting of an absorption
peak when converted to the anionic form. The difference
in absorption is measured at 295-300 nm of two solutions
of equal concentrations, one containing excess KOH and
the other excess HC1. This difference was used to calculate
the amount of phenolics based on the calibrated response
of p_-phenylphenol.
The method was adapted to the characteristics of actual
samples which showed a differential response at 295-300 nm,
similar to £-phenylphenol , which shows a difference
maximum at 297 nm and absorptivity of 120 nm. Different
phenols show significant variations in location of the
maximum and magnitude of absorptivity at 295-300 nm; thus
the calculated values should be compared only to similar
samples, and not taken as absolute values. Absolute values
would necessitate isolation of the phenolic fraction with
determination of absorptivity.
Analyses have shown significant differential absorbances
at 410 and 450 nm, indicating the presence of unaccounted,
colored (phenolic) materials.
2) Apparatus
a) Spectrophotometer, Gary Model 14 or equivalent,
and matched 1-cm cells.
b) Vacuum oven set at 45-55°C and storage desiccator
to maintain vials at constant weight.
c) Balance, sensitivity -0.02 mg.
-------
-67-
d) Mechanical shaker.
e) Small mouth bottles and vials (2x7 cm) with
Teflon-lined screw lids. The glass lips are ground
flat with emery cloth to assure leak-proof seals.
f) Sintered glass, filter funnels (medium), volumetric
flasks and pipets.
g) Steam heated bath and a nitrogen supply terminated
with medicine dropper nozzles for evaporation under a
stream of flowing nitrogen gas.
3) Reagents
Alcoholic KOH, IN. Dissolve 56.1 g KOH (assay 99.5%
minimum) in 56 ml of distilled water, cool, and dilute
with methanol to 1 liter at room temperature. Store
in polyethylene bottle.
4) Procedure
a) Weigh by difference to ±0.1 mg the collected
particulates. Remove the particulates by scraping
with a razor blade when Andersen filters are used,
weigh to ^0.1 mg, transfer to an extraction bottle
and extract using 10 to 50 ml of benzene for amounts
0.2 to 25 mg. When a sample on a porous glass
filter is analyzed, cut the filter into small sections
and transfer to an extraction bottle; extract using
50 to 600 ml of benzene for 0.01 to 0.7 g of
collected particulate. Shake for a minimum of 4 hours.
Tape the lids to prevent unscrewing and leakage.
b) Collect the extracts by filtration using sintered
glass funnels. Transfer all filter segments to the
funnel. Rinse several times with benzene, using a
glass rod to press dry the filter cake.
-------
-68-
c) Evaporate most of the benzene in the filter flask
by heating on the steam cone with a stream of nitrogen
directed to the surface. Quantitatively transfer to
vial, predried to constant weight of ±0.04 mg using
benzene rinses. Complete the evaporation of the
benzene as described. Do not let the benzene tempera-
ture exceed 60°C, and do not let the vial remain on
the steam cone when evaporation is complete. Remove
the last benzene trace by storing 5 minutes in a vacuum
oven at 10 mm pressure and 45-55°C. Store in a desiccator
containing barium oxide for at least 10 minutes to
equilibrate, and weigh by difference the residue to
-0.04 mg.
d) Dissolve in approximately 1 ml/rug of methanol or
a minimum of 5.00 ml .
e) Repeat steps (a) through (c) using an unused glass
filter as blank.
f) Scan the base line characteristics of the matched,
1-cm cells from 680 to 220 nm with alcoholic KOH in
the sample cell and with methanol containing 1 drop
of concentrated HC1 per 5 ml in the reference cell.
g) Without altering the balance, scan from 680 to
220 nm appropriate, equal aliquots of solution (d)
each diluted to 5.00 ml to give a differential absorbance
less than 0.5 at 300 nm with the material in the sample
cell diluted using alcoholic KOH and that in the reference
cell diluted using methanol containing HC1 (1 drop/5
ml). Record the differential, net absorbance (A/UQQ) at
295-300 nm, the dilution and aliquot volumes, and
the wavelength and differential absorbances of any
peak responses greater than 300 nm.
-------
-69-
h) Repeat (g) using solution from (e).
5) Calculations
a) Differential phenolic absorbance (AA)
The differential phenolic absorbance is calculated as
obtained in 1-cm cells if 9 percent of the benzene soluble
fraction were diluted to 5 ml using IN KOH in methanol
with a corresponding dilution using HC1 in the reference
cell .
AAQnn x 0.018 x V x T
A A = yu.u
AM • g
where
AA-00 = measured difference, absorbance units
V = the dilution volume, ml
T = the volume containing all benzene solubles, ml
B = the aliquot of T used, ml
0.018 = obtained from 0.09 T 5
b) Micrograms (yg) of phenolics calculated as para-
phenylphenol
yg = AA x 463 (Note 7a)
c) Wt. percent phenolics in benzene solubles (%PB)
The weight percent phenolics is taken as the average
of maximum and minimal values, based on exclusion
and inclusion of the blank correction.
ygp - 1/2 ygpc 1/2 ygpc
%PB = ~~mgR x 10i mgR x 10
-------
-70-
where
ygp = the amount found in the sample, yg
ygpc = the amount found in the blank, yg
= the benzene solubles from the sample, mg
d) Wt. percent phenolics in particulate sample (%pp)
PP
X 10 r>
"PP 100
where
%D is calculated
b
(mgR - mgR)
% = 2 B_ x 100
mgs
6) Precision
Particulate samples of known composition were not analyzed.
Known dilutions of £-phenylphenol showed a linear absorbance
(295 nm) up to 0.6 within ±0.02. Blanks indicated a
variability or contamination of 30 yg per run calculated
as £-phenylphenol. The precision is dependent on sample
size and phenolic content. The weight percent phenolics
in benzene solubles is calculated as the difference of
two calculations of maximum and minimum amounts. Precision
(i.e. ±1/2 ygp(0 ranges from ±0.1 percent absolute with
19.8 mg of benzene solubles to ±0.3 percent for 4.7 mg
and 1.1 percent for 1.2 mg.
7) Notes
The equation is derived from absorptivity (a).
AA x volume
mg
-------
-71-
The absorptivity of £-phenylphenol is 120. Thus
AA x 5 x 103 100
The factor 100/9 relates the value of the 9 percent
aliquot to that of all of the benzene soluble fraction.
c. Determination of Acidity
1) Principle
Sodium 4-nitrophenate is used as both indicator and excess
titrant to measure acidity.
+ RC02H
The change in the absorbance of the 4-nitrophenate anion
is determined spectroscopically in the presence and
absence of the sample. The difference is related to
the acidity calibrated using known benzene acid mixtures.
2) Interferences —
Since the acidity is related to benzoic acid, the results
are most meaningful in relative comparisons. The acidic
materials in the benzene soluble fraction have been
characterized via infrared as organic carboxylic acids.
Weaker acids are partially accounted for, and strong acids
would be excessively accounted. Benzoic acid is 30.4
percent ionized and phenol only 4.7 percent. Phenol
produces one-sixth the indicator absorbance change as
the same weight of benzoic acid.
Inert, colored impurities do not interfere because the
absorbance of the sample is used to establish a base line.
Unsuspected interferences can be detected by variations
-------
-72-
in certain spectral features. Acidity is determined by
a decrease of the absorbance peak at 390 nm which is
related to the 4-nitrophenoxide anion. Acidity can also
be determined by an increase of the absorbance peak at
310 nm, related to the unionized 4-nitrophenol. The
ratios of AA3ig/AA390 were -°-53 -0.04 when pure benzoic
acid and phenol were used. Gross interferences are
detected by observed ratio variations greater than
-0.5 ±0.2. The exact variation from -0.53 can be utilized
to calculate an estimated deviation. The indicator system
also shows an isosbestic at 335-340 nm; the difference in
absorbance should thus agree closely with that of the
sample less indicator if interferences are absent. The
magnitude of the disagreement can be used as a measure
of interference.
It was found that some samples contained a yellow, unknown
impurity with an absorbance peak at 380 nm, shifting to
400-450 nm upon addition of excess caustic. This shift
is observed when determining the phenolic content
described earlier. Maximum interferences calculated
from spectral data indicates that the acidity results
could be low by 10 to 30 percent. Maximum interference
is not expected because calculated corrections in most
cases produced abnormal ratios of AA3,0/AA3gQ. Minimal
interference is calculated to be less than 2 percent
relative, assuming that the unknown impurity is phenolic
and only 5 percent ionized.
3) Apparatus
a) Spectrophotometer, Gary Model 14 or equivalent,
and matched 1-cm cells.
b) Vacuum oven set at 45-55°C and storage dessicator
to maintain vials at constant weight.
-------
-73-
c) Balance, sensitivity -0.02 mg.
d) Mechanical shaker.
e) Small mouth bottles and vials (2x7 cm) with
Teflon-lined screw lids. The glass lips are ground
flat with emery cloth to assure leak-proof seals.
f) Sintered glass, filter funnels (medium),
volumetric flasks and pipets.
g) Steam heated bath and a nitrogen supply terminated
with medicine dropper nozzles for evaporation under a
stream of flowing nitrogen gas.
4) Reagents
a) 4-Nitrophenate Indicator Solution. Sodium
4-nitrophenate is prepared by first dissolving 5.16 g
4-nitrophenol (Eastman Kodak) in 44.6 ml 0.75N sodium
hydroxide in ethanol. The solution is evaporated to
dryness. The residue is triturated and washed using
200 ml petroluem ether, and then dried at 1 mm at
50°C for 2 hours.
Then 11 to 12 --0.1 mg is dissolved and diluted to
100.0 ml using spectroscopic-grade methanol.
b) Benzoic acid, primary standard grade.
5) Calibration
a) Weigh 19 to 21 ±0.05 mg of benzoic acid into a
500-ml volumetric flask, dissolve and dilute to
volume using methanol.
b) Add 1.00, 2.00, and 5.00-ml aliquots of solution from (e)
page 68, respectively to 25-ml volumetric flasks. Then
add a 2.50-ml aliquot of the 4-nitrophenate indicator
solution to each flask and also to a fourth flask
to be used as a blank. Dilute all to volume using
methanol and mix the contents.
-------
-74-
c) Adjust the spectrophotometer to permit recording
i . .
a negative absorbance of 0.25 at.; 390 nm. Determine
the base line characteristics from 280 to 400 nm,
using the blank solution in the sample and reference
1-cm, matched cells. Then measure the difference
absorbances of the three dilutions vs. the blank
from 280 to 400 nm as illustrated in Figure 12.
d) The absorbances at 390 and 310 nm are plotted vs.
micrograms of benzoic acid per 25 ml as illustrated
in Figure 14.
6) Procedure
a) Add appropriate and equal aliquots of solution (d)
page 68, to two of three 5.00-ml volumetric flasks.
Add 0.50 ±0.2 ml of the indicator solution to the first and
third flasks. Dilute all three flasks to volume using
methanol and mix the contents.
b) Measure the absorbance of the sample in the
second flask from 480 to 240 nm in a 1-cm cell with
methanol in the reference cell. A typical scan is
shown as I in Figure 13.
c) Measure the absorbance difference of the other
two solutions from 480 to 240 nm without changing
the balance. The solution containing both sample
and indicator is placed in the sample cell. A
typical scan is shown as II in Figure 13.
7) Calculations
a) Acidity as micrograms of benzoic acid in benzene
solubles (y
-------
0,6
Figure 12
Difference Spectra of
4-Nitrophenate (0.29 mg
per 25 ml) Solutions
.C.OUB C
0*3
0,0
6'&
Fi gure 13
Spectra Obtained Using
Benzene Solubles From
Participates of Run 28
z CM! 3
\m-rn
N6TSBCOK
190 320 360 406 HKO
-------
-76-
Figure 14
•I
~J
LLi
£
0
-L
I- r
I
t
-O.i -
0s?
N PRESENCE, OF 12>e.Nz.o\c
IN
m*
^^
NE3SB
50
Zoo
-------
-77-
H x V x T
M90C02H ~ 25 x B
where
W = the value obtained from the calibration
graph based on the measured value of
AA39Q, yg/25 ml
V = the absorbance dilution volume, ml
T = the volume containing all benzene solubles, ml
B = the aliquot of T used, ml
b) Acidity of particulates calculated as percent
benzoic acid (% Ap)
' V 9 rt r n i-i ~ ^ 9 R r'
%n _ Wl/UnM D U
M p» ~*
'P rug;: xTO
where
y9BC = t'ie amount calculated for the blank, ug
c) Acidity of benzene solubles calculated as percent
benzoic acid (% AR)
(v9nirn H ~ ^Sor)
01 n = |flLU0n oL
/0 HR mgn^- mgn)10
K D
8) Precision
Particulate samples of known composition were not analyzed.
Precision and accuracy are dependent on the relative amounts
in the samples and blanks. Unused filters and solvent
showed acidity blanks of ±15 yg calculated as benzoic acid.
9) Notes
a) The extreme non-linearity at higher concentrations
is shown in Figure 15.
-------
-78-
Figure 15
IOOO
-------
-79-
b) An appropriate aliquot is one producing an
absorbance difference at 390 nm less than -0.25 as
shown in Figure 13. The response sensitivity
decreases with larger amounts as shown in Figure 15.
An appropriate aliquot in one series was 0.20 ml
of solution containing from 0.5 to 7 mg/5 ml of the
benzene soluble fraction.
d. Ultraviolet Fluorescence
Automobile exhaust particles were extracted with cyclohexane
and the ultraviolet and fluorescence spectra were run. The
absorbance at 255my and the fluorescence area using an
exciting wavelength of 290my were used to calculate relative
amounts of UV absorbing and fluorescent compounds^present.
The total amount of absorbing and fluorescent compounds do
not seem to vary significantly from one run to the next;
however, the amount present in a given sample weight increases
with non-leaded gasoline and with the decreasing particle
size.
A quick standard procedure for the determination of relative
amounts of aromatic • organic materials present, in automobile
exhaust particles was developed. Since limited funding was
available to develop separation procedures and determine
individual components., a general procedure of determining the
ultraviolet absorbance and a value for fluorescence was used.
These techniques detect the aromatic organics present including
the poly-nuclear aromatics. Samples were received on
Andersen glass plates and in bottles. The bottled samples
had been obtained by sweeping out the inside of the dilution
tube and from trays that were located beneath slits in the
di1uti on tube.
-------
-80-
1) Procedure
a) Sample Handling - The participate matter from the
Andersen glass plates was scraped loose with a razor blade
and transferred to a small tared watch glass with a small
camel hair brush. The sample weight was obtained using
a Mettler micro balance. The sample was then transferred
to a 15 ml screw cap centrifuge tube (the cap of the tube
should be lined with foil or Teflon) and 2-10 ml of cyclohexane
(purified by passing through a silica column) was added
depending on expected organic concentration.
Andersen plates with <1 mg of particulate present were
handled by placing the glass plate in a petri dish
and adding 5 ml of the cyclohexane. The dish was rotated
in such a manner as to rinse the filter thoroughly; then
the solution was transferred to a screw-cap centrifuge
tube. The procedure was repeated with an additional 5
ml of solvent and thy solution evaporated to 2 ml by passing
a stream of nitrogen over the solution. The sample weight
was obtained by weighing the filter before and after use.
Approximately 10 mg of the bottled samples were weighed
in a small porcelain boat and transferred to the 15 ml
screw-cap centrifuge tubes and 10 ml of solvent added.
The centrifuge tubes were capped tightly and the caps prevented
from loosening by wrapping with rubber tape. The tubes
were placed on their sides in an automatic shaker and shaken
for a minimum of 5 hours. The rubber tape was removed
and the solution centrifuged until clear and then the liquid
was decanted into screw-cap bottles.
b) UV Absorption Measurements and Calculations - A
Gary Model 15 spectrophotometer was used with 1-cm
silica cells. When adequate solution was not
available, a 1-cm semi-micro cell (volume =0.5 ml) was
-------
-81-
used. The solutions were scanned from 400-220my, diluting
when necessary to keep the absorbance less than 2.0. All
the samples gave very similar shaped spectra with a distinct
maximum at 255my. The absorbance at 255my was used as
a measure of the organic content. A relative value of
UV absorbing material present was obtained by calculating
the absorbance for 1.0 mg of residue in 1.0 ml of solvent x
1000. An estimation of the relative total absorbing material
present on an Andersen plate can be obtained by multiplying
the sample weight in mg times the number obtained above.
c) Fluorescence Measurements and Calculations - An
Aminco-Bowman spectrophotof1uorometer equipped with a Moseley
model 135AMX-Y recorder and standard 1-cm cells, polished
on all sides, was used for the fluorescence measurements.
When adequate solution was not available, a semi-micro
cell (Volume =0.5 ml), polished on all sides, was used
by placing the narrow portion facing the excitation source
and the wide portion (1 cm of solution) facing the detector.
Various excitation wavelengths were examined (290, 330,
and 353my) with 290my giving, in general, the most detailed
and intense spectra. Exceptions to this are Plate 5 from
Runs 9, 11, 12, 13, 14, and 16 and all of Run 17, where
the 353my exciting wavelength gives a more intense spectra
(353my is used by some authors for determining poly-nuclear
2
aromatic compounds). The area in in. x 100 under the
fluorescence peaks at an excitation wavelength of 290my
was determined with a planimeter. A relative value of the
fluorescence area for 1.0 mg of residue in 1.0 ml of solvent
at a sensitivity setting of 0.01, with all slits at 2 mm,
the wavelength (x) scale on the recorder set at 20 fixed
and the intensity (y) scale on the recorder set at 5 fixed.
An estimation of the relative total fluorescent material
present on an Andersen plate can be obtained by multiplying
the sample weight in mg times the number obtained above.
-------
-82-
e. The Determination of Benzo(g)pyrene in Auto Exhausts
Samples of auto exhaust particulate collected on Andersen
plates and on 142 mm glass fiber filters were submitted
for the determination of benzo(a)pyrene. Weights of the
particulate were provided by weighing the filters on a four-
place balance before and after exposure to the diluted auto
exhaust. Particulate weights varied from 0.2-35.2 mg.
Procedure:
When available a sample of at least 10 mg (on either one or
two filter papers) was used for analysis. The filters were
folded and rolled with the particulates toward the inside of
the roll and tied with copper wire. The rolls were Soxhlet
extracted for at least six hours (with siphoning four to six
times per hour) with 75 ml of benzene. The extracts were
evaporated under a stream of filtered air at room temperature
to ^3 ml. This concentrate was filtered through a M-fritted
glass filter into a tared vial. The flask and filter were
washed three times with ^2 ml of benzene for each wash. The
combined filtrates were evaporated to dryness at room tempera-
ture with a stream of filtered air.
The residues obtained from both sample and blank filters were
weighed and the difference between them designated "benzene
soluble weight" for each sample. The residue was dissolved
in 0.2 ml of methylene chloride and a 10-40 yl aliquot was
spotted in 2-pl increments of a pre-conditioned Alumina TLC
plate along with a known standard of benzo(a)pyrene in methylene
chloride. The TLC plates were conditioned by heating at 120°C
for 1.5 hours and desiccating overnight in a 45 percent relative
humidity chamber (saturated aqueous zinc nitrate). The TLC
plate was developed in an unsaturated tank containing 20 ml
of ethyl ether in 200 ml of n-pentane to a height of 15 cm
-------
-83-
(^45 minutes). The benzo(a)pyrene spots were identified
by comparison of Rf's; with that of the standard spot under
an ultraviolet lamp. The spots, marked with a pencil, were
circumscribed with a #15 cork borer and scraped from the
plate into vials. All TLC work was performed as much as
possible in a dimly lighted area to avoid decomposition of
the benzo(a)pyrene. Five ml of 5 percent acetone in n-pentane
was added to the alumina in the vial and it was agitated
for 15 minutes on a mechanical shaker. The slurry was filtered
through a F sintered glass filter into a vial, washing the
alumina four times with ^2 ml of 5 percent acetone in n-pentane
with a 45-second soak period between each wash. The combined
filtrates were evaporated to dryness at room temperature using
a stream of filtered air. The benzo(a)pyrene residue was taken
up in 2.0 ml of concentrated sulfuric acid. This solution
was evacuated for five minutes to remove trapped air bubbles
and its fluorescence was measured in a 1-cm cell at 540 nm
while exciting at 470 nm on an Amino-Bowman Spectrophotof1uoro-
meter using a #4 slit arrangement and a sensitivity of 30.
Standards and blanks were carried through the entire TLC
procedure. The blanks were subtracted from all fluorescence
readings and the net fluorescence values for each sample were
used to calculate the amount of benzo(a)pyrene present.
Throughout all steps in the procedure, the sample were refri-
gerated when not actually being processed and exposure of
the samples to light was kept at a minimum.
-------
-84-
IV. EXPERIMENTAL RESULTS
A. INTRODUCTION
Results are presented in this section in much the same order as
is evident in the Procedures Section. There are many complex
relationships to be observed between fuel, oil, and particulate
trace metals as an example, which will be explored in depth in the
Discussion Section rather than here. Due to the complexity of
designating each specific run in the ensuing tables and figures,
each will be referred to by run number. A ready reference table
(Table 10) is included for convenience in relating these run
numbers to such details.
Results are presented in final compiled form. Appendices providing
the basic data from which compilations have been based are provided
where appropriate. Details regarding specific analytical procedures
have been discussed in detail in the preceding (Experimental Procedures)
section of this report.
B. ENGINES AND VEHICLES
The following engine and vehicle types have been used during this
study. More than one of each type may have been used, for example,
the Chevrolet 350 CID equipped vehicles. [Note Table 11 (Run
Number Designations).]
-------
-85-
TABLE 10
RUN NUMBER DESIGNATION
Run Engine/ Vehicle
No. Vehicle D No.
3
4
5
6
6B
7
7B
8
9
11
12
13
14
15
16
17
,18
19
20
21
22
23
24
25
27
28
29
30A
30B
31
32
33
34
35A
35B
35 C
36A
36B
37
38
39
39C
390
39E
40
41
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E '
E
E
E
E
E
E
E
V
V
V
V
E
V
V
E
E
V
V
V
V
V
V
V
V
V
V
V
V
V
E
V
-
-
-
-
,
-
-1*
-
-
-
-
-
-
-
-
-
•
-
-
-
00497
00497
00628
D0628
e
00282
00282
-
- -
01207
D9680
09680
09680
09680
01171
01171
D0565
09559
61313
61313
61313
61313
-
61313
Year
1970
It
n
H
»
U
n
M
B
*
•
t*
"
a
H
H
a
N
H
a
,*
M
a
u
n
1971
1970
1970
1971
1971
197l'
1969
1969
1969
1969
1971
1971
1970
1969
• 1971
19?1
1971
1971
1971
1971
tnqine uata
Make
Chevrolet
"
n
H
II
H
H
* H
n
O
H
n
H
II
H
a
H
u
t
a
it
n
\ - a
u
n
"
0 H
n >
1
Pontiac
Chevrolet
Chevrolet
Pontiac
Pontiac
Plymouth
Dodge
Dodge
Dodge
Dodge
Chevrolet
Chevrolet
"
11
11
"
.11
"
Pontiac
Chevrolet
CID
350
"
"
H
II
n
"
ii
n
u
M
11
M
H
n
n
"
M
H
"
II
n
11
n
u
n
400
350
350
400
400
318
440
440
440
440
350
350
"
»
"
II
II
"
400
350
Lor
Hours
48
"
n
n
11
"
it
n
u
n
"
11
n
n
n
11
"
"
n
"
"
»
5
5
5
5
48
2
0
48
48
5
5
0
0
0
0
6
6
6
0
0
0
0
48
5
.75
.75
.75
.75
.25
.67
.75
.75
.67
.67
.67
.67
.0
.0
.0
.67
.67
.67
.67
.75
101 1 1 oni nq
Mode MPH
SS
11
11
11
"
11
, "
11
11
n
CY
SS
CY
SS
SS
CY
SS
11
11
"
"
»
- "
"
"
..
"
HS CY-FTP
SS
SS
SS
SS
CS CH-FTP
HS CY-FTP
HS CY-FTP
CS CY-FTP
SS
SS
SS
HS CY-FTP
CS CY-FTP
HS CY-FTP
HS CY-FTP
SS
SS
60
n
"
"
"
11
11
"
"
11
-
60
-
60
60
-
60
11
»
".
11
11
11
11
"
.,
-
-
60
60
60
60
-
-
-
-
60
60
60
-
-
-
-
60
60
Fuel Used
IND HO-30
IND HO-30
IND HO-0 0.06 ml TEL
IND HO-15 + MM
IND HO-15 + MM
IND HO-0 t 3 ml TEL
IND HO-0 + 3 ml TEL
IND HO-0 + 3 ml TEL + 1 T EDE
IND HO-0 + 3 ml TEL + 1 T EDC
IND HO-30
IND HO-30
IND HO-30 + Additi ve I
IND HO-30 + Additive I
Diluent ai r blank
IND HO-0 Trace TEL
IND HO-0 Trace TEL
IND HO-30 + Additive II
IND 110-30 (AMOCO 200 oi 1 )
IND HO-30 + Additive III
AMOCO 0.5 TEL 91 RON
AMOCO no TEL 91 RON
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 .cc TEL
AMOCO no TEL 91 ROM
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
AMOCO no TEL 91 RON
AMOCO no-TEL 91 RON
Fuel Type A 2.65 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
AMOCO no TEL 91 RON
AMOCO no TEL 91 RON
Fuel 'Type A 2.66 cc TEL
Fuel Type A 2/66 cc TEL
AMOCO no TEL (2 runs) (P.C.M'.}
AMOCO no TEL (P.C.M.)
AMOCO no TEL (P.C.M-. }
AMOCO no TEL (P.C.M.)
AMOCO 0.5 TEL 91 RON
AMOCO no TEL (P.C.M.)
Run Engine/ Vehic
No. Vehicle D No
42A
42B
42C
43
44
45
46A
46B
48A
48B
49A
49B
49C
49D
50
51A
51B
51C
53A
538
53C
54
56A
56B
56C
58A
58B
58C
58D
58E
59
60A
60B
60C
61
62A
62B
62C
63
65
66A
66B
66C
67
Legend
V
V
V
V
E
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
E
E
E
V
V
V
V
V
E
V
.V
V
V
V
' V
V
V
V
V
V
V
V
CS ' =
CY =
E =
EDB =
EDC =
60337
60337
60337
D1171
. -
D1169
D1171
D1171
D1169
"
u
»
"
11
D1220
D1220
01220
D1220
D0234
D0234
D0234
D0235
-
-
D1171
"
11
"
"
-
D1169
D1169
D1169
D1169
00234
D0234
D0234
D0234
D1169
D1220
D1220
01220
D1220
RUN NUMBER DESIGNATION
,. Enqine Data Conditioning
I e
Year
1970.
1970
1970
1971
1971
1971
"
"
11
"
11
n
«
"
11
11
"
it
1970
11
"
11
1970
1970
1970
1971
"
11
u
11
"
"
"
"
1970
1970
1970
, 1970
1970
1971
1971
1971
1971
1971
Cold Start
Cycled
Engine
Ethylene Di bromide
Ethylene Dichloride
Make
Chevrolet
Chevrolet
Chevrolet
Chevrol e t
Pontiac
Chevrolet
11
"
»
"
"
"
»
11
' ii
"
"
11
"
•
"
ir
Chevrolet
„
"
"
»
'
11
Chrysler
Chevrolet
"
«
»
CID
350
350
350
350
400
350
II
II
11
II
II
"
»
"
11
II
II
"
II
II
11
II
350
"
n
"
"
n
"
n
383
350
"
»
11
Hours
0.
0.
5.
5.
48
5.
0.
"
11
u
"
0.
0.
0.
5.
0.
0.
0.
0.
0.
0.
0.
18
24
24
0.
0.
0.
0.
5.
48
0.
0.
0.
6.-
67
67
75
75
75
67
38
67
67
75
67
67
38
67
67
38
60
Mode MPH
CS
HS
CS
HS
CS
HS
CS
HS
HS
HS
CS
HS
HS
CS
HS
HS
CY-FTP
CY-FTP
SS
SS
SS
SS
CY-FTP
CY-FTP
CY-FTP
CY-FTP
CY-FTP
LA4
CY-FTP
CY-FTP
SS
CY-FTP
CY-FTP
LA4
CY-FTP
CY-FTP
LA4
SS
-
-
60
60
60
60
-
-
-
.-
-
-
-
-
60
-
-
-
-
-
-
60
Dow cycle
67
67
67
67
75
67
67
38
0
0.67
0.67
»
n
0.38
'
CS
HS
HS
HS
CS
HS
HS
CS
HS
HS
5.75
"
"
5.
.75
0.67
0.67
0.38
u
Fuel s
FTP =
HS -
IND =
LA4 =
MM =
CS
HS
HS
5.75
SS
SS
CY-FTP
CY-FTPN
LA4
LA4
SS v
SS
CY-FTP
Cy-FTP
LA4
SS
CY-FTP
CY-FTP
LA4
SS
SS
CY-FTP
CY-FTP
LA4
SS
30
60
-
-
-
-
60
60
-
-
-
- -
-
-
60
60
-
-
-
60
A, B, C = Commercial fuels
California 7 Mode P.C
Hot Start
Indol ene
Federal 23 Mode
Motor Mix
Chemical Name
Dosac
L§_
Fuel Used
AMOCO no TEL (P.C.M.)
AMOCO no TEL (P.C.M.) 2 runs
AMOCO no TEL (P.C.M.)
AMOCO no TEL
Fuel Type B no TEL 91 RON
AMOCO 0.5 TEL 91 RON
AMOCO' no TEL 91 RON
AMOCO no TEL 91 RON
AMOCO 0.5 TEL 91 RON
AMOCO 0.5 TEL 91 RON
AMOCO 0.5 TEL 91 RON
AMOCO 0.5 TEL 91 RON
AMOCO 0.5 TEL 91 RON
AMOCO 0.5 TEL 91 RON
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type C no TEL 91 ROM
Fuel Type C no TEL 91 RON
Fuel Type C no TEL 91 RON
IND 0 91 RON (P.C.M.)
IND 0 91 RON (P.C.M. )
IND 0 91 RON (P.C.M.)
IND 0 91 RON
IND 0 91 RON
IND 0 91 RON
IND 0 91 RON Cooled dilutier air
IND 0 91 RON
AMOCO 0.5 TEL
AMOCO 0.5 TEL
AMOCO 0.5 TEL
AMOCO 0.5 TEL
AMOCO 0.5 TEL
Fuel Type C no TEL 91 RON
Fuel Type C no. TEL 91 ROM
Fuel Type C no TEL 91 RON
Fuel Type C no TEL 91 RON
Amoco 0.5 TEL 91 ROII-Di luent air blank
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
Fuel Type A 2.66 cc TEL
.M. = Proprietary Catalyst Muffler
RON - Research Octane Number
SS = Steady State
T = Theory
V = Vehicle
Additive I Amine salt of- mixed alkyl phosphate
Additive II N-Normal butyl para-amino phenol
Additive III 2,6-Di-tert-buty1-para-cresol
12 lbs/1000-bbls
76.9 lbs/1000 bbls
18.0 lbs/1000 bbls
-------
-86-
TABLE 11
TEST ENGINES AND VEHICLES
Test Engines
1970 Chevrolet 350 CID 2 bbl V-8
1971 Pontiac 400 CID 2 bbl V-8
1971 Chrysler 383 CID 2 bbl V-8
Test Vehicles
1969 Chevrolet Impala 350 CID
1970 Chevrolet Impala 350 CID
1971 Chevrolet Impala 350 CID
1970 Ford Galaxy 500 351 CID
1971 Plymouth Fury III 318 CID
1969 Dodge Charger 440 CID
Engine specifications for the dynamometer studies are listed below
These engines were set to manufacturer's specifications for each
respective model year.
1970 Chevrolet 350 CID V-8
Spark plugs
Points dwell
Timing
Idle Speed
Carburetor
Horsepower
Compression ratio
1971 Pontiac 400 CID V-8
Spark plugs
Points dwell
Timing
Idle speed
Carburetor
Horsepower
Compression ratio
AC 455 .035" gap
28-32°
4° BTC
780 rpm
2 bbl Rochester
255 @ 4800 rpm
9.0:1
AC R475 .035" gap
30° .016" gap
8° BTC
750 rpm
2 bbl
265 @ 4400 rpm
8.2:1
-------
-87-
1971 Chrysler 383 CID V-8
Spark plugs
Points dwell
Timing
Idle speed
Carburetor
Horsepower
Compression ratio
Champion J11Y
30-34°
0°
750 rpm
2 bbl
275 @ 4400 rpm
8.5:1
.035" gap
C. DILUTION TUBE
1. Dilution Ratios
Table 12 indicates the average air-exhaust dilution ratio at
the sampling zone of the dilution tube for each specific run
by run number. Note that engine dynamometer runs use only one-half
the engine exhaust while vehicle runs use the full exhaust.
Dilution ratios for cycled vehicle studies are based upon the
average vehicle exhaust output volume for the cycle. The tube
is designed to operate at 520 scfm (standard cubic feet per minute),
rather than monitoring a constant dilution ratio between engine
and vehicle tests.
2. Dilution Tube Profile - Sampling Zone
The majority of the mass emission rate and cumulative mass
distribution data depends upon the assumption that a true
proportional sample is taken at the sampling zone. In order to
determine the stability of the sampling zone, several evaluations
have been conducted as noted below:
Engine/Vehicle at Cruise Condition
1) Temperature profile
2) Flow rate profile
3) Mass profile
Vehicle Under Cyclic Operation
1) Temperature variations at single point in sampling zone
2) Flow rate variations at single point in sampling zone
-------
TABLE 12
DILUTION TUBE AIR-EXHAUST
Run No.
3
4
5
6
7
8
9
11
13
16
18
19
20
21
22
23
29
31
32
40
44
52A
52B
52C
52D
56B
56C
59
ENGINE STAND
Ai r/Exhaust
Pi 1 ution Ratio
2.64
1 .39
1 .74
1.78
1.91
11 .74
11.95
11.93
11 .89
11.33
13.23
12.48
13.13
11 .34
11.77
12.13
10.11
10.10
9.94
10.51
10.78
10.82
25.68
24.48
10.90
32.76
13.20
12.06
RUNS
Sampling Zone
Flow Rate (cfm)
497.80
494.52
509.10
518.15
518.76
524.00
522.56
520.94
52l'.ll
524.92
513.52
522.59
535.69
522.58
519.77
522.59
524.80
527.65
520.30
525.63
524.47
524.46
522.36
522.36
521.54
522.30
522.60
520.31
RATIOS AND FLOW
RATES BY RUN NUMBER
CHASSIS DYNAMOMETER RUNS (Steady
Run No.
24
25
27
28 .
30
33
34
37
38
41
42
43
44
50
54
• 58
61
63
65
67
State Operation)
Air/Exhaust Sampling Zone
Dilution Ratio Flow Rate (cfm)
5.22
6.47
5.00
4.39
3.96
4.54
4.14
6.78
5.70
5.04
6.60
6.13
4.58
4.32
3.39
5.58
5.20
5.37
4.76
--
526.80
525.63
532.90
524.00
524.00
520.32
519.89
522.76
526.00
525.60
525.60
522.77
520.00
508.44
522.17
524.00
524.00
524.00
524.00
524.21
I
00
00
-------
-89-
Table 13 shows the flow rates and temperature profiles in both
planes numerically. Figure 16 indicates the temperature profile
in the horizontal and vertical planes in the sampling zone under
vehicle/engine cruising mode (a.l above). Likewise Figure 17
indicates the flow rate profile similarly (a.2 above) using
an Alnor Series 6000 Velometer.
Table 14 shows the dilution tube flow profile both horizontally
and vertically during steady-state operation of a vehicle on
the chassis dynamometer using a Model 60 Anemotherm velocity
meter. This data is shown graphically in Figure 18. Table 15
shows dilution tube flow profile taken from an engine stand run
using the same .instrument as above. Again this data appears
grahically in Figure 19.
It can be noted that the flow is relatively constant in the
center portion of the tube and that there are variations near
the walls of the tube. It was also noted that they were
usually lower at the entry port than on the far wall. To
investigate this, an experiment was run where the tube was probed
from right to left horizontally and then from left to right.
The values were recorded in both cases. In the right (entry
for probe) to left, the right values were lower than center
and the left values were higher. When the tube was probed from
left to right, the left (probe entry) values were lower and the
right were higher. When an average of readings was taken, the
data resulted in nearly a straight line. Apparently air leakage
around the probe entry port, tube wall temperature and probe
design make the differences in flow readings at the walls.
The mass profile in the sampling zone has been determined by
two methods: 1) Comparison of actual collected particle mass
in the Andersen separators and/or 4 cfm filters where two or
-------
-90-
TABLE 13
DILUTION TUBE SAMPLING ZONE TEMPERATURE
FLOW RATE PROFILE
ENGINE DYNAMOMETER
Vertical Probe
?>•- Horizontal Probe
Air Flow
(fpm)
410
410
410
405
400
400
400
400
395
400
405
380
390
Temperature Range
Flow Rate Range
— >•/ ru
CS
(0
Temp. <" ?
°F ou-
170 2"
170 3"
171 4 "
171 5 "
171 6 "
171 7"
171 8"
171 9"
170 10"
170 11"
169 12"
167 13"
167 14"
Vertical
Hori zonta
TOTAL
Vertical .
Horizonta
TOTAL
Air Flow
(fpm)
385
385
390
390
405
400
395
390
400
400
405
410
420
Profile:
1 Profile:
Prof i le:
1 Profile:
Temp.
°F
168
170
171
171
171
172
172
172
172
172
171
171
169
167-171°F
168-172°F
167-172°F
380-410 Uni
385-420 Uni
380-420
2.2%
2.2%
2.9%
ts 7.9%
ts 9.0%
10 %
-------
Figure 16
-------
Figure 17
DILUTION TUBE FLOW PROFILE
ENGINE DYNAMOMETER
ALNOR VELOMETER
Vertical ®
Horizontal D
-------
-93-
Figure 18
. 1
T ' "
i :
1
I
r
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.O
L.
| _ ^ .„ ..
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<
12
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r^ 'rJo
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T r
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7
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B5C
1 . .. . >
. _ _ _...-...
- . i . - - .j. - - _ .
:::""'•'. ;:::: _ 4 LL • IT
.. T ft TT
Ul LU 1 1 UN TUBE Fl
CHASSIS DYNAI
2250 RPM - 17" 1
- Mnrlpl fif) Anemntl
,rL_____
0£S
^^^
< X
c c **
^ " " 1 '
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2
y
7
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r
2
- - • - - --- - -- -
.... »:. -:•::-.: i-::::-
E • > t en *e~
- — -
-
...
-
4-
£"
1 1 1
.OW PROFILE
IOMETER
Manifold Vacuum
lerm Meter
-
_
-
-
-
-
-
r
rv
--
}'
>m .
--
**
T
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t
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'(
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-
-
i-
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Vertical
Horizontal
-
*.
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-
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L.
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i
r
- 4
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4
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i
1-
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f" i
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j.
i"
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1,
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4:
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1
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-------
-94-
Figure 19
DILUTION TUBE PROFILE
ENGINE STAND STEADY-STATE OPERATION
Model 60 Anemotherm Meter
Run 44
tt
-------
-95-
TABLE 14
DILUTION TUBE FLOW PROFILE
CHASSIS DYNAMOMETER
2250 RPM - 17" Manifold Vacuum
Horizontal Probe Vertical Probe
Inches (f pm) (f pm)
385
390
400
400
405
400
400
410
2
4
6
8
10
12
14
15
360
390
400
400
405
410
410
420
TABLE 15
DILUTION TUBE FLOW PROFILE - RUN 44
ENGINE STAND - STEADY-STATE OPERATION
Horizontal Probe Vertical Probe
Inches (f pm) [fpm)
2 380 385
4 400 390
6 400 390
8 400 400
10 400 405
12 405 410
14 405 415
15 410 420
-------
-96-
TABLE 16
DILUTION TUBE MASS PROFILE AT SAMPLING ZONE
X
(In.)
1 .75
3.75
5.75
7.75
9.75
11 .75
13.75
15.75
MEAN
a
100 (a
1.75
3.75
4.75
5.75
7.75
9.975
10.75
11 .75
13.75
15.75
MEAN
a
100 (a
Time
(Min)
20
20
20
20
20
20
20
20
/Mean)
20
20
20
20
20
20
20
20
20
20
/Mean)
Traverse Net Wt.
(yq)
93
102
122
95
108
97
108
107
104
9.4
9.0
107
121
117
103
128
123
97
--
107
110
113
10.2
9.0
Reference Net Wt.
(yq)
98
86
95
100
112
75
107
--
96
12.5
13.0
113
92
104
100
115
112
--
in
128
127
111
11 .7
10.5
Ratio
0.949
1 .186
1 .284
.950
.964
1 .293
1 .009
1 .075
0.178
16.6
0.947
1 .315
1 .125
1 .030
1.113
1 .098
--
--
0.836
0.866
1 .041
0.156
15.0
Note: For the purposes of statistical calculations, the (--) data
were omitted because they fell out of * 2a confidence limits. As
a result of these tests, we feel that the particle concentration
profile of a sampling tube should be such that 100 (a/Mean) <10.0%.
The 10% deviation can be attributed to filter handling and measurement
errors, variations in engine operation, and variation of diluent air
conditions, such as humidity and temperature.
-------
-97-
three separate collectors were used during a single run, and
2) a mass profile in the vertical and horizontal axis using
47 mm Gelman Type A filters at 14 liters/min at selected points
sampling for 20 minutes each during a run. These data are
presented in Table 16, page 96.
Comparison of collected weights in the Andersen samplers
is shown by run number in Table 17.
TABLE 17
PARTICULATE MASS COLLECTED BY ANDERSEN SAMPLERS
(By Run Number)
(Engine Stand Runs)
Andersen Samplers at 1 cfm (Grams)
Run No. il fJL £1
6 0.0427 0.0481 0.0417
12 .0999 .1032 .1006
13 .0727 .0704 .0606
14 .0402 .0419 .0396
15 .0007 .0006 .0005
16 .0077 .0088 .0053
18 .1270 .1242 .1222
20 .1141 .1029 .1122
22 .0076 .0080 .0079
31 .0312 .0411 .0372
32 .0035 .0035 .0043
Table 18 indicates mass collected by multiple 4 cfm total
filters at the sampling zone.
The temperature and flow rate variations during cyclic vehicle
operation are shown in Figures 20-22 and 23-25, respectively.
-------
-98-
TABLE 18
PARTICULATE MASS COLLECTED BY 4 CFM GELMAN A
FILTERS BY RUN NUMBER
Mass Collected (gms) by 4 cfm Filters
Run No.
Filter #1
Filter #2
47A
47C
47E
47F
48A
48B
48C
48D
48E
48F
51A
51B
51C
53A
53B
53C
58A
58B
58C
58D
58E
59
60A
60B
60C
61
62A
62B
62C
63
.1499
.0690
.1752
.1210
.0071
.0060
.0065
.0058
.0146
.0054
.0244
.0092
.0064
.0080
.0048
.0040
.0023
.0009
.0006
.0009
.0055
.1534
.0079
.0039
.0028
.0321
.0026
.0015
.0007
.0100
.1504
.0695
.1773
.1227
.0066
.0061
.0065
.0075
.0139
.0056
.0242
.0099
.0067
.0068
.0047
.0043
.0023
.0011
.0007
.0008
.0055
.1593
.0083
.0040
.0028
.0303
.0025
.0015
.0009
.0100
-------
-99-
Figure 20
Tube Temperature Monitor at Sampling
Zone. Probe Position at 8" Horizontal
California 7-Mode Cycle-Cold Start
Nominal dilution tube total
flow = 525 scfm
l_L_L.'i^i_'i^J
SO
-------
-100-
Figure 21
Tube Temperature Monitor at
Sampling Zone. Probe Position at
8" Horizontal
California 7-Mode Cycle-Hot Start
Nominal dilution tube total
flow = 525 scfm
26
24
22
20
18
16
14
12
10
8
6
4
2
26
2B
50
SO
DEGREES FAHRENHEIT
125 ISO i:
DEGREES FAHRENHEIT
125 ISO t;
Temperature, °F
-------
-101-
Figure 22
Tube Temperature Monitor at
Sampling Zone. Probe Position
at 8" horizontal ;
Federal Cycle (LA-4) - Hot Start
Nominal dilution tube total
flow = 525 scfm
17J
Temperature, °F
-------
-102-
Figure 23
Dilution Tube Flow Monitor at
Sampling Zone. Probe Position
at 8" Horizontal
California 7-Mode Cvcle-Hot Start
Nominal dilution tube total
flow = 525 scfm
35
30
25
20
to
01
-15
10
600
500
400
; • t
3. 'i :'.'_t.r3-t—
J - — 3-»^_ f
300
.1-.
200
100
Flow, fpm, at 8" Horizontal
-------
-103-
Figure 24
Dilution Tube Flow Monitor at
Sampling Zone. Probe Position
at 8" Horizontal
California 7-Mode Cycle-Cold Start
Nominal dilution tube total
flow = 525 scfm
4-i- • «3 i-J I - .I... i 4 ' I
7~ TSETtl; i i 1 i 1~'
i i ' ' ; Pi "!:LE:-^^r!
600
Fliow, TT
' > : i i . '
,-!a|t'••!$"; !hkir:i:20ritial!
i ' ' •
-------
-104-
Figure 25
Dilution Tube Flow Monitor at
Sampling Zone. Probe Position
at 8" Horizontal
Federal Cycle (LA-4) - Hot Start
Nominal dilution tube total
flow = 525 scfrn
20
% 15
•u
c
•r—
3E
C
« 10
E
60
50 40 30 20
Flow, fpm, at 8" Horizontal
10
-------
-105-
D. TEST FUELS AND OILS
1. Physical Properties
The physical properties of each test fuel used in this study
is shown in Table 19. Sufficient fuel of each type was obtained
for the anticipated total requirement. Additional analysis
was not conducted unless an additional shipment was received.
Similarly, trace metal analysis was conducted for each test
fuel; this data is presented in Table 20.
The physical properties of the engine oils used in this study
and the run number relationships are shown in Table 21.
TABLE 21
ENGINE OIL PHYSICAL PROPERTIES
AMOCO SAE 30
Property
Gravity, °API
Flash, °F
Pour, °F
Viscosity, °F, SUS, ext.
Viscosity, 100°F, SUS
Viscosity, 210°F, SUS
Viscosity index
Color ASTM
Sulfated ash, % wt.
Carbon residue, % wt.
API classification
U s e d i n
AMOCO 100
AMOCO 200
26.4
450.0
0
75,000
555
66
95
5
1.0
1.3
MS-DM
Runs 3-18
27.1
495.0
-5
80,000
568
66
94
4.5
0.5
-
MS-DM
Runs 19-67
The trace metal analysis of these oils, both new and after
selected test runs are shown in Tables 22 and 23.
-------
TABLE 19
PHYSICAL ANALYSIS OF TEST FUELS
Distillation
286 *F
IB?
5
10
20
30
40
50
63
70
80
90
- 95
EP
* Recovery
" Sesidae
: LOSS
RVP
Octanes:
CON
SON
FIA:
: Saturates
: Oleflns
Z Arsr;at1cs
TEL (cc/gal)
• C ; ,. , . 1 rt a i* '
• ••>. loac 4
••Second lead
::•::) • I-
1
.0
.7
.3
.0
.6
.5
.4
.0
.6
.266
Motor Fuel
Fuels A, 8, C - Commercial fuels
-------
TABLE 20
TEST FUEL TRACE METALS CONTENT
(Wt. J)
Fuel Ref.
Indolene HO 30
Indolene HO o
Incolene HO-30
Indolene 0 91 Oct
AMCCO No Pb
AMOCO 0.5 Pb
AMOCO*0.5 Pb
AMOCO AMOTOHE
Fuel Type B No Pb
Fuel Type A
Indolene* 0 91 Oct
Indolene Motor Fuel
0.5 Pb
Indolene Motor Fuel
No Ph
Fe
<.0001
.033
.0012
.00009
.00005
.00009
<. 00005
< .00005
< .00005
< .00005
.0001
<. 000025
<. 000025
N1
<. 00005
.c.OOOl
< .00005
<. 00005
<. 00005
<. 00005
<. 00005
< .00005
<. 00005
<. 00005
<. 00005
<. 000025
<. 000025
Cu
< .00002
.00005
< .00003
< .00003
<. 00003
< .00003
< .00003
< .00003
<. 00003
<. 00003
<. 00003
< .000003
<. 000003
A1
<.0001
.c.OOOl
<. 00005
<. 00005
<. 00005
<. 00005
.0004
.0006
.0002
<. 00005
.0006
< .000025
<. 000025
Ca
<.0001 <
< .0001
<.0001 <
<.0001 <
<.0001 <
<.0001 <
•c.0001 <
<.0001 <
.0001 <
<.0001 <
•e.OOOl <
<. 000025
<. 000025
H
.0001
.0003
.0001
.0001
.0001
.0001
.0001
.0001
.0001
.0001
.0001
--
_.'
M£
<.0001
.0002
< .00005
< .00005
<. 00005
<. 00005
< .00005
< .00005
<. 00007
<. 00005
<. 00005
<. 000025
<. 000025
Mn
<. 00005
.0002
< .00003
<. 00003
<. 00003
< .00003
< .00003
< .00003
<. 00003
<. 00003
<. 00003
<. 000005
<. 000005
Cr
<.0001
<.0001
<. 00005
<. 00005
<. 00005
< .00005
<. 00005
< .00005
<. 00005
< .00005
<. 00005
< .000025
<. 000025
Sn
<.0001
.0002
< .00005
<. 00005
<. 00005
<. 00005
<. 00005
< .00005
< .00005
< .00005
<. 00005
< .000025
<. 000025
In
<.0003
.0007
<.0001
<.0001
<.0001
< .0001
< .0001
<.0001
•c.OOOl
< .0001
< .0001
<. 00007
<. 00007
l\_
< .0001
<.0001 <
<. 00005 <
< . 00005 <
<. 00005 <
<. 00005 <
<. 00005 <
< .00005 <
<. 00005 <
<. 00005 <
<. 00005 <
< .000025
<. 000025
Sb
--
.00005
.00005
.00005
.00005
.00005
.00005
.00005
.00005
.00005
.00005
--
..
c
86.35
86.25
82.3
82.3
84.6
83.5
85.60
85.70
86.20
85.48
85.6
85.56
85.69
H
13.09
13.09
12.60
13.09
13.45
12.96
13.4
13.4
12.7
14.30
13.7
13.22
13.45
'Different shipments
-------
-108-
TABLE 22
TRACE METAL ANALYSIS OF NEW ENGINE OIL
Element
Fe
Ni
Cu
Al
Ca
Si
Mg
Mn
Pb
Cr
Sn
Zn
Ti
P
Mo
COMBUSTION CHAMBER
AMOCO 100
.0002 wt. %
<.0001
<. 00002
.0001
.0017
.0001
.089
.0001
.0006
<.0001
<.0001
.081
<.0001
.05
<.0001
DEPOSITS
AMOCO 200
.0003 wt. !
<.0003
<.0001
<.0003
.0005
.11
<.0001
<.0005
<.0003
<.0003
.10
<.0003
E.
Combustion chamber deposits have been collected, weighed, and
analyzed for major elements; and, in selected cases for trace
elements. These data have been collected only on the engine
dynamometer studies; however, Table 24 indicates deposit weights
by run number. Table 25 shows major elemental analysis and
Table 26 trace metal analysis.
F. EXHAUST GASES
Total unburned hydrocarbons, saturated hydrocarbons, carbon monoxide,
and nitric oxide gaseous exhaust emissions have been determined
during each engine dynamometer study. The fuel and fuel additions
were found to have significant effects on such emissions during the
-------
TABLE 23
USED ENGINE OIL TRACE METAL ANALYSIS
(Weight Percent)
El ement
Fe
Ni
Cu
Al
Ca
Si
Mg
Mn
Pb
Cr
Sn
Zn
Ti
P
Mo
Run 5
Oil Filter
.012
<.0005
.0003
< .0005
.0057
<.0005
.083
<.0005
.12
.0008
< .0005
.078
< .0005
< .1
<.0001
Run 13
Oil Filter
.012
<.0005
.0002
.0013
.0028
.0010
.084
< .0005
1.3
.0055
< .0005
.082
< .0005
<.3
.0012
Run 13
Crankcase
.012
< .0005
.0002
.0012
.0026
.0030
.088
<.0005
1 .3
.0048
<.0005
.076
< .0005
< .3
.0011
Run 23
Crankcase
.012
< .0005
.0003
.0012
.0012
.0026
.12
.0005
1 .1
.0009
< .0005
.092
< .0005
-
_
Run 29
Crankcase
.0053
.0002
.0003
.0006
.0015
.0019
.13
.0003
.018
<.0002
.0007
.084
< .0002
-
_
Run 31
Crankcase
.0057
< .0005
.0003
.0009
.0008
.0028
.12
.0005
.91
< .0005
.0005
.098
< .0005
.029
_
Run 43
Crankcase
.0053
<.0002
.0003
.0003
.0021
.0007
.096
.0002
.12
< .0002
<.0002
.078
< .0002
.064
.0003
Run 44
Crankcase
.0033
< .0002
.000
.0005
.0027
.0004
.11
.0002
.055
< .0002
< .0002
.088
< .0002
.074
.0003
o
vo
-------
-110-
TABLE 24
COMBUSTION CHAMBER DEPOSITS
Run
No.
3
4
5
6
7
8
9
U}
14}
16
1.71
18
19
20
21
22
23
29
31
32
40
44
59
Engi ne Operation
(Hours)
103.7
128.8
126.1
127.0
126.1
128.9
127.3
179.5
139.7
180.2
132.6
123.1
124.1
125.1
125.5
123.5
122.6
123.6
124.0
123.0
131 .2
100.0
4 Left
Cylinders
61 .235
73.846
9.7744
49.9348
44.056
69.230
97.930
93.98
55.30
11.80
94.69
77.35
59.53
25.50
8.47
85.54
14.58
61 .60
18.56
18.73
17.22
23.32
Deppsit (Height in Grams)
4 Right
Cylinders Total
54.418 115.653
69.200 143.046
9.3032 19.0776
45.8379 95.7727
43.280 87.330
66.130 135.360
75.790 173.720
91.48 185.46
64.70 139.00
10.05 21.85
94.60 188.85
54.41 131.76
45.25 104.78
20.00 45.50
7.03 15.50
74.98 160.52
15.78 30.36
66.23 127.83
21.39 39.95
21.75 40.48
18.80 36.02
23.62 46.94
-------
-m-
TABLE 25
COMBUSTION CHAMBER DEPOSIT ANALYSIS
Run
No.
4
5
6
7
8
9
12}
14
16
17*
18
19
20
21
22
23
29
31
40
44
59
Weicjht Percent
Pb
64,6
5.9
54.9
72.0
59.8
67.9
66.4
65.6
4.44
62.1
64.4
64.9
40.0
4.92
65.0
<0.7
48.7
32.0
4.0
43.7
Fe
0.26
1 .10
0.27
0.2
0.18
0.217
0.177
0.190
0.587
0.240
0.076
0.186
0.38
0.779
0.108
0.23
0.31
0.18
0.20
0.71
C
5.7
55.9
12.0
11.0
7.8
7.4
6.01
6.08
55.0
6.5
5.2
4.8
25.7
49.3
4.7
52.9
14.4
-
-
23.2
In
8.21
0.55
8.19
0.6
20.67
0.55
9.10
9.12
0.19
8.03
7.42
8.14
3.68
0.24
6.92
0.94
6.3
-
-
1.63
Cl
10.81
0.57
9.78
0.28
0.58
13.55
8.99
9.85
0.40
8.41
11.48
12.11
3.37
0.37
11 .08
3.10
11 .2
-
-
3.35
-------
TABLE 26
ENGINE COMBUSTION CHAMBER DEPOSITS - TRACE METALS
(Wt. %)
Run
No. Nj_C_u.AJ_ C_a Sj_ M_£ Mil C_r in ' lH II
17 <0.010 0.038 0.44 0.075 0.069 1.60 0.013 0.046 0.049 2.10 ,<0.010
18 <0.010 0.005 0.33 0.016 0.056 0.27 0.007 0.023 <0.010 0.25 . <0.010
19 <0.010 0.007 0.10 . <0.010 0.045 0.12 <0.005 0.014 <0.010 0.069.<0.010
20 <0.010 0.009 0.41 . <0.010 0.12 0.13 0.015 0.030 <0.010 0.064 <0.010
21 <0.010 0.051 0.12 0.024 0.066 1.30 0.009 0.013 <0.010 0.79 <0.010
22 <0.010 0.075 0.17 0.054 0.065 3.30 0.012 0.012 <0.010 1.8 <0.010
23 <0.010 0.005 0.028 0.014 0.062 0.73 <0.005 0.007 <0.010 0.32 <0.010
29 0.0002 0.0003 0.0006 0.0015 0.0019 0.130 0.0003 <0.0002 0.0007 0.084 <0.0002
31 . <0.010 0.012 0.034 0.019 0.10 0.58 <0.005 .<0.010 . <0.010 0.35 .<0.010
40 <0.010 0.040 0.110 0.027 0.027 0.88 0.006 . <0.010 .<0.010 0.70 <0.010
44 <0.010 0.022 0.230 0.046 0.013 0.64 0.007 .<0.010 . <0.010 0.73 <0.010
IVJ
I
-------
-113-
75-hour engine stabilization sequence. Figures 26, 27, and 28
indicate the percentage change in these emissions, as an average
of all five (5) conditioning cycles, from 0 engine hours to
75 engine hours.
Graphical representation of actual hydrocarbon emissions during
the conditioning sequence, sampling sequence, and cruise mode
vehicle studies are shown in Appendix A.
The level of aldehydes present in a cold trap condensate of
exhaust gas sample and determined polarographically is shown
in Table 27.
TABLE 27
EXHAUST GAS CONDENSATE ALDEHYDES
Aldehydes
Run No. Mode (ppm of Collected Condensate)
56 2250 rpm:
Before catalyst 590 ppm HCHO
After catalyst 290 ppm HCHO
G. PARTICULATE
1. Mass Emission Rates
Total particulate mass emission levels by run number are
shown in Tables 28 and 29. The mass emission rates are
presented in grams/mile and include all emitted particulate
unless otherwise noted. Additionally, the mass emission rates
are shown by sampling technique, i.e. Andersen-Filter at 1 cfm,
single Gelman A glass fiber filter at 4 cfm, etc.
2. Mass Distribution
Table 30 indicates the mass medium equivalent diameter of emitted
particles for the runs indicated. These data are based on
dilution tube and Andersen sampler samples. The cumulative
mass distribution curves from which these values are obtained
are contained in Appendix B.
-------
Average of all Cycles
loo
8°
01
o
1*
4"
JO
Iff
10
Figure 26
Percent Change in Total and
Saturated Hydrocarbon Emissions
-ID
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-------
Figure 28
Percent-Change in Carbon Monoxide
. ?•
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-------
.117-
TABLE 28
ENGINE STAND RUNS - PARTICULATE MASS EMISSIONS
(Emissions Grams per Mile)
Run No.
3
4
5
6*
6
7*
7
8
9
11
12
13
14
15*
16
17
18
19
20
21
22
23
29
31
32
40
44
52R
52R
52L
52L
55**
55**
55**
56C
59
Code:
Dilution
Mode Tube Andersen
SS - 60 mph
>
0.000598
.000762
-
.002242
-
.006015
.017426
.008622
.007324
Dow Cycle .007833
SS - 60 mph . .012634
Dow Cycle .004030
SS - 60 mph
SS - 60 mph .002962
Dow Cycle .001693
SS • 60 mph .006700
.006407
•>
.006683
.000642
.001944
.001944
.00085
.00905
.00063
.00056
' .00076
.0005
SS - 30 mph .0001
SS - 60 mph .0001
SS •• 30 mph .0005
SS - 60 mph .0003
SS - 30 mph .00015
Dow Cycle .0007
SS - 60 mph .00152
SS - 60 mph .00035
SS Steady State
THF Total Hot Filter
* Blank dilution air only
R Rich Carburetor Mix
L Lean Carburetor Mix
** = Platinum Muffler
*** = 142 mm Gel man Type A glass
0.02751
.03734
.000481
.000659
.014860
.001145
.024635
.064896
.033991
.039996
.043608
.039670
.031209
.000072
.002792
.003677
.043537
.033556
.037601
.004858
.002636
.029578
.00169
.01247
.00114
.00452
.00235
.0152
.0405
.0344 .
.0186
.0127
.0105
.0156
.0032
.00319
fiber f1
Back-up
1 cfm
-
0.068436
.002675
.002986
.013297
.004722
.131804
.073328
.035797
.069925
.078990
.083688
.105388
.002366
.010515
.005048
.096835
.052133
.049195
.013223
.008561
.056243
.00055
.04321
.00141
.00631
.01100
.0155
.0011
.0016
.0083
.1038
.0383
.0713
.0259
.0235
Her operating
Total
0.02751
.109040
.002987
.003645
.030399
.005868
.162455
.155641
.07841
.117246
.130431
.135999
.140629
.002438
.016267
.010419
.147074
- .092097
.093480
.018724
.013241
.091014
.00310
.06474
.00320
.01141
.01412
.0312
.0417
.0361
.0274
.1168
.0489
.0876
.03064
.0271
at 4 cfm
4 cfm
Filter*** Other
0.0026 THF
0.0670 .0499 THF
.0016
.0126
.0135
.0308
.0406
.0361
.0269
.1205
.0737
.0978
.0135
flow
-------
-118-
TABLE 29
CHASSIS DYNAMOMETER
(Emissions Grams per Mile)
Vehi cl e
Run No.
24
25
27
28
30
33
34
35A
35B
35C
36*A
36*B
37
38
39C
39A
39B
39D
39 E
41
42A
42B
42C
43
45
46
46
46
46
46
46
46
SS
SS
SS
SS
HS
SS
SS
cs
HS
HS
CS
SS
SS
SS
cs
HS
HS
HS
HS
SS
cs
HS
SS
SS
SS
cs
cs
cs
cs
HS
HS
HS
Mode
- 60
- 60
- 60
- 60
FTP
- 60
- 60
FTP
FTP
FTP
FTP
- 60
- 60
- 60
FTP
FTP
FTP
FTP
FTP
- 60
FTP
FTP
- 60
- 60
- 60
FTP
FTP
FTP
FTP
FTP
FTP
FTP
mph
mph
mph
mph
mph
mph
mph
mph
mph
mph
mph
mph
mph
Mi
10
10
7
8
19
30
30
12
35
53
53
53
2
3
3
1 eage
,000
,360
,900
,260
,000
500
,000
,400
-
-
700
-
,885
,000
500
-
-
-
-
600
,000
,000
,000
,500
,000
,770
-
-
-
-
_
Di 1 uti on
Tube
0.0059
.0051
.0004
.0016
-
.0000
.0302
-
-
-
-
-
.0007
.0005
-
-
-
-
-
.0000
-
-
.0005
.0002
.0001
-
-
-
-
-
-
_
Andersen
0.0364
i0357
.0343
^0433
-
.0010
.0355
-
-
-
-
-
.0279
.0286
-
-
-
-
-
.0014
-
-
.0007
.0018
.0042
-
-
-
-
-
-
.
Back-up
1 cfm
0.0817
.0738
.0668
.0746
-
.0108
.1357
-
-
-
-
-
.1069
.1007
-
-
-
-
-
.0392
-
-
.0075
.0094
.0182
-
-
-
-
-
-
-
= Total
0.1241
.1147
.1064
.1196
-
.0119
.2015
-
-
-
-
-
.1355
.1299
-
-
-
-
-
.0408
.0097
.0093
.0088
.0115
.0225
-
-
-
-
-
-
-
4 cfm
n 1 ter
0.1160
.0935
.0855
. 1054 {
. 1558 ^
.0032
.1760
.5795
.4014
.5761
.2019
.0162
.0849
.0896
.0059
.0119
.0144
.0068
.0102
.0446
.0037
.0588
.0106
.0507
.0409
.0426
.0400
.0362
.0477
.0400
0 the i
, 109***
.079***'
.101***
_ ;-\ 7 i; * * * 1
-------
TABLE 29 (Contd.)
Run No.
46H
48C
48**E
48**A
48**B
48**D
HS
CS
CS
HS
HS
HS
48**FF HS
49A
49B
49C
50
51A
51B
51C
53A
53B
53C
54
58A
58B
58C
58E
60A
606
60C
61
62A
62B
62C
63
65
66A
66B
66C
67
Code:
CS
HS
HS
SS
CS
HS
HS
CS
HS
HS
SS
CS
HS
HS
SS
CS
HS
HS
SS
CS
HS
HS
SS
SS
CS
HS
HS
SS
Vehicle
Mode Mileage
FTP
FTP 4,250
FTP
FTP
FTP
FTP
FTP
FTP 5,000
FTP
FTP
- 60 mph 3,000
FTP 3,400
FTP
LA4
FTP 13,000
FTP
LA4
- 60 mph 13,100
FTP 10,000
FTP
LA4
- 60 mph
FTP 9,101
FTP
LA4
- 60 mph
FTP 17,750
FTP
LA4
- 60 mph
- 60 mph
FTP 9,286
FTP
LA4
- 60 mph
•"Temperature = 15°F
**Temperature = 20°F
Dilution Back-up
Tube Andersen 1 cfm =
...
.
-
_
_
.
.
_
.
_
.0029 .0447 .1086
_
_
_
-'
_
.
.0000 .0006 .0200
...
-
_
.0002 .0060 .0100
-
. -
_
.0026 .0039 .0128
-
-
_
.0001 .0027 .0065
.0001
.
.
-
.0040 .0485 .1005
CS = Cold Start HS
FTP = California 7 Mode SS
4 cfm
Total Filter
.0353
.0554
.1214
.0583
.0443
.0566
.0468
.0911
.0519
.0639
.1565 .1189
.2071
.0813
.1091
.0617
.0404
.0708
.0206 .0089
.0196
.0085
.0108
.0162 .0020
.0690
.0336
.0466
.0193 .0113
.0217
.0127
.0068
.0093 .0036
.0001 .0004
.1742
.0988
.0605
.1530 .1202
= Hot Start
= Steady State
***Beta-Gauge LA4
****Thermo-Systems, Inc., mass
monitor
Federal 23 Mode
-------
-119-
TABLE 30
MASS MEDIUM EQUIVALENT DIAMETER
EXHAUST PARTICIPATE
Run No.
4
6
7
e
9
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
27
28
29
31
32
33
34
37
38
40
41
42
43
44
45
47
47
50
52
52
52
52
54
55
55
55
56
56
RPM
1200
2250
2250
2250
1200
1200
2250
1200
Dow Cycle
2250
1200
Engine (E)
Vehicle (V)
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
E
V
V
V
V
E
E
E
V
V
V
V
E
V
V
V
E
V
E
E
V
E
E
E
E
V
E
E
E
E
E
MMED Pb MMED
0.10
1.5
«0.10
0.65
1.1
•v.0.10
•x.0.10
•v.0.10
<0.10
«0.10
<0.10
0.7
0.13
<0.10
•v.0.10
«0.10
<0.10
<0.10
«0.10
<0.10
<0.10
<0.10
<0.10
<0.10
1.0
«0.10
0.29
<0.10
<0.10
0.37
«0.10**
<0.10**
<0.10
«0.10
<0.10
•vO.10 <0.10
<0.10 <0.10
<0.10
1.42****
0.50***
3.20****
3.20***
<0.10
«0.10*
<0.10
«0.10
0.42**
«0.10**
Code:
= Less than
« Much less
» Approximately
*Plat1num muffler
**Propr1ctary catalyst muffler
***Lean carburetor, ml x
****R1ch carburetor mix
-------
-120-
3. Major Element Distribution ,
The mass medium equivalent diameters for major elements
present in exhaust particles collected is presented by run
number in Table 31. Cumulative mass distribution curves from
which these values were extrapolated are shown in Appendix C.
4- HC1, NH3> and H,,0
The level of HC1, NH3, and FLO present in exhaust particles
as determined by mass spectrometry is shown in Table 32 by
run number. Refer to analytical section for the significance
and validity of comparing one run to another. Data is
presented by major size fraction for each run.
5. Trace Metal Analysis
The trace metal content of collected exhaust particles as
determined by emission spectrometry is presented in Table 33
by run number and sample source.
X-ray flourescence analysis of the small amount of particulate
collected during run 56C (catalyst equipped vehicle) is shown
in Table 34. Results are in ratios of amount present. Percentages
could not be calculated reliably due to low sample weight.
TABLE 34
X-RAY FLUORESCENCE ANALYSIS
RUN 56C - SLIT SAMPLES A, B, C
Slit
Pb
Ba
Br
Zn
Fe
Mn
Ca
K
Cl
S
P
*Results on Sample A are on the composite
after removing magnetic portion
Sample letter also refers to sample location
(see Figure 1)
Values Expressed •
A,*_
5.7
0.2
0.14
0.5
1.1
0.2
0.14
0.08
1.0
3.3
2.3
B^
4.1
0.2
0.1
3.6
4.6
0.1
0.1
0.5
0.4
2.4
1.3
in Ratios
C_
1.1
0.1
0.06
1.4
0.5
_
0.1
0.06
0.4
1.1
0.8
-------
-121-
TABLE 3]
ENGINE STAND RUNS ONLY
ELEMENTAL MASS MEDIUM EQUIVALENT DIAMETER - Pb/Cl/Br/Organic
Run No. Pb (MMED) Cl (MMED) Br (MMED) Organics (MMED)
4
6
7
8
9
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
27
28
29
31
32
33
34 •
37
38
40
41
42
43
44
45
50
54
tO.lO .«0.10 <0.10
3.1 0.5 2.7
«0.10
0.35 - -uO.lO
2.0 1.2
^0.10 'x.O.lO 'vO.lO
•x-0 . 1 0 -vO . 1 0 -v.0 . 1 0
•vO . 1 0 -\,0 . 1 0 -\,0 . 1 0
<0.10 <0.10 <0.10
1.5
1.2 - -
-
. <0.10 >10.0 <0.10
. <0.10 . <0.10 . <0.10
-
1.35 1.90 . <<0.10
. <0.10 . <0.10 . <0.10
-
-
•
. <0.10 6.0 <0.10
•x.0.10 3.3 <0.10
<0.10 <0.10 <0.10
' - - -
;
-
-
-
-
-
-
-
-
-
-
-
0.68
0.2
,«0.10
0.3
<0.10
<0.10
<0.10
«0.10
«0.10
_
0.4
1.5
-
-x.0.10
0.42
. «0.10
<0.10
<0.10
<0.10
. <0.10
-
1.15
0.9
<0.10
-
-
•vO.10
-
-
0.31
-
-
-
<0.10
1.8
_
< = less than O.lOji
« = much less than
^ = approximately
-------
-122-
FRACTIONS OF HC1, NH.
TABLE 32
AND H20 PRESENT IN EXHAUST PARTICLES
(Relative Units/mq Sample)
(Determination by Mass Spectrometry)
Run No.
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
7
8
8
8
8
8
9
9
9 ,
9
9
9
9
11
11
11
11
11
11
11
Location
AP-5
6
Filter
AP-1
2
3
4
5
6
Filter
S-l
2
3
4
5
6
7
AP-1
2
5
S-l
2
3
3'
4
5
6
7
AP-1
2
3
4
5
6
AP-1
2
3
4
5
6
Filter
AP-3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
0.018
.074
.148
.013
.013
.017
.051
.143
.247
.258
.0017
.003
.03
.03
.03
.03
.03
.337
.211
.010
.002
.003
.002
.004
.003
.002
.002
.002
.078
.025
.031
.052
.071
.086
.000
.001
.001
.002
.005
.012
.007
.022
.042
.068
.049
.060
.075
.031
.016
.022
.065
.093
.070
.026
.011
.010
.010
.025
.036
.029
0.059
.097
.099
.013
.014
.019
.048
.089
.089
.133
.027
.096
.070
.086
.11
.12
.10
.264
.188
.075
.28
.27
.29
.23
.28
.28
.28
.26
.027
.017
.033
.063
.114
.068
.026
.027
.030
.045
.081
.116
.125
.020
.041
.072
.066
.046
.043
.033
.034
.069
.164
.138
.080
.016
.017
.026
.062
.152
.089
.046
"HC1
0.002
.006
.113
.004
.002
.002
.023
.134
.183
.161
0
0
0
0
0
0
.002
.081
.081
.004
0
.002
.001
.008
.001
0
0
0
.072
.012
.026
.037
.054
1.38
.001
.000
.000
.001
.000
.003
.001
.008
.012
.033
.016
.030
.014
.002
.001
.002
.010
.006
.018
.005
.003
.003
.003
.006
.007
.012
Sample Wt
(mg)
1.15
0.40
8.70
28.20
17.10
11 .25
.00
.90
.30
.90
10.10
10.40
10.25
50
15
70
2.00
0.50
0.50
0.80
9.45
9.35
10.57
1.20
10.50
10.50
9.90
10.80
8.55
6.70
6.30
3.25
2.65
10.20
12.23
15.85
15.46
8.66
5.05
2.61
7.06
9.70
6.40
7.80
9.50
9.90
9.70
10.30
10.00
75
20
60
6.15
10.40
8.90
10.20
80
80
40
10.80
Code: AP- = Andersen collection plate-number (see Table 6 for size cutoff)
S- = Slit-number
SW- = Sweepings-letter
-------
-123-
TABLE 32 (Cont.)
Run No.
12
12
12
12
12
12
12
13
13
13
13
13
13
13
14
14
14
14
14
14
14
16
16
16
16
16
16
16
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
Location
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
S-l
AP-1
2
3
4
5
6
7
Filter
S-l
AP-1
2
3
4
5
6
7
Filter
S-l
S-7
NH,
J
0.006
.006
.003
.017
.051
.068
.072
.027
.009
.007
.008
.022
.033
.030
.028
.008
.006
.008
.043
.084
.092
.157
.019
.012
.005
.008
.003
.007
.172
.031
.008
.006
.004
.004
.002
.052
.027
.012
.009
.009
.011
>.003
.001
.027
.008
.005
.011
.036
.073
.071
>.122
•V, 0
.030
.011
.008
.0183
.054
.123
.096
>.055
.019
.070
H-0
0.019
.017
.019
.041
.057
.050
.039
.021
.020
.031
.067
.127
.074
.037
.023
.012
.017
.034
.067
.062
.042
.318
.255
.216
.142
.273
.188
.231
.333
.588
.180
.206
.244
.294
.066
.050
.054
.090
.146
.110
.068
>.054
.15
.027
.017
.019
.039
.075
.067
.047
>.050
.14
.022
.014
.018
.0315
.058
.064
.056
>.063
.068
.072
HC1
0.007
.008
.005
.005
.024
.045
.036
.005
.002
.002
.002
.008
.005
.009
.006
.001
.001
0
.009
.007
.048
.012
.007
.004
.007
.005
.006
.000
.013
.016
.006
.005
.007
.008
.003
.051
.009
.032
.029
.037
.021
>.009
.004
.006
.002
.002
.003
.015
.030
.022
>.05
-u 0
.008
.001
.001
.0013
.007
.065
.078
•x, 0
.005
.014
Sample Wt.
(mg)
10.61
10.36
9.84
6.45
6.74
7.90
6.41
10.70
11.30
9.00
5.10
3.55
3.55
9.10
7.40
9.61
7.66
3.62
3.30
1.90
6.21
1.17
1.17
0.87
0.50
0.65
0.55
0.30
1.05
0.30
0.70
0.65
0.55
0.40
1.20
12.30
7.74
9.83
9.42
11.13
9.24
13.81
11.31
14.2
19.16
16.15
6.48
4.68
4.40
7.95
4.60
8.07
17.16
17.12
12.02
6.56
5.74
3.58
8.85
0.81
11.73
8.95
-------
-124-
TABLE 32 (Cont.)
Run No.
21
21
21
21
21
21
21
21
21
21
22
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
23
23
23
24
24
24
24
24
24
24
24
25
25
25
25
25
25
25
25
28
28
28
28
28
28
28
29
29
29
29
29
29
29
29
Location
NH
H,0
HC1
AP-1
2
3
4
5
6
S-l
2
3
4
AP-1
2
3
4
5
6
Filter
S-l
2
3
4
AP-1
2
3
4
5
6
7
Filter
S-l
2
3
4
5
AP-1
2
3
4
5
g
\J
7
Filter
AP-1
2
3
4
5
6
7
Filter
AP-1
2
C.
3
A
H
5
6
Filter
AP-1
2
3
4
5
6
Filter
Total Hot
0.22
.074
.038
.027
.032
.059
•x, 0
•x, 0
•x, 0
.002
.005
.002
.006
.012
.009
.008
> .001
•V. 0
•x, 0
•x, 0
•X. 0
1.024
0.009
.012
.029
.077
.189
.179
> .154
•x, 0
•X, 0
•v. 0
•X, 0
.002
.015
.0087
.013
.037
.160
.23
.47
>.037
.032
.0094
.012
.046
.095
.11
.40
>.027
.039
.01
.01
.024
.078
.100
>.025
.006
.011
.005
.008
.018
.340
>.002
•X, 0
0.14
.086
.095
.15
.21
.24
.44
.59
.56
1.10
0.300
.293
.250
.330
.465
.664
> .109
.45
.53
.64
.67
.003
.019
.032
.150
.377
.248
.157
> .077
.33
.28
.36
.36
.82
.017
.014
.025
.160
.23
1.49
0.27
>.052
.028
.031
.078
.084
.26
.35
.28
>.048
.027
.02
.023
.094
.087
.330
.027
.20
.19
.32
.22
.22
.87
>.026
0.038
.0028
.0011
.0018
.0018
•X, 0
.014
.014
•x, 0
-X, 0
.018
.021
.008
.010
.006
.015
>:.002
.002
•x, 0
.42
.001
•x. 0
-X, 0
•X, 0
.002
.010
.029
.071
> .133
-X, 0
•X, 0
•x, 0
•x, 0
•V, 0
.0013
•X, 0
•V. 0
•V, 0
•X, 0
•X, 0
.021
> .034
.002
•X, 0
-X, 0
•X, 0
.071
•x, 0
.30
>.055
.0008
.0008
.0008
.003
.0006
•x, Q
.004
•X, 0
•x, 0
•X, 0
•x, 0
•x, 0
^ o
•x, 0
•X..001
Sample Wt.
(mg)
3.04
2.31
1.57
1.10
0.71
0.37
10.85
9.61
3.08
0.26
0.705
0.40
0.85
0.70
1.20
0.40
3.05
10.31
10.20
11.73
2.33
8.3
9.9
7.05
3.00
2.40
1.70
3.90
8.30
9.21
11.08
10.76
3.19
0.94
5.12
4.94
3.80
0.66
0.55
0.31
1.18
8.66
53
93
74
18
0.66
0.70
1.17
9.38
80
66
40
19
26
C.31
7.42
0.18
0.21
0.36
0.38
0.16
0.14
7.31
11.05
-------
-125-
TABLE 32 (Cont.)
Sample Wt.
Run No. Location NH, H,0 HC1 (mg)
——— ———— —o —c—
31 AP-1 0.019 0.019 0.002 8.44
31 2 .026 .022 .003 4.60
31 3 .038 .031 .004 3.32
31 4 .041 .12 .0002 1.30
31 5 .12 .11 .007 1.09
31 6 .10 .24 0 0.4
31 Filter >.134 >.048 >.47 12.53
31 4 cfm >.14 >.003 >.13 9.04
33 Filter -x. 0 .053 .001 9.17
33 Filter .019 .046 .002 9.0
34 AP-1 .375 .260 .073 0.93
34 2 .177 .585 .029 2.68
34 3 .043 .113 .010 2.55
34 4 .039 .163 .010 2.08
34 5 .055 .128 .010 2.89
34 6 .075 .215 .010 0.98
34 7 .048 .058 .011 4.03
34 Filter .009 .038 .002 9.46
36 Filter CS .003 .048 .002 8.69
36 Filter SS .001 .021 -x. 0 9.53
38 S-l -x, 0 .076 .001 15.0
38 3 .087 .121 .041 12.75
38 5 .328 .169 .507 7.02
38 7 .507 .402 .153 1.31
38 Filter .557 .174 .235 2.18
AP-1
2
3
4
5
6
Filter
4 cfm
Filter
Filter
AP-1
2
3
4
5
6
7
Filter
Filter CS
Filter SS
S-l
3
5
7
Filter
AP-1
2
3
4
5
6
Filter
S-l
3
5
Filter
S-l
5
7
Filter
SW-A
E
F
G
AP-1
2
3
4
5
6
7
Filter
— o
0.019
.026
.038
.041
.12
.10
>.134
>.14
-X, 0
.019
.375
.177
.043
.039
.055
.075
.048
.009
.003
.001
•x, 0
.087
.328
.507
.557
.028
.024
.016
.016
.029
.091
.07
.005
.001
.001
.002
-v 0
0
•x, 0
•x, 0
.366
.447
.002
.464
.015
.013
.031
.030
.027
.115
.036
•x, 0
— c—
0.019
.022
.031
.12
.11
.24
>.048
>.003
.053
.046
.260
.585
.113
.163
.128
.215
.058
.038
.048
.021
.076
.121
.169
.402
.174
.120
.087
.142
.146
.163
.370
.057
.214
.299
.331
.303
.077
.437
.5217
.13
•x, 0
.004
.029
.004
.978
.567
.847
1.000
0.838
1 .055
0.328
.328
0.002
.003
.004
.0002
.007
0
>.47
>.13
.001
.002
.073
.029
.010
.010
.010
.010
.011
.002
.002
•v, 0
.001
.041
.507
.153
.235
-X, 0
•V 0
•X, 0
•X, 0
-v. 0
-v. 0
.007
. -x, 0
* 0
> 0
•x/ 0
•X, 0
-x, 0
-X, 0
-X, 0
-x, 0
•V, 0
0
-X, 0
•X, 0
0
0
0
0
0
0
0
40 AP-1 .028 .120 -x, 0 0.77
40 2 .024 .087 -v. 0 2.03
40 3 .016 .142 -v. 0 2.28
40 4 .016 .146 -v. 0 1.5
40 5 .029 .163 -v. 0 1 .66
40 6 .091 .370 -v. 0 0.24
40 Filter .07 .057 .007 8.38
41 S-l .005 .214 • -v. 0 1.77
41 3 .001 .299 -v. 0 6.47
41 5 .001 .331 -y 0 2.01
41 Filter .002 .303 -x, 0 9.9
42 S-l -x, 0 .077 -v. 0 3.42
42 5 -v 0 .437 -v. 0 2.32
42 7 -v. 0 .5217 -x- 0 0.35
42 Filter -v. 0 .13 •«. 0 11.0
43 SW-A .366 -x. 0 -v. 0 4.8
43 E .447 .004 -v. 0 3.1
43 F .002 .029 0 9.98
43 G .464 .004 -v. 0 0.74
44 AP-1 .015 .978 -v. 0 0.21
44 2 .013 .567 0 0.23
44 3 .031 .847 0 0.37
44 4 .030 1.000 0 0.36
44 5 .027 0.838 0 0.54
44 6 .115 1.055 0 0.33
44 7 .036 0.328 0 0.40
44 Filter % 0 .328 0 7.4
-------
-126-
TABLE 32 (Cont.)
Run No.
45
45
45
45
45
45
45
45
46
46
46
46
46
48
48
48
48
48
48
53
53
53
53
53
53
56B*
56B*
56C**
56C**
56C**
56B*
568*
56B*
56B*
56B*
56B*
56C**
56C**
56C**
56C**
56C**
56C**
Location
AP-1
2
3
4
5
6
7
Filter
AP-1
2
4
5
6
AP-1
2
3
4
5
6
AP-1
2
3
4
5
6
SW-J
H
G
I
K
AP-1
2
3
4
5
6
AP-1
2
3
4
5
6
HC1
0.063
.213
^ 0
-V, 0
.085
.018
.103
.037
.024
.026
.012
.003
•V 0
.019
.004
.010
.0009
.015
•V, 0
.003
.069
.17
.004
.006
.014
.008
.20
.004
.007
.008
0.319
2.246
2.30
0.862
1.83
0.329
.525
.048
.596
.673
.939
.538
.543
.6
.655
1.091
0.795
.495
1.67
0.42
, 1.41
( 0.79
.48
.30
4.82
.60
.55
.56
.65
.76
-v, 0
-v, 0
-v, 0
•v, 0
«, 0
* 0
i, 0
0.014
•v, 0
-------
TABLE 33
EXHAUST PARTICULATE - TRACE METALS
Run
No.
11
12
29
31
34
38
Fe
0.16
.19
.15
.24
.18
.15
.098
3.5
4.3
3.0
4.9
3.1
2.5
1.6
0.95
1 .3
0.16
.14
.31
.39
.19
.16
.18
2.1
3.4
2.4
3.5
4.7
4.3
2.5
0.1
.1
.09
< .05
< .05
< .05
.04
.18
23.0
27.0
1 .3
Ni
<0.01
< .01
<'.025
< .025
< .025
< .025
< .01
.017
.012
.011
.014
.011
.029
< .010
< .010
< .010
< .01
< .01
< .01
< .025
< .025
< .025
< .01
<.4
i!o
0.6
.7
.6
1 .9
0.3
.09
.07
< .05
< .05
< .05
< .05
< .03
< .01
.036
< .02
< .05
Cu
0.018
.025
.034
.040
.034
.054
.008
.010
.011
.010
.011
.019
.016
.009
.008
.010
.038
.025
.032
.027
.027
.028
.006
.4
.4
.4
.3
.4
.3
.1
.04
.05
.06
.02
.01
.02
< .01
.005
.053
.024
.055
Al
0.032
.08
.048
.11
.11
.12
.023
.080
.062
.055
.075
.076
.13
.063
.064
.043
.074
.027
.044
.043
.072
.11
.010
.6
1 .0
1 .1
1 .0
1 .0
3.7
35.5
0.1
.1
.4
.2
.1
.2
.1
.097
.094
.044
.500
Ca
0.13
.10
.18
.30
.36
.23
.095
.031
.063
.025
.032
.036
.088
.078
.050
.12
.17
.17
.15
.29
.27
.29
.058
2.3
1 .8
2.0
1 .8
1 .5
4.1
44.5
0.2
.3
.4
.3
.1
.3
.2
.48
1.3
0.51
2.6
Si
0.039
.038
.036
.068
.050
.038
< .01
.046
.060
.039
.087
.095
.084
.13
.054
.079
.061
.03
.034
< .025
.072
.046
< .01
.5
1.8
2.7
1.2
1.6
11.7
2.6
0.08
.4
.3
.08
.07
.09
.1
.10
.1
.07
.08
\ •-
Mg
0.066
.063
.11
.32
.43
.16
.005
.71
.15
.33
.57
.48
.65
.46
.33
.38
.086
.083
.073
.14
.22
.20
.027
1.8
1 .8
1.6
1 .5
1 .2
5.0
11.7
0.2
.2
.2
.1
.1
.1
.1
.087
.16
.078
.25
Mn
<0.005
< .005
< 01
< .01
< .01
< .01
< .005
.074
.060
.036
.067
.036
.10
.015
.011
.012
< .005
<.005
< .005
< .01
< .01
< .01
< .005
< .2
.3
.2
.2
.2
.8
.1
.03
.02
.01
.02
.02
.01
.01
< .005
.074
.062
< .01
Cr
<0.01
.012
< .025
< .025
< .025
< .025
< .01
.075
.059
.054
.085
.056
.13
.043
.030
.034
< .01
< .01
< .01
<.025
< .025
< .025
< .01
< .4
< . 4
< .4
< .4
< .4
< .6
< .2
< .05
< .05
< .05
< .05
<.05
< .05
<.03
<.01
.022
.020
< .05
.1^111* i t
Sn
<0.01
< .01
< .025
< .025
< .025
< .025
< .01
.019
.017
.010
.015
.012
.016
< .01
< .01
< .01
< .01
< .01
< .01
< .025
.027
< .025
< .01
< .4
< .4
< .4
1.4
0.4
< .6
< .2
< .05
< .05
< .05
< .05
< .05
< .05
< .03
<.01
< .01
<.02
< .05
1 V ^ 1 1 lr /
Zn
0.068
.059
.09
.14
.14
.11
.09
4.4
9.3
5.4
7.0
9.7
4.2
0;51
.32
.41
.069
.051
.061
.11
.11
.088
.069
< .8
.8
.8
1.2
1.1
< 1 .0
2.9
0.1
.2
.2
< .1
< .1
< .1
< .05
.088
.28
.16
.12
Ti
<0.01
< .01
<.025
< .025
< .025
< .025
< .01
< .010
< .010
< .010
< .010
< .010
< .010
< .010
< .010
< .010
< .01
< .01
< .01
< .025
.70
< .025
< .01
< .4
< .4
< .4
< . 4
< .4
< .6
.8
< .05
< .05
< .05
< .05
< .05
< .05
< .03
< .01
.01
.02
.05
Mo
.
-
-
-
-
-
-
0.010
.007
.007
.008
.005
.008
.006
.004
.005
_
_
.
-
_
_
-
_
-
-
-
.
-
-
_
_
-
-
.
.
-
-
< .005
< .01
< .025
Co
.
-
-
-
-
-
-
_
_
.
-
-
.
.
-
-
_
.
.
-
.
_
-
_
-
-
-
.
-
-
_
-
-
-
-
-
-
-
0.035
< .01
< .025
Cd
_
-
-
-
-
-
-
_
-
-
•
-
-
.
-
-
^
-
.
.
_
_
-
_
-
-
-
-
0
-
_
.
-
-
-
.
-
-
<0.005
< .01
< .025
ro
Sample
Source*
AP-1
2
3
4
5
6
Filter
S-l
S-2
SW-A
B
C
0
E
F
G
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter**
AP-1
2
3
4
5
6
Filter
Filter
SW-F
H
*Code: AP- = Andersen Plate-number S- = Slit-number SW- = Sweepings-letter
**Values could be suspect due to sample size and impurities of the blank.
-------
TABLE 33 (Cont.)
Run
No.
40
41
42
43
44
45
46
48
53
56
Fe
0.38
5.0
4.4
2.5
0.22
.10
.15
7.1
21.0
4.1
19.0
51.0
2.1
1.0
53.0
44.0
-
1 .0
11 .0
1.8
0.07
0.46
33.0
23.0
36.0
43.0
51.0
28.0
42.0
29.0
58.0
13.0
29.0
0.90
4.5
3.6
5.6
4.5
2.6
2.6
0.34
N1
<0.05
< .02
< .02
< .05
<.05
< .05
<.01
< .05
< . 10
< .50
< .02
.032
<.05
< .05
.024
.095
.3
<.02
<.02
<.05
< .05
<.05
<.02
<.05
<.5
.036
.035
< .1
.030
.011
.040
.013
.022
< .05
.008
' .004
.07
.01
.006
.004
.1
Cu
0.05
.052
.058
.24
.06
.04
.009
4.8
0.43
.04
.11
.44
.28
.18
.048
.67
-
.044
.038
5.2
0.02
.03
.13
.82
2.1
0.060
.21
14.0
0.49
.056
.094
.33
.080
.090
.03
.03
.30
.10
.06
.08
.09
Al
1.3
0.046
.044
.22
.14
< .05
.21
.58
2.2
1 .7
2.2
1 .0
0.39
4.5
0.10
.27
1.0
0.070
.090
.35
<.05
.12
.32
.33
3.0
0.12
.19
.40
.30
.26
.44
.12
1.1
0.32
.10
.10
1.8
1.0
0.20
.20
.13
Ca
2.9
<0.02
.028
.17
.30
.15
.57
5.2
7.9
3.0
1.8
2.3
0.51
13.6
0.12
.39
1.0
0.072
.084
.60
.29
.38
.19
.24
1.5
0.12
.09
2.6
0.44
.22
.46
.72
8.50
2.2
0.09
.10
.08
.10
.10
.10
.78
S1
4.3
0.20
.10
.05
.2
.1
.2
.3
.3
.5
.4
.2
.3
3.6
0.06
.2
.8
.08
.20
.30
.1
<.l
.3
.3
< .5
.1
.06
.5
.1
.1
.2
.04
.70
< .10
_
-•
_
_
_
_
.
M£
0.94
.66
1.0
0.60
.30
.22
.19
.27
< .10
< .50
.20
.16
.095
3.8
0.23
.60
.50
2.2
2.5
1.8
0.11
.61
3.2
0.14
3.0
0.10
.11
.60
.22
.16
.26
.14
1.5
0.27
5.1
5.2
3.9
5.1
4.0
4.3
.12
Mn.
<0.01
.016
.014
< .01
< .01
<.01
<.005
.070
.050
< .1
.14
.19
< .01
< .01
.13
.17
< .2
.008
.018
< .01
< .01
< .01
.11
.050
. < .1
.14
.15
< .03
.13
.092
.18
.030
.100
< .01
.06
.04
.20
.10
.04
.06
< .02
Cr
Sn
0.05 <0.05
< .02
< .02
<.05
< .05
< .05
.016
<.05
< .1
< .5
.023
< .02
< .05
.23
.019
< .05
< .20
<.02
< .02
<.05
< .05
< .05
<.02
< .05
< .5
< .01
< .01
< .01
< .02
< .01
< .02
< .01
.020
< .05
<.05
< .05
.5
.2
< .05
.07
.68
< .02
< .02
< .05
< .05
< .05
<.01
< .05
< .1
< .5
< .02
< .02
< .05
<.05
< .01
< .05
< .2
< .02
<.02
< .05
< .05
< .05
< .02
< .05
< .5
< .01
< .01
< .01
< .02
< .01
<.02
< .01
<..02
<.05
< .05
< .05
< .05
< .05
< .05
< .05
.1
Zn
<0.01
.92
.66
.95
.80
.52
.062
1.1
2.8
2.7
0.60
.76
2.0
0.86
.59
.84
.80
1.7
1.7
1.9
<0.10
1 .2
1.9
2.9
3.0
10.0
10.0
3.6
2.1
1.2
2.2
2.4
4.5
<0.1
4.7
3.6
3.0
4.8
3.6
3.0
<0.01
Ti
<0.05
<.02
< .02
< .05
< .05
< .05
< .01
< .05
< .10
< .5
< .02
< .02
< .05
< .05
< .01
< .05
< .02
<.02
< .02
< .05
< .05
< .05
<.02
<.0.5
< .5
<.01
< .01
<.01
<.02
< .01
< .02
< .01
<.02
< .05
<.003
< .003
< .003
< .003
< .003
< .003
< .1
Mo
_
<0.01
< .01
< .025
-
-
-
< .025
< .06
< .25
< .01
< .01
< .025
-
.007
< .025
< .13
< .01
< .01
< .025
_
-
<.01
-------
-129-
6. Crystalline Species
X-ray diffraction analysis was made of selected exhaust particle
samples. The crystalline species present in shown by run
number in Table 35.
TABLE 35
X-RAY DIFFRACTION ANALYSIS OF EXHAUST PARTICLES
Run No.
8
Source
Andersen
Plate 6
Filter
Crystalline Species Present
Pb Br,
UP 1875* chief constituent on AP**-6
and filter
11
Andersen
Plate #6
Filter
Andersen
Plate #6
Filter
Pb C12
UP 1875 (high Cl) and 5-10% PbCl2 on AP-6
UP 1875 only, filter
Pb (Cl, Br)2
UP 1875 present (20-30%) on AP-6 and filter
12
Andersen
Plate #1
Pb (Cl, Br)2
UP 1875 5-10% on AP-1, 10-20% on filter
13
Andersen
Plate #6
Filter
Pb (Cl, Br)2
UP 1875 10-20% on AP-6 and 20-30% on filter
14
Andersen
Plate #6
Filter
Pb (Cl, Br)2
UP 1875 50% on AP-6 and 30-40% on filter
*UP 1875 = Unidentified Pb-Cl-Br structure
**AP = Andersen Plate
-------
-130-
Table 35 (Contd.)
Run No. Source
15
Andersen
Plates #1 ,
#4, and #6
Crystalline Species Present
Quartz; Calcite; NaCl ; NH4C1 - all
weak 1ines
16
17
Andersen
Plates #1,
#3, and #6
Andersen
Plates #1,
#3, and #6
Pb (Cl, Br)2;
Pb (Cl, Br)2; NH4C1;
4Pb-Pb S04 (trace)
OH
OH
42
Dilution tube
Slit samples
Fe
NaCl major component
Fe0 10-20
Fe203
10-20
a FeOOH 10-20
Quartz <5
Dilution tube
Sweepings
NaCl major component
5-10
5-10
Quartz <5
Fe304
Fe2°3
45
Dilution tube
Sweepings
Pb (Cl , Br)2
Fe0 20-30
Fe203
Fe
10-20
- Cl:Br 1:1, major componei
46
Dilution tube
Slit samples
Dilution tube
Sweepings
Fe3°4
Fe2°3
ZnO
Fe
Fe3°4
Fe203
ZnO
Fe
40-60
30-40
10-20
^5
40-60
20-30
20-30
^5
-------
-131-
7. Particle Morpheus
Particle morpheus has been examined by optical microscopy,
transmission electron and scanning electron microscopy. Optical
techniques have been used to evaluate particle birefringence,
and general size and shape. Another study conducted by this
laboratory for the Environmental Protection Agency^ ', Office
of Air Programs was directed toward the examination of the
fate of exhaust particles in the exhaust system itself. That
study found the birefringent techniques showed a decrease in
discrete particle crystalline character as the particles
approached the tailpipe. Not surprisingly, in a similar examin-
ation of the exhaust particles collected after emission from
the tailpipe in this study the birefringence was found to be
very low, indicating that most particles are broken up,
conglomerates, with very few single, discrete particle species.
Examples are shown in Figures 29 through 32.
The transmission electron microscope (TEM) was employed in
this study to examine the very fine particles being emitted
from the engine. Representative examples are shown in
Figures 33 through 36. During examination of exhaust particulate
with the TEM, particle size was observed to decrease markedly.
Further investigation showed that this was caused by the
vaporization of condensed organics on particles (which apparently
act as a condensation nucleation site during air dilution and
cooling of the exhaust) due to the high intensity electron
beam.
The scanning electron microscopy (SEM) in combination with an
X-ray fluorescence detector had been used to examine individual
exhaust particles. Typical exhaust particles are shown in
Figures 37-42. The capability in separating elemental components
in exhaust particles is shown in Figures 43-70. Specific analysis
of selected runs are discussed in detail.
-------
-132-
Run No. 21
Particle documentation on Plate 1 of the Andersen sampler is
found on Figure 43 and Figure 45. Figure 44B is typical of
the fines on Plate 1. Spectrum Figure 46 recording Pb:Br:Cl
is typical of particle type Figure 43 C and D. The log-type
crystals (Figure 44 B and C) have less chlorine than those
of Figure 43 C and D. This log-type crystal is more easily
found near impingement areas indicating higher density.
In an extensive search of Plate 1, no particles were found
which did not contain lead. Likewise, some of the particles
with spectra of Pb:Cl:Br were non-crystalline (Figure 44 D).
Iron was present in many particles but no correlation between
the presence of iron and the morphology of the particle could
be made.
X-ray analysis data was collected at impingement points. Each
area examined, Plates 1, 4, 7, and the final filter (Figures 47,
48, 49, 50, respectively), revealed the presence of Pb:Br:Cl.
The ratio of chlorine to bromine decreases from Plate 1 to 7
with a similar ratio on the final filter as was found on
Plate 1. Small amounts of iron are found on Plates 1 and 7
with copper and zinc being on the final filter. Figure 51
is a spectrum of an unused or blank filter paper.
Run No. 24
X-ray data was collected at impingement points on Plate 1
(Figure 52) and Plate 4 (Figure 53). The spectrum includes
Pb:Br:Cl and Si with the chlorine to bromine ratio being
decreased on Plate 4. The base line on the spectra suggests
the presence of organics.
Run No. 25
X-ray analysis is recorded on Plates 1, 4, 7 and Filters 1,
2 and 3 (Figures 54, 55, 56, 57, 58, 59, respectively). The
elements present in all of these positions are Pb:Br:Cl and
-------
-133-
Si with the only difference being in the ratio of one element
to another. The additional elements of K, Ca, Ba, and Zn
found in the filter samples is due principally to the filter
and not the particulates. The base line on the spectra from
Plates 1 and 7 indicate the presence of high organics.
Run No. 39
X-ray analysis is recorded from impingement points on
Plates 3 and 6 (Figures 60 and 61). The major component is
iron with minor amounts of Cl, Ca, Cr, and Cu. Peaks are also
recorded at 1.48 Kev, which could be bromine or aluminum or a
combination of both, and at 2.31 which could be the lead M
energy line or the Ka energy line of sulfur. Lead is
definitely present due to the La energy band, but sulfur may
also be present.
Run No. 41
X-ray spectra from impingement points on Plates 4 and 7
(Figures 62 and 63) show high amounts of sulfur to be present.
Other elements in lesser amounts include Al, Si, K, Ca, Cr, Mn,
Cu, Zn, and Pb. More iron and silicon is found on Plate 7 than
on Plate 4.
Run No. 42
Very little particulate was collected from this run. X-ray
analysis was made on Plates 1, 4, and 7 (Figures 64, 65, 66)
with several impingement points being scraped together to have
enough particulate for a good analysis. Elements found on
each of these plates include Si, P, Pb, S, Cl, Ca, Cr, Mn, Fe,
Cu, Zn, Br, and possibly Al. Plate 7 also includes Ag and K.
The silver may be due to the conductive paint used to attach
the substrate to the specimen stub.
-------
-134-
Individual particle analysis from Plate 1 indicates various
species of participate with Pb:Br:Cl being the most frequent.
These Pb:Br:Cl particles had the crystalline shape of the
typical particles, Figure 45 A or B. Particles and X-ray
analysis of the individual particles are shown in Figures 45,
67, 68, 69, and 70.
The individual particles from Plates 4 and 7 are very small
and not well defined; therefore, no individual particle
analysis was made on these plates.
(Text continues on page 165)
-------
-135-
Figure 29. Exhaust Particulate on
Andersen Plates by OM - From Run #9
40OX
T 3
T 6
M
-------
-136-
Figure 30. Exhaust Particulate on
Andersen Plates by OM - From Run #8
T1
40OX
T 3
T 6
M
-------
-137-
Figure 31. Exhaust Particulate on
Andersen Plates by OM - From Run #15
400X
T 3
T 6
-------
-138-
Figure 32. Exhaust Particulate on
Andersen Plates by OM - From Run #11
T 1
400X
T 3
T 6
M
-------
-139-
Figure 33.
Andersen
Exhaust Particulate on
Plates by TEM - From Run #13
T 1
400X
T 3
M
-------
-140-
Figure 34. Exhaust Particulate on
Andersen Plates by TEM -
From Run #2, Plate #1
Magnification - lig,700x
-------
-141-
Figure 35. Exhaust Particulate on
Andersen Plates by TEM -
From Run #2. Plate #6
•*,' «•
V * *
jrfiiyfr***
i^§;
Magnification - 119,700x
-------
-142-
Figure 36. Exhaust Particulate
Millipore Filter by TEM -
From Run #2
~
on
* ^ ~ . *»
** -A.';1*:
•*
* ~ * "W-"».'IIW» ^c ^>* *'i
<-7A^ - SP T^s- --
:w •»!
•«» . %«
...» • J^ r i JHBk
Magnification - 119,700x
-------
-143-
Figure 37. Exhaust Particulate on
Andersen Plates by'SEM - From Run #1
-------
-144-
Figure 38. Exhaust
Andersen Plates by
Particulate on
SEM - From Run
-------
-145-
Figure 39. Exhaust Particulate on
Andersen Plates by SEM -
From Run #2, Plate #6
-------
-146-
Figure 40. Exhaust Particulate on
Andersen Plates by SEM -
From Run #2, Plate #1
-------
-147-
Figure 41. Exhaust Particulate on
Andersen Plates by SEM -
From Run #1, Plate #1
Magnification - lO.OOOx
-------
-148-
Figure 42. Exhaust Particulate on
Andersen Plates by SEM -
From Run #1, Plate #1
Magnification - lO.OOOx
-------
-149-
Figure 43. Exhaust Particulate on
Andersen Plates by SEM -
From Run #21, Plate #1
GR-21-1
5, 000 X
-------
-150-
Figure 44. Exhaust Particulate on
Andersen Plates by SEM -
From Run #21, Plate #1
GR-21-2
5, 000 X
-------
-151-
Figure 45. Exhaust Particulate on
Andersen Plates by SEM -
From Run #42, Plates 1, 4, and 7
GR-42-1
5, 000 X
10, 000 X
10, 000 X
10, 000 X
D
-------
-152-
•-:H-:U M'i: !,!! 'I;' "
Figure 46 __
' X-tAY SPECTRUM ~r
jTyplcil of Particle
^Figure 43 C and 0
Figure 47
X-RAY SPECTRUM
Andersen Plate 1
Run 21
-------
-153-
Figure 48
X-RAY SPECTRUM
Andersen Plate 1
Run 21
T
.J
i i
Figure 49
X-RAY SPECTRUM ! -
Andersen Plate 7
Run 21 ;
-------
-154-
Mgure 58
j.^ X-RAY SPECTRUH
i.h Final F1H«r
r-r I
Figure 51
X-RAY SPECTRUM
Filter Blank
-------
-155-
X-RAY SPECTRUM
Andersen Plate 1
Run 24
Figure S31
X-RAY SPECTRUM
Andersen Plate 4
Run 24
I
-------
-156-
Figure 54
X-RAY SPECTRUM
Andersen Pl«t« 1
Run 25
X-RAY SPECTRUM
! i , i Andersen Plate 4
Run 25
-------
-157-
Mgure 5 6
X-*A¥ SPECTR'IW
Andersen Plate 7
Run 25
X-RAY SPECTRUM
Filter 1 !
-------
-158-
Hgure
•; '-I | K-RAY SPECTRUM
iTTTl Filter 2
X-RAY SPECTRUM
Filter 3
-------
-159-
Figure 60
X-RAY SPECTRUM
Andersen Plate 3
Run 39
-------
-160-
, Figure 62
X-RAY SPECTRUM
Andersen Plate 4
Run 41
! I ! ; ! Figure 63
' 'l X-RAY SPECTRUM
! Andersen .Plate 7
Run 41
-------
-161-
Figure 64
X-RAY SPECTRUM
Andersen Plate 1
Run 42
X-RAY SPECTRUM
Andersen Plate 4
-------
-162-
X-RAY SPECTRUM
Andersen Plate 7
Figure 67
X-RAY SPECTRUM
Individual Particle
of Figure 49A
Run 42
-------
-163-
X-RAY SPECTRUM
Individual Particle
of Figure 49B
Figure 69
I
X-RAY SPECTRUM |
Individual Particle
of Figure 49C
Run 42 f
iiu _.j i L j.
-------
-164-
Figure 70
X-RAY SPECTRUM 1-
Indlvidual Particle
of Figure 490 j
Run 42 1
-------
-165-
8. Organics
Micro methods have been employed for the determination of
benzene solubles, ultraviolet absorptivity, ultraviolet
fluorescence, phenolics, and total acidity of exhaust particle
size fractions. The details of the procedures have been
previously described in the Analytical Methods Section
of this report.
In addition, a relative organic concentration has been determined
by mass spectrometry, and detailed organic analysis of a
single test run exhaust particulate sample was determined
utilizing high resolution mass spectrometry.
Table 36 indicates the relative organic content of exhaust
particles by size fraction and run number determined by mass
spectrometry utilizing methods described earlier.
A hydrocarbon type analysis was made of particulate matter
collected in Run 27 by high resolution mass spectrometry using
the characteristic hydrocarbon fragment ions for the various
types as well as the parent ions for the polyaromatic compounds.
This analysis used only the CH ions; no attempt was made to
correct this fragment spectrum for those fragments due to the
heteratom compounds that were present. The hydrocarbon type
analysis is shown in Table 37. The major difference between
-------
-166-
Run Sample
No. Source*
3 AP-5
6
Filter
4 AP-1
2
3
4
5
6
Filter
S-l
2
3
4
5
6
7
5 AP-1
2
5
S-l
2
3
3'
4
5
6
7
6 AP-1
2
3
4
5
6
7 AP-1
2
3
4
5
6
Filter
8 AP-3
4
5
6
Filter
9 AP-1
2
3
4
5
6
Filter
11 AP-1
2
3
4
5
6
Filter
12 AP-1
2
3
4
5
6
Filter
Level
(mg)
3.317
5.264
1.137
0.084
.109
.131
.387
3.120
1 .654
.877
.020
.11
.066
.093
.066
.066
.060
2.565
1.895
4.222
0.059
.11
.083
.10
.10
.074
.086
.083
.200
.123
.232
.668
2.168
1.276
0.253
.193
.193
.376
1.389
1 .285
0.628
.180
.426
1.028
1.046
0.735
.302
.253
.225
.533
1 .671
2.167
2.527
0.187
.222
.332
.547
1.704
2.227
1 .999
0.130
.144
.155
.387
1.047
1 .440
1.219
TABLE 36
RELATIVE ORGANIC LEVEL SY SIZE FRACTION - MASS SrCCTROKCTRY KETIIOC
(Organic Relative Level/rig Sample)
Organic
Sample Wt.
(gm)
1.15
0.40
8.70
28.20
17.10
11.26
5.00
4.90
3.30
4.90
10.10
10.40
10.25
7.50
9.15
4.70
2.00
0.50
0.50
0.80
9.45
9.35
10.57
1.20
10.50
10.50
9.90
10.80
8.55
70
30
25
65
10.20
12.23
15.85
15.46
8.66
5.05
2.61
7.06
70
40
7.80
9.50
9.90
9.70
10.30
10.00
7.75
3.20
1.60
6.15
10.40
8.90
10.20
5.80
3.80
4.40
10.80
10.61
10.36
9.84
6.45
6.74
7.90
6.41
Run
No.
13
14
16
17
18
19
20
21
Sample
Source*
AP-1
2
. 3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
S-l
AP-1
2
3
A
5
6
7
Filter
S-l
AP-1
2
3
4
5
6
7
Filter
S-l
7
AP-1
2
3
4
5
6
S-l
2
3
4
Organic
Level
(ing)
-* -J '-
0.147
.173
.290
.517
1.646
1.971
1.700
0.115
.068
.077
.127
.593
.905
1 .034
1.955
1.740
1 .074
0.655
1 .686
2.550
0.585
2.017
4.053
1 .154
1 .250
1 .507
2.788
0.863
.339
.424
.636
.978
1.785
2.132
>0.808
.100
.171
.154
.176
.312
.749
1.148
1 .081
>0.767
.024
.093
.079
.083
.196
.343
.580
.669
>.098
.045
.140
.52
.15
.14
.47
.56
.84
.55
.14
.63
.55
Sample Wt.
(gm)
10.70
11 .30
9.00
6.10
3.55
3.55
9.10
7.40
9.61
7.66
3.62
3.30
1.90
6.21
1 .17
1.17
0.87
.50
.65
.55
.30
1.05
0.30
.70
.65
.55
.40
1.20
12.30
7.74
9.83
9.42
11.13
9.24
13.81
11 .31
14.2
19.16
16.15
6.48
4.68
4.40
7.95
4.60
8.07
17.16
17.12
12.02
6.56
5.70
3.58
8.85
0.81
11.73
8.95
3.04
2.31
1 .57
1.10
0.71
0.37
10.85
9.61
3.08
0.26
*Code: AP-
S-
Andersen Plate-numer
S11t-numbcr
-------
-167-
TABLE 36 (Cont.)
Run
Mo.
22
23
24
25
28
29
31
33
Sample
Source*
AP-1
2
3
4
5
6
Filter
S-1
2
3
4
AP-1
2
3
4
5
6
7
Filter
S-l
2
3
4
5
AP-1
2
3
4
5
6
7
Filter
AP-1
2
3
4
5
6
7
Filter
AP-1
2
3
4
5
6
Filter
AP-1
2
3
4
5
6
Filter
Total Hot
AP-1
2
3
4
5
6
Filter
4 cfm
Filter
Flltor
Organic
Level
(mg)
1 .240
1 .624
1.318
1 .538
2.035
5.049
>1.719
0.095
.14
.079
.088
.013
.016
.030
.078
.413
.808
1 .051
>1 .366
0.055
.082
.030
.079
.350
.015
.021
.026
.16
.58
1.10
0.95
>.118
.030
.035
.055
.140
.33
.54
.61
>.17
.036
.036
.039
.18
.22
.57
.024
.180
.085
.160
.070
.16
.59
>.048
.395
.196
.071
.12
.22
.27
.44
>.354
>.31
.067
.102
Sample Wt.
(qm)
0.705
.40
.85
.70
1.20
0.40
3.65
10.31
10.20
11 .73
2.33 .
8.3
9.9
7.05
3.00
2.40
1.70
3.90
8.30
9.21
11 .08
10.76
3.19
0.94
5.12
4.94
3.80
0.66
.55
.31
1 .18
8.66
4.53
5.93
3.74
1.18
0.66
0.70
1.17
9.38
5.80
6.66
6.40
2.19
1 .26
0.31
7.42
0.18
.21
.36
.38
.16
.14
7.31
11 .05
8.44
4.60
3.32
1 .30
1 .09
0.4
12.53
9.04
9.17
9.0
*Code: AP- - Andersen Plate-number
S- •-= SI 1 t-nuiiilu!r
SW- •- Sweep) rigs - letter
Run
No.
34
36
38
40
41
42
43
44
45
46
48
53
Sample
Source*
AP-1
2
3
4
5
6
7
Filter
Filter CS
Filter SS
S-l
3
5
7
Filter
AP-1
2
3
4
5
6
Filter
S-l
3
5
Filter
S-l
5
7
Filter
SW-A
E
F
G
AP-1
2
3
4
5
6
7
Filter
AP-1
2
3
4
5
6
7
Filter
AP-1
2
4
5
6
AP-1
2
3
4
5
6
AP-1
2
3
4
5
6
Organic
Level
(nig)
0.917
2.140
0.842
1 .120
2.071
4.493
4.286
1.693
1 .326
0.038
.063
.210
.750
.682
.706
.148
.146
.136
.250
.219
.725
.155
.213
.042
.035
.094
.079
.151
.235
.007
.047
.099
.020
.186
.585
.702
.904
.464
.645
.479
1 .433
0.346
.525
3.04
3.855
2.06
2.35
0.589
.609
.067
1 .06
1 .145
0.989
.987
1 .138
3.14
0.759
1 .42
1 .175
0.888
1 .429
0.51
1.16
1 .00
0.74
.63
4.48
Sample Wt .
(gm)
9.17
2.68
2.55
2.08
2.89
0.98
4.03
9.46
8.69
9.53
15.0
12.75
7.02
1 .31
2.18
0.77
2.03
2.28
1 .5
1 .66
0.24
8.38
1 .77
6.47
2.01
9.9
3.42
2.32
0.35
11 .0
4.8
3.1
9.98
0.74
.21
.23
.37
.36
.54
.33
.40
7.4
0.15
.04
.03
.07
.05
.21
.21
11 .02
0.26
.18
.16
.26
.18
.20
.20
.10
.11
.19
.12
.20
.10
.10
.15
.20
.20
-------
-168-
the two samples, A and B, is the greater abundance of aromatics
in Sample A and, although not evident from this table, the
presence of what appears to be more lubricating oil in Sample B
than in Sample A. Sample A contains a large amount of the
CnH2n-8 type of wnich most is C8H8*
TABLE 37
HYDROCARBON CHAIN TYPE ANALYSIS
HIGH RESOLUTION MASS SPECTROMETRY
Sample A* Sample B
Hydrocarbon 7 mg 10% Organic 122 mg <1.0%
Type ___ Organic
Volume %
CnH2n
CnH2n
CnH2n
CnH2n
CnH2n
CnH2n
CnH2n
CnH2n
CnH2n
CnH2n
CnH2n
C..H-
+ 2
- 2
- 4
- 6
- 8
- 10
- 12
- 14
- 16
- 18
- 20
21.0
23
14
3
26
10
1
0.8
0.02
0.83
0.45
0.05
46.
20
14
3
16
<0.
0.
0.
0.
-
0.
_
0
1
1
63
15
-
35
_
CnH2n - 22
CnH2n - 24
CnH2n - 26
CnH2n - 28
CnH2n - 30
0.09
0.14
0.48
Possible Structures
R
U-C =
*Sample A - 7.20 mg, 10% organic, from Andersen plates
3, 4, 5, 6 from three different Andersen samplers from the
same run.
Sample B 122.25 mg <1% organic sweepings from dilution tube.
-------
-169-
CHQ Types - Both samples contain aromatic oxygenated compounds
of the C Hpn 6 0 type and what can be unsaturated ketones
and/or aldehydes through Cj.
CH00 Types - Both samples contain the aromatic oxygenated
-------
-170-
Sample A - 7.20 mg, 10% organic, Andersen Plates 3, 4, 5, 6;
taken from three different Andersen samplers from the
same run.
Sample B - 122.25 mg, <1% organic, dilution tube sweeping sample.
The table also indicates the percent of ion types for an alcohol,
a ketone, and an ester so that a comparison may be made with
the sample values. It is evident that although the heteratom
types are present, the bulk of each sample is hydrocarbon.
A portable cycloidal mass spectrometer was used to monitor the
hot engine exhaust at the manifold and in the tailpipe just
past the muffler during Run 16 while in the conditioning
sequence. Results are shown as mass spectra in Figures 71-78.
Table 39 reflects data on the organic content of collected
exhaust particles by run number and source. The weight percent
solubility in benzene/methanol and the relative ultraviolet
absorbance value are further measures of total organic content
of the collected exhaust particulate. Table 40 shows only
the UV absorbance of Runs 3-17, whereas Table 41 shows the UV
fluorescence levels. Table 42 provides data on the further
analysis of the benzene soluble fraction of collected exhaust
particulate. The analytical procedures used are presented in
the Experimental Procedures Section.
Analysis of benzene extracts of collected exhaust particles
for various carbonyls via polarographic techniques is shown
in Table 43. Values shown are corrected for solvents and
reagents used during determinations.
Further analysis of benzene soluble fractions by Pulse
Polarography is shown in Table 44. See the Experimental
Procedures Section for method.
-------
-171-
ao-o +
Figure 71
MASS SPECTRAL PROFILE
CVO-E 3 umtFOLO
10-0
.A. A .A.
Figure 72
MASS SPECTRAL PROFILE
CVO-E 3 MANIFOLD
Repeat
A
90
-------
-172-
BO-O +
Figure 73
MASS SPECTRAL PROFILE
Exhaust
PTff.Oi CYCLE 3
1X>-0 . ,
1
IES iso ITS an
eo-o
Figure 74
MASS SPECTRAL PROFILE
Exhaust
PIPE, IN crcue 3
Repeat
10-0
'< L
A
100 IB 190 ITS
-------
-173-
ED-O
Figure 75
MASS SPECTRAL PROFILE
Exhaust
PIPEiIN CYCLE *
10-0
ED-O
Figure 76
MASS SPECTRAL PROFILE
Exhaust
PIFtilN CfDLE *
Repeat
VL
A. A
tas
-------
-174-
I I I I I
VrMrv,
Flgure 77
MASS SPECTRAL PROFILE
Exhaust
PIPE. IN CYCLE 3
75 100' 125 150 173 et»
EO-0
Figure 78
MASS SPECTRAL PROFILE
Exhaust
PIFEiIN CYCLE 5
Repeat
10-0
A
A. A
79 100
tao
200 aa 290
-------
-175-
TARLE 39
ORGANIC ANALYSIS OT COLLECTED EXHAUST PAnTICULATES BY RUM NUMBER
Run No. Sample Source
19 1 cfm Millipore filter
1 cfm Glass fiber filter
20 1 cfm Glass fiber filter
1 cfm Millipore filter
21 1 cfm Millipore filter
22 1 cfm Glass fiber filter
1 cfm Glass fiber fi Her
23 1 cfm Glass fiber filter
Andersen Plates 1,2,3
Andersen Plates 4,5,6
24 4 cfm Glass fiber filter
4 cfm Glass fiber filter
25 4 cfm Glass fiber filter
4 cfm Glass fiber filter
28 4 cfm Glass fiber filter
29 1 cfm Glass fiber filter
Total exhaust hot filter
Andersen Plates 1,2,3,4
Andersen Plates 5,6,7
30 4 cfm Glass fiber filter
(Steady State)
1 cfm Glass fiber filter
(Steady State)
4 cfm Glass fiber f i Her
(FTP-Cy)
1 cfm Glass fiber filter
(FTP-Cy)
31 1 cfm Glass fiber filter
4 cfm Glass fiber filter
Andersen Plates 1 ,2,3,4
Andersen Plates 5,6,7
Total exhaust hot filter
34 4 cfm Glass fiber filter
40 4 cfm Glass fiber filter
43 1 cfm Millipore filter
44 4 cfm Glass fiber filter
45 1 cfm Millipore filter
53 4 cfm Glass fiber filter
4 cfm Glass Fiber filter
Amount Collected
(ing)
164.7
18.9
21.1
153.5
39.2
27.1
30.2
149.0
70.9
20.9
159.2
161.7
139.5
118.8
171.0
12.0
31.1
4.4
1.7
116.0
31.6
13.3
5.1
127.3
735.6
24.4
12.8
462.7
196.2
145.5
6.5
156.4
12.6
4.3
6.8
Benzene and
Methanol
Solubl e
(wt. %r
5.4
8.6
7.8
5.6
38.3
54.6
50.5
7.8
0.8
4.7
1.7
1.9
2.5
2.3
3.6h
6-?h
16.6"
70. Ou
35.0"
3.7
6.0
(<1.5)k
k
5.1
2.6
2.7
3.3 .
(<0.5)k
20.9
6.4h
<6k
2.4
k
5.6
13.4
Acidity
Calc. as
PC02H (%)
0.29
.68
.23
.41
7.8
0.34
.83
.34
.04
.38
.11
k
.23
.14
.35
1.6
9
Not calc.
Not calc.
0.38
.44
.68
,<1.5
0.54
.09
.62
.70
9
0.40 - 0.05
0.80 * 0.05
4.5
1.0
1.3
k
0.53
Phenol i cs
Calc . as
00H (%)
0.08
.08
.06
.21
1.8
0.21
.31
.10
.02
.12
.02
.01
.03
.03
.04
.02
9
Not calc
Not calc
0.03
.04
k
k
0.08
.05
k
k
9
0.07
.20
1.1
.44
.41
::?ik
Rel . UV Va'lue
(per mq)
2880
3500
3290
3000
20,800
9410
8140
2720
279
1970
500
550
630
610
710
1700
190
5050
1350
1210 ±40
1290
1020
960
1230
380
310
1080
15k
4420
1990
6450
3040
3450
1140
3590
(f) Corrected l>y subtraction of blank
considered
©Value for benzene soluble material
©Value for blank greater or same magnitude as
sample; calculation not meaningful.
-------
-176-
TABLE 40
*
RELATIVE AMOUNTS OF UV ABSORBING MATERIAL
PRESENT ON ANDERSEN PLATES
Run. #
Plate #2
mg sample.
Absorbance*
Plate #4
mg sample
Absorbance*
Plate #5
.mg sample
Absorbance*
1
1
.1
1
1
Bl
1
1
3
4
4
5
6
7
8
9
1
2
3
4
5
ank
6
7
7.
24.
1
1
0.
0.
8.
5.
22.
1
5.
24.
1
1
9.
4.
8.
0.
1.
0.
93 ;
6
8
13
56
3
7
4
1
7
9
49.-;
1
1 1
9
240
520
560
810
680
720
380
730
'640
370
500
300
2400
3500
8670
2.
13.
6.
0.
2.
8.
8.
7.
6.
8.
5.
4.
0.
0.
19
7
27
18
71
7a
27
86
34
55
34
44
3
6
750
850
680
360
2620
830
1000
1810
1780
860
1950
480
34400
10700
1.
6.
3.
3.
4.
5.
7.
3.
2.
0.
1.
40
15
54
92
93
39
32
38
65
1
6
0
2020
4620
1550 -,
2940
4460
4220
2360
3440
1160
assuming
0.1 mg
13400
17500
6940
*Values are calculated on a basis of Absorbance @255my for 1.0 mg
of sample in 1.0 ml of solvent x 1000. A relative value for the
total amount UV absorbing material on a particular plate can be
obtained by multiplying the sample weight in mg times the above
value.
mg sample = Sample weight in milligrams
-------
ATIVE
Run •#
13 -
14 -
AMOUNTS OF
PRESENT 1
(See Notes
Sweeping A
B
C
D
E
F
G
Slit 1
2
3
Sweeping A
B
C
. D
E
Slit 1
2
-177-
TABLE 40A
uv ABSORBING
ft SLEEPING Aff
at Bottom of
.Sample Wt.
in mg
9.49
9.41
9.31
8.95
8.85
7.69
12.1
11.1
7.90
9.49
13.4
9.83
11.9
8.70
4.48
8.87
10.0
Relative Relative
Absorbance Fluorescent
Values Values
340 320
180 110
180 110
600 300
800 350
910 340
770 290
40 20
50 30
20 20
210 160
90 50
40 30
270 140
1010 510
50 30
30 10
-------
-178-
TABLE 41
RELATIVE AMOUNTS OF FLUORESCENT MATERIAL
PRESENT ON ANDERSEN PLATES
Plate #2 Plate #4 Plate #5
mg sample mg sample mg sample
Run # Fluorescence* Fluorescence* Fluorescence*
3 7.93 240 2.19 570 1.40 1580
4 24.6 190 13.7 440 6.15 1790
4 10.8 240 6.27 350 3.54 880
5 0.13 840 0.18 500
6 8.56 260 2.71 1320 3.92 1750
7 15.3 310 8.73 470
8 22.7 130 8.27 420
9 15.4 140 7.86 280 4.93 320
11 24.1 60 6.34 250 5.39 190
12 19.7 70 8.55 180 7.32 190
13 14.9 110 5.34 320 3.38 550
14 8.49 100 4.44 230 2.65 180
assuming
15 0.1 650 <0.1 0.1 mg
Blank 5400
16 1.1 290 0.3 3570 0.6 2260
17 0.9 1480 0.6 2380 1.0 1480
*Values are calculated on the basis of area (in. x 100, with a
planimeter) for 1.0 mg of sample in 1.0 ml of solvent, with instru-
ment settings of excitation wavelength = 290my, slits = 2mm, sen-
sitivity = 0.01, and vertical scale of recorder at a setting of 5.
A relative value for the total amount of fluorescent material on a
particular plate can be obtained by multiplying the sample weight
in mg times the above value.
-------
-179-
TABLE 42
ANALYSIS OF BENZENE SOLUBLE FRACTION OF COLLECTED EXHAUST PARTICULATES BY RUN NUMBER
Benzene Soluble**
Run
No.
19
20
21
22
23
24
25
28
29
30
31
34
40
43
44
45
53
Soluble Insoluble
Methanol Methanol
Sample Source
1 cfm Milllpore fi
1 cfm Glass fiber
1 cfm Glass fiber
1 cfm Milllpore fi
1 cfm Milllpore f1
1 cfm Glass fiber
1 cfm Glass fiber
1 cfm Glass fiber
Andersen Plates 1 ,
Andersen Plates 4,
4 cfm Glass fiber
4 cfm Glass fiber
4 cfm Glass fiber
4 cfm Glass fiber
4 cfm Glass fiber
1 cfm Glass fiber
Total exhaust hot
Andersen Plates 1 ,
Andersen Plates 5,
4 cfm Glass fiber
(Steady State)
1 cfm Glass fiber
(Steady State)
4 cfm Glass fiber
(FTP-Cy)*
1 cfm Glass fiber
(FTP-Cy)
1 cfm Glass fiber
4 cfm Glass fiber
Andersen Plates 1 ,
Andersen Plates 5,
Total exhaust hot
4 cfm Glass fiber
4 cfm Glass fiber
Iter
filter
filter
Her
Her
filter
filter
filter
2.3
5,6
filter
filter
filter
filter
filter
filter
filter
2,3,4
6,7
filter
filter
filter
filter
filter
filter
2,3,4
6,7
filter
filter
filter
1 cfm Mlllipore filter
4 cfm Glass fiber
1 cfm Milllpore
4 cfm Glass fiber
4 cfm Glass fiber
filter
filter
filter
(%)
5.4
8.6
7.8
5.6
38. 3m
54.2
50.6
7.8
0.8
4.7
1.7
1.9
2.5
2.3
3.6h
6'7h
16.6*
70.0*
35. Oh
3.7h
L.
6.0h
(< 1 .5 )
k
5 lh
'i 6
2:?h
3.3h ,,
(<0.5)k
20.9
6.4
<6
2.4
k
5'. 6
13.4
(*)
1 .5
0.0
0.3
.8
.8
13.9
9.6
3.3
0.0
1.3
0.2
0.3
0.3
0.3
g
g
g
g
g
g
g
g
g
g
g
g
g
g
8.4"
0.0
0.0
0.1
0.0
40.0
1.5
Absorp-
tivity
(255 nm)
53
41
38
54
54
17
16
35
35
42
29
29
26
27
21
29
1.2
7.2
3.9
34 1
23
k
k
25
15
12
33
k
21
31
k
124
k
20
27
Acidity
Calc. as
PCO,H (»)
— £ "
5.3
7.9
3.0
7.3
•v.20
1.6
0.7
4.4
5.3
8.1
6.7
k
9.9
6.8
9.8
23.8
g
k
k
10.2
7.4
k
(< 14)
10.6
3.8m
23. 2m
21. Om
g
2.0 i 0.3
12.4 * 0.9
k
41.9
k
k
4.0
Phenol tcs Ratios of Chromogenics
Calc. as to Phenol 1cs
OpOH
1 .6 *
0.9 t
0.7 t
3.7 t
4.6
0.4 ±
0.6 ±
1.3 t
2.8
2.5
0.9 i
0.6 ±
1.2 t
1.2 ±
1.1 t
1.5 t
g
k
k
0.8 t
0.7 i
k
k
1.6 i
2.0 ±
k
k
g
0.35
3.1 t
k
17.3
k
<1.2k
<0.8
(X) 330 nm 420
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
.2
.5
.5
.4
1.1
.1 0.7
.1 0.4
.1 0.6
-
-
.1 0.8
.1 0.9
.1 0.8
.1 0.6
.2
.1
g
. -
.3
.7
-
-
.2
.1
-
-
g
-
.1 0.7
1.4
-
2.1
1 .0
1.1
0.
.
-
0.
.
0.
0.
.
-
0.
0.
0.
0.
0.
1.
g
-
0.
0.
0.
0.
2.
0.
-
•_
g
0.
i.
0.
i .
0.
_
0.
nm 450 nm
7
6
8 - „
0.4°
3
.
4
5 0.5
0.5n
0.4n
7
7
4 0.3
4 0.3
6 0.6
2
g
-
8 0.7
5n
2
8
4
7
-
.
g
3 0.4
1
5
5
8
_
4 0.5
*FTP-Cy = California 7 mode cycle
§Not considered
Value for benzene soluble material
Value for blank greater or same magnitude as
sample; calculation not meaningful
**See Procedure on page e3
(m) Accuracy may be poor because of large blank
correction
S Broad absorbance peak
Insolubles consisted of a black tar and a
viscous liquid having the IR characterization
of aliphatic hydrocarbon (i.e. absorbance peaks
at 2900, 1460. 1370, and 750 cm'1.
-------
-ISO-
TABLE 43
BENZENE EXTRACTS OF EXHAUST PARTICIPATES - POLAROGRAPHIC METHOD
(Values in Micrograms/ml)
Run No
19
19
20
20
21
22
22
Blanks
23A
23B
23
24
**25
**25
28
29
29
30
30
30
30
31
31
40
44
45
53
53
Source
Filter 1/2 cfm
1 cfm
1/2 cfm
1 cfm
1 cfm
1 cfm
1 cfm
f Solvent Blank
I Glass Filter
I,. Membrane Fil ter
Andersen 1,2,3
Andersen 4,5,6
Filter 1 cfm
4 cfm
4 cfm
4 cfm
4 cfm
Andersen 1 ,2,3,4
Andersen 5,6,7
Filter 4 cfm
1 cfm
4 cfm
1 cfm
1 cfm
" (4) 4 cfm
4 cfm
4 cfm
1 cfm
4 cfm
4 cfm
HCHO
*
<1
0.4
<2
<5
1 .0
*
<1
<2
<2
<2
*
<1
13
<2
<1
5.6
<1
<1
11
5.4
<4
2.1
9.5
4.3
1.7
1.5
1 .8
<2
1 .6
CH0CHO
<5
<2
<2
<2
17
<2
*
<2
<5
<5
*
<5
<2
<10
<5
<5
4.0
1 .5
2.4
<10
2.5
*
<5
<5
<5
<2
<5
9.2
<5
<5
0CHO
<6
<3
<3
*
<6
<6
*
<3
<6
<6
<6
<6
<3
<6
<6
*
<6
<3
<3
<10
<6
<6
<6
6.5
4.8
3.7
4.2
<6
<6
<6
00CO
*
14
8.3
16
29.0
17
31
22
22
20
*
*
<20
13
<20
<20
17
19
7.4
44
16
12
27
32
11
17
<20
<20
55
24
*Interference prevents determination.
**Run 25 two 4-cfm filters were used on the same run and
same sample probe.
-------
-181-'
TABLE <+»t
ANALYSIS OF PARTICULATE BENZENE SOLUBLES VIA PULSE POLAROGRAPHY
FOR SELECTED TEST RUNS
Run
No. Sample Source
19 1 cfm H11l1pore filter
1 cfm Glass fiber filter
20 1 cfm Glass fiber filter
1 cfm M11l1pore filter
21 1 cfm MUllpore filter
22 1 cfm Glass fiber filter
1 cfm Glass fiber filter
23 1 cfm Glass fiber filter
Andersen Plates 1,2,3
Andersen Plates 4,5,6
24 4 cfm Glass fiber filter
25 4 cfm Glass fiber filter
4 cfm Glass fiber filter
28 4 cfm Glass fiber filter
29 Andersen Plates 1.2,3,4
Andersen Plates 5,6,7
30 4 cfm Glass fiber filter
1 cfm Glass fiber filter
(Steady-State)
4 cfm Glass fiber filter
(FTP-Cy)
4 cfm Glass fiber filter
(FTP-Cy)
31 1 cfm Glass fiber filter
4 cfm Glass fiber filter
40 4 cfm Glass fiber filter
44 4 cfm Glass fiber filter
45 1 cfm Millipore filter
53 4 cfm Glass fiber filter
4 cfm Glass fiber filter
- Benzene solvent
Glass filter blank
MllUpore filter blank
© Net after subtraction of blank residue weight.
©Not detected. For 2-ml allquots the detection
limits are 2 gg/ml for H2CO; 5 wg/ml for RCHO calc.
as CH3CHO; 6 gg/ml for ArCHO calc. as C6H5CHO;
6 u9/ml for Pb.
©When value of u<]/m!. Is less than the blank value,
the calculated, uncorrected value is expressed
as "less than." Gelman glass filters and solvent
gave blanks of 22 gg/ml calc. as (CHCO.
Benzene
and
Hethanol
pg/ml (Gross)
Participate Soluble
Analyzed
(nig)
75.7
18.9
21 .1
36.9
39.2
27.1
30.2
149.0
57.0
18.7
159.2
139.5
118.8
171.0
4.4
1.7
116.0
31.6
13.3
5.1
127.3
735.6
145.5
156.4
12.6
4.3
6.8
-
-
.
Residue
4.08
1.63
1.65
2.06
n
14.65
15.26
11.56
0.45
0.88
2.55
3.20
2.49
6.1
0.49
0.07
4.3
1.9
n
n
6.5
18.2
9.32
3.82
n
0.24
0.91
0.05
0.4 0.2
30.0 2
Vol.
(ml)
5
5
5
5
5
10
10
10
5
5
5
4
4
5
5
5
5
5
5
5
5
10
-10
5
5
5
5
5
5
5
Aromatic
Ketone as
31
17
. ND
ND
48
13
ND
37
ND
22
19
27
ND
20
ND
ND
38
10
ND
8
640q
82
130r
430*
1
ND
NO
ND
NO
1
14
1
16
8.3
29
17
31
ND
1
1
13
ND
ND
17
19
7.4
44
16
12
27
32
11
17
ND
NO
24
55
12 to 23
4 to 22
NO
RCHQ
NO9
ND
NO
ND
17 as CH3CHO
1 as H,0
12
ND
ND
ND
1.3 as H2CO
ND
ND
5.6 as H?CO
4.0 as CH3CHO
1 .5 as CH,CHO
2.4 as CHjCHO
11 as H2CO
5.4 as H2CO
ND
2.1 as H2CO
9.5 as H2CO
6.5 as C6H5CHO
4.3 as H2CO
4.8 as C6HsCHO
1.7 as H2CO
3.7 as C6H5CHO
1 .5 as H2CO
4.2 as C6H5CHO
1.8 as H2CO
9.2 as CHaCHO
1.6 as H.CO
ND
ND
ND
ND
% 1n Soluble Residue
Total Carbonyl
Calc. as h
Pb {C*HC),CO
3.8 <1.7
5.2
<1 .8
<1 '.5
m
0.9
<0.4
3.2
m
m
3.7
3.4
<1.9
1.6
m
m
4.4
2.6
m.n
m.n
49. 2q
4.5
13. 9r
56.3*
m
m
m
m
m
m
1
<4.8
<2.0
m
<1 .1
0.6 to
<1 .7
m
m
<2.5
<2.5
<3.2
0.8 to
m
m
2.5 to
<4.2
m.n
. m.n
1.6 to-
< .1 . 0
<2.5
<2.6
m
m
m
m
m
m
2.0
2.5
5.1
3.3
iNot determined; background Interference great.
>Calculation not meaningful.
©Residue weight same magnitude as blank.
Interference likely (see Run 44 and note t).
©0.012X (wt.) Pb via emission spectroscopy
gives 10.1% Pb in benzene soluble.
3 ppm Pb via emission spectroscopy
equivalent to 0.4% Pb in paniculate.
-------
-182-
V. DISCUSSION OF RESULTS
The results presented herein are based upon the generation,
collection, and analysis of exhaust particles in a well defined
system and under carefully controlled laboratory conditions.
Initially, our challenge was to develop repeatable and
reproducible means of generating, collecting, and analyzing
exhaust particles. This required establishment of operational
procedures which eliminated as many variables as possible, yet
which provided an operational mode not uncommon to the automotive
engine. Basic decisions with that in mind, dictated that initial
studies be conducted using engines attached to laboratory dynamometer
operated under carefully controlled conditions. A "conditioning
sequence" with each test fuel was found to be necessary in order
to stabilize engine emissions, deposits, and the exhaust system.
The particle sampling operation under air diluted conditions at
60 mph road load provided a not uncommon operational mode for the
engine and yet allowed particle sampling under conditions somewhat
related to the actual vehicle emission environment on the roadway.
^
It is known that fuel composition and additives, particularly
tetraethyl lead, effect automotive exhaust emissions, both gaseous
and particulate. Initial experiments, then, dictated that a single
fuel base be used and that TEL levels be varied in order to allow
assessment of the validity and repeatability of the complete
particulate investigation system. These studies were followed by
an examination of the effect of lead scavengers, and then of various
fuel additives. In all of these runs, a single engine type (Chevrole
350 CID) was used. Following successful completion of this test
sequence, we examined fuel composition effects and engine variation
effects.
-------
-183-
The next phase in the project dictated operation of actual vehicles
with the same type engines, fuels, and operating conditions in
order to establish the validity of the engine dynamometer studies.
Subsequent vehicle studies examined the effect of cycled operation,
cold starts, hot starts, mileage, and catalytic systems on emitted
particulate mass and composition.
the objective, then, of this study has been to determine if fuel
composition and fuel additives have a discernible effect on exhaust
particulate mass and composition. When discernible effects were
observed in carefully controlled dynamometer studies, the relationship
to actual vehicles operated under realistic conditions was evaluated.
Now that the basis upon which the data reported herein has been
established, it is appropriate to address several specific topics.
The particulate sampling system, in this study the dilution tube
and proportional samplers, is the key to the data generated in
this study. In reality it dictates the definition of emitted exhaust
particulate. We have found this "definition" to be critical, particularly
with non-leaded fuel studies. We have operated the dilution tube
system as a constant volume device, with all runs operating at
the same total volume flow rate, to maintain isokinetic sampling
in the sampling zone. As a result, specific dilution ratios vary
depending upon whether we were sampling from one-half the engine
under steady-state conditions (engine dynamometer studies) or operating
in cycled mode with complete exhaust in the chassis dynamometer
as noted in Table 12. As a result, the sampling temperature can
vary substantially from run to run.
The impact of sampling temperature (dilution ratio) became apparent
when non-leaded fuel vehicle studies began. In an attempt to
quantify the magnitude of this effect, detailed sampling studies
were conducted on Runs 29 and 31 (leaded [31] and non-leaded
fuels [29]) using the total exhaust hot filter on one exhaust system
-------
-184-
from the right bank of cylinders and the dilution tube system on
the other bank of cylinders. The results, shown in Table-45,
clearly indicate that sampling temperature has a direct impact on
the organic fraction associated with exhaust particulatev
TABLE 45
COMPARISON OF PARTICULATE COLLECTED WITH
TOTAL EXHAUST HOT FILTER AND WITH THE
ANDERSEN SAMPLER AFTER EXHAUST AIR DILUTION
Hot Filter Andersen Sampler'
Run 29
Emitted (gm/mile)
Pb (wt. %)
Pb (gm/mile)
NH3 content (relative
amount/ing)
HC1 content (relative
amount/mg)
Aromatic content
(relative UV absorbance
per mg)
Benzene/methanol solubles
(wt. %)
0.0026
9.0
0.000224
0
0
190
16.6
0.0035
4.3
0.00015
0.056
2700
61
Run 31
Emitted (gm/mile)
Pb (wt. %)
NH3 content (relative
amount/mg)
HC1 content (relative
amount/mg)
Aromatic content
(relative UV absorbance
per mg)
Benzene/methanol solubles
(wt. %)
0.0499
4.8.5
0
0
15
<0.5
0.065
51.9
0.068
0.023
870
3.0
*Does not include large particles lost in dilution tube
-------
-185-
In certain size fractions of emitted exhaust participate, collected
under air diluted conditions, the organic content from non-leaded
fuel is as high as 70 percent. The implication seems obvious;
exhaust particulate must be defined in terms of sampling temperature.
Further examination of the data for those runs in which both
Andersen samplers operating at 1 cfm and a single total filter
operating at 4 cfm were used indicated that the 4 cfm filter exhibits
lower particulate mass collected. Examination of the temperatures
at which these devices operate during a sampling run suggests that
the same temperature-dependent phenomenon is occurring (Table 46)
which is further noted in the emission rate calculation (Table 47).
TABLE 46
FILTER TEMPERATURE DURING SAMPLING RUN
Dilution Tube Sampling Filter Temperature (°F)
Run No. Zone Temperature (°F) Andersen Back-up 4 cfm Filter
50 167.2
58 144.2
61 147.0
67 147.2
TABLE 47
MASS EMISSION RATES
Particulate Mass Emissions (gms/mile)
Run No. Andersen + Filter (1 cfrnj4 cfm FiTter
50 0.1565 0.1189
58 .0162 .0020
61 .0193 .0113
67 .1530 .1202
Obviously, much of the organic material associated with exhaust
particulate is volatile at tailpipe temperatures and only becomes
81 .5
92.0
90.0
87.5
143.5
142.0
137.0
136.1
-------
-186-
"particulate" after air dilution and cooling. The effect of
dilution rates and filter face velocity has not been examined,
although one might expect further effects there also.
In one study, Run 48, 4 cfm collection filters were stabilized at
room temperature, the grams/mile particulate emission rate determined,
and the filter then heated in an oven at various temperatures, cooled,
reweighed, and heated to a higher temperature, etc. The results of
this study are shown in Table 48. Again, the impact of organic
levels is obvious.
TABLE 48
EMITTED PARTICULATE MASS ON 4 CFM FILTERS FOR RUN 48 AS A
FUNCTION OF FILTER POST-COLLECTION TEMPERATURE TREATMENT IN OVEN
(Grams/Mile Emitted)
Collected
Run No. @ (°F)
Room Temp.
Weight
0.0605
.0519
.0554
.0494
.0460
100°F
0.0528
-
.0502
.0460
.0443
150°F
0.0468
.0383
.0349
.0383
.0340
200°F
0.0315
.0204
.0221
.0247
.0221
250°F
0.0213
.0196
.0170
.0221
.0204
48A 86
B 89
C 80
D 77
E 85
A review of the data indicates that the temperature sensitivity
during sampling is most significant using non-leaded fuels. True
particulate emission rates and chemical characterization must
involve definition of sampling temperature and collection device.
Dilution ratio effects, at constant sampling temperatures, have not
been examined herein although this factor may also be important and
should be investigated.
It is apparent that a nearly "real" measurement of mass emission
rate must be conducted using an air-dilution approach. Further,
the air diluted exhaust sample must be as close to ambient
-------
-187-
( 1ft)
temperatures as is practical. Techniques employed by Bergmarr 0/
(1 g\
and Essov , and suggested by AMA fail to consider this important
factor and, therefore, can be expected to exhibit mass emission
rates significantly lower than when employing the techniques used
herein and by Habib-p '.
The validity of the mass emission rates depends upon the fact that
the proportional sampling devices in the sampling zone of the
dilution tube are, indeed, taking a true proportional sample.
Temperature flow-rate and mass profile data on the dilution tube
have been presented in the Results Section. Mass profiles, under
steady-state engine operation, are within 10 percent which is the
factor which should appropriately be applied against the mass
emission rate values calculated. Profiles during cyclic vehicle
operation have not been conducted regarding mass distribution because
no suitable real time mass monitor is available. Temperature and
flow-rate, at a fixed position in the sampling zone, show relatively
stable flow rates (CVS system) and temperature fluctuations consistent
with vehicle cycle. Sampling during vehicle cyclic operation with the
resultant temperature fluctuations add an additional complexity to
the mass emission rate assessment due to the temperature effect
factors noted above.
Comparison of total mass emission rates from Chevrolet 350 CID
engines operated at 60 mph road load conditions on the engine
dynamometer and in a vehicle on the chassis dynamometer, indicate
that the vehicle emission rates are somewhat higher, even though
sampling temperature and dilution ratio are quite different, due,
no doubt, to the use of the complete exhaust in the vehicle study
and only one-half the exhaust in the dynamometer study. Table 49
reviews the appropriate data.
-------
-188-
TABLE 49
TOTAL MASS EMISSION RATES FROM CHEVROLET 350 CID ENGINES ON
THE ENGINE DYNAMOMETER AND IN VEHICLES. MASS BY DILUTION
TUBE PARTICULATE WEIGHT AND ANDERSEN SAMPLER - FILTER
Run No.
28
50
Equivalent/
Actual
Mileage
22
21
23
4590*
4590*
4590*
43
58E
45
61
27
2500
10,000
3000
9100
7900
8260
3000
Engine/Vehicle
Engine stand
(70 Chev 350 CID)
Engine stand
(70 Chev 350 CID)
Engine stand
(70 Chev 350 CID)
Vehicle (71)
D1171
Vehicle (71)
D1171
Vehicle (71)
D1169
Vehicle (71)
D0234
Vehicle (70)
D0628
Vehicle (70)
D0628
Vehicle (71)
D1220
Fuel
AMOCO 91 RON
0 TEL
AMOCO 91 RON
1/2 cc TEL/gal
Fuel A
AMOCO 91 RON
0 TEL
AMOCO 91 RON
0 TEL
AMOCO 91 RON
1/2 cc TEL/gal
AMOCO 91 RON
1/2 cc TEL/gal
Fuel A
Fuel A
Fuel A
Mass Emissions
(gm/mile)
0.0132
.0187
.0910
.0115
.0162
.0225
.0193
.1064
.1196
.1565
*Based upon equivalent 3150 miles during cycling, and one-half
of 2880 miles during 48-hour, 60 mph road load sampling run.
Whether comparison between the 1970 and 1971 Chevrolet 350 engines
is valid is not proven in this study. No significant engine
changes were made, however. The major trends between non-leaded,
low leaded, and fully leaded regular fuel appear to hold for the
engine and vehicle studies.
-------
-189-
Four vehicles have been run at selected mileages under steady-
state cruise conditions (Table 50) and under cyclic conditions
(Table 51). The data on mass emission rates are summarized in
these tables.
TABLE 50
MASS EMISSION RATES FOR SELECTED VEHICLES WITH CONTROLLED
FUELS AS A FUNCTION OF MILEAGE
(Mass Emissions via Dilution Tube Samples and Andersen/Filter)
Fuel
AMOCO 91 RON
0 TEL
AMOCO 91 RON
1/2 cc TEL
Fuel C 91 RON
0 TEL
Fuel A
Vehicle No.
D1171
D1169
D0234
D1220
Total Mass Emissions
Run No.
43
58E
45
61
53
62
50
67
Mileage
2,550
10,000
3,000
9,101
13,000
17,750
3,000
9,286
(gm/mile)
0.0115
.0162
.0225
.0193
.0206
.0093
.1565
.1930
Significant changes are noted for vehicle D1171 which exhibit
an increase in particulate emissions, and for vehicle D0234
where a decrease is noted. Vehicle D0234 in Run 62 was barely
operable and severe valve recession was observed when the engine
was inspected. No significant change in particle MMED was
observed in any of these comparisons.
-------
-190-
TABLE 51
MASS EMISSION RATES FOR SELECTED VEHICLES WITH CONTROLLED
FUELS AS A FUNCTION OF MILEAGE - CYCLIC OPERATION
(Mass Emission by 4 cfm Filter)
Fuel
AMOCO 91
0 TEL
Vehicle No. Run No,
RON
D1171
AMOCO 91 RON
1/2 cc TEL
D1169
Fuel C 91 RON
0 TEL
Fuel A
D0234
D1220
36
46
Total Mass Emissions
Mi leage (gm/mi le)
700 0.2019 FTP cold start,
cold soak
.0162 FTP, hot start
3,770 .0507
.0409 FTP,
.0426 cold start
.0400
58
48
60
53
62
51
66
.0362
.0477
.0400
.0353
10,000 .0196
.0085
4,250 .1214
.0554
.0583
.0443
.0566
.0468
9,101 .0690
.0336
13,000 .0617
.0404
17,750 .0217
.0127
3,000 .2071
.0813
9,280 .1742
.0988
FTP,
hot
FTP,
FTP,
FTP,
FTP,
FTP,
hot
FTP,
FTP,
FTP,
FTP,
FTP,
FTP,
FTP,
FTP,
FTP,
FTP,
I
start
col
hot
col
col
I
d
d
d
start
start
start,
cold soak
start
start
col
hot
col
hot
col
hot
col
hot
col
hot
d
d
d
d
d
start
start
start
start
start
start
start
start
start
start
-------
-191-
The results are somewhat mixed, but there appears to be a trend
toward decreased particle emissions with increased mileage for the
non-leaded fueled vehicles under cycled conditions. The trend for
low-leaded fueled vehicles is mixed depending upon cold or hot
starting of the test sequence.
These tables also provide data which reflect the effect of cold
start cycled tests vs. hot start on mass emissions. Data for many
more runs of this nature are presented in the Results Section in
Table 29. In all cases, except for Run 39A which was a catalyst
equipped vehicle, cold start emissions are greater than hot start
particulate emissions. It is suggested that the catalyst acts as
a cold trap for volatile organics during cold start. These materials
condense on the cold catalyst surface during start-up and are then
oxidized as the catalyst reaches operating temperature. Such a
theory would support the lower emission rate during cold start.
Several runs have been made comparing cycled vehicle operation mass
particulate emission rates as a function of the cycle driven. A
summary of this data is presented in Table 52.
TABLE 52
PARTICULATE MASS EMISSION RATES AS A FUNCTION OF
VEHICLE CYCLE
(4 cfm Filter)
Run No. FTP, Cold Start FTP, Hot Start LA-4. Hot Start
49 0.0911 0.0519 0.0516
.0639
51 .2071 .0813 .1091
53 .0617 .0404 .0708
58 .0196 .0085 .0108
60 .0690 .0336 .0466
62 .0217 .0127 .0068
66 .1742 .0988 .0605
-------
-192-
In most cases, the LA-4 hot start cycle results in participate
emissions somewhat greater than the FTP hot start cycle but less
than the FTP cold start cycle. LA-4 cold start tests were not
run during this project because the FTP cold start cycle was used
as the basis for cycled data comparison and vehicle scheduling
did not allow the necessary soak period. In all probability, the
LA-4 cold start would be somewhat higher than the FTP cold start
emission rate. It is important to note that the FTP cycle was
repeated sufficiently for 40 minutes vehicle operating time in
order to obtain ample quantities for mass measurements. The LA-4
was run for the specified 23 minutes. As a result, the true mass
emission rates under cold start conditions for one or two FTP
cycles would likely be much greater than indicated herein. The
LA-4 procedure, on the other hand, is of sufficient duration that
the cold start probably will not have a severe impact on the
particulate mass emission rate.
As noted earlier in this discussion, exhaust catalytic reactors
have a pronounced effect on particulate emissions (when using
non-leaded fuel, of course) during cold start vehicle operation.
Table 53 presents other comparisons regarding catalyst effects.
The data suggests that particulate emission rates from new
catalysts (Runs 41 and 56) exceed emission rates from non-catalyst
equipped engines perhaps due to purging of loss material from the
packed catalyst bed. Cold start particulate mass emissions are
lower when using a catalytic reactor 1n the exhaust system. The
effect of the catalytic reactor used in Run 56 on aldehyde emissions,
as reported in the Results Section (Table 27), should also be noted
here.
Further effects of catalytic devices and air/fuel ratios on particulate
emissions and aldehyde emissions is reported under EPA Contract
EHS 70-101 using similar engines and procedures to those used
herein. In summary, the catalytic devices studied increased
particulate emissions and substantially reduced aldehyde emissions.
Lean air/fuel ratios result in somewhat higher particulate emission
rates.
-------
-193-
TABLE 53
EFFECT OF EXHAUST CATALYTIC REACTORS ON PARTICULATE
EMISSION RATES WITH NON-LEADED 91 RON FUEL
Run No.
(Packed Bed Proprietary Devices)
Operational Mode
Engine/Vehicle
Data
With Reactor:
39
71 Chev 350 CID
Vehicle 61313
500 miles
41
42
56
Vehicle 61313
71 Chev 350 CID
Vehicle 60337
53,000 miles
70 Chev 350 CID*
Engine
FTP cycle, cold start
FTP cycle, hot start
60 mph - cruise
60 mph - cruise
60 mph - cruise
Particulate Emission
(gm/mile)
0.0059
.0119
.0144
.0068
.0102
.0408
.0088
.0292
Without
16
43
58E
Reac
70
tor:
Chev
71 Chev
Vehicle
2,500 mi
71
10,
350
350
les
Chev 350
000 miles
C
C
C
I
I
I
D
D
D
60
60
60
mph
mph
mph
- cruise
- cruise
- cruise
.01
.01
.01
627
15
62
*Catalytic reactor was added to exhaust system after 75-hour
stabilization sequence.
Only a limited evaluation of the effect of engine make is possible
from the data generated. The basis for such a comparison is
shown in Table 54. These data are from engine dynamometer tests
with the fuel noted and suggested that the 1971 Pontiac 400 CID
engine has significantly lower particulate emissions than the
1970 Chevrolet 350 CID engine. Limited data on the 1971 Chrysler
383 CID suggests that it is similar to the Pontiac engine in
particulate emissions.
-------
-194-
TABLE 54
EFFECT OF ENGINE MAKE ON PARTICULATE EMISSIONS
ENGINE DYNAMOMETER TEST
Particulate Emitted
Engine Run No. Fuel (gm/mi 1 e) MMED
70 Chev 350 CID 22 AMOCO 91 RON 0 TEL 0.0133 <0.1
21 AMOCO 91 RON 1/2 cc TEL .0187 <0.1
23 Fuel Type A .0910 <0.1
71 Pontiac 29/32 AMOCO 91 RON 0 TEL .0032/.0031 1
400 CID 40 AMOCO 91 RON 1/2 cc TEL .0114 0.37
31 Fuel Type A .065 ^0.1
71 Chrysler 59 AMOCO 91 RON 1/2 cc TEL .01206 *0.1
383 CID
No realistic appraisal of engine make effect on particulate emissions
from vehicles is possible. Many vehicles and makes have been
examined using several fuels. The trends observed in the engine
dynamometer studies are valid; i.e. higher lead content fuels result
in higher particulate emissions. Eight 1969-1971 Chevrolet 350 CID
engine vehicles operating on Fuel Type A have been evaluated.
Mileages range from 3,000 to 35,000. Particulate emission rates at
60 mph cruise condition range from 0.1064 gm/mile to 0.1565 gm/mile,
the average being 0.1299 gm/mile and the high value being from a
1971 low mileage vehicle.
During Runs 28 and 31, several particulate mass measurement techniques
were evaluated. They included the total exhaust hot filter, a
Beta-gauge/tape sampler, a Piezoelectric Crystal Monitor, the
Andersen/filter combination at 1 cfm, and a 4 cfm total filter. The
first three devices were provided by the Division of Chemistry
and Physics, EPA. Tests were conducted under steady-state cruise
conditions with engines and vehicles, and under vehicle cyclic
operation. The results of this cooperative study have been presented
(12)
in the Results Section and have been publishedv '. In general,
the Andersen Sampler/filter provides the best measure of exhaust
-------
-195-
particulate mass emissions. The 4 cfm filter suffers from
temperature and face velocity effects discussed earlier. The Beta-
gauge approach provides an excellent mass measurement method for
leaded fuels but its threshold sensitivity is too low for emissions
from non-leaded fueled engines. The crystal monitor gave results
consistently lower than all other techniques and was inoperable
during cyclic vehicle operation. At this point in time, no device
appears to be available to provide real time data on particulate
emissions. The total exhaust hot filter suffers from the temperature
effects discussed earlier but much more severely than does the
4 cfm diluted sample filter.
Nineteen particulate samples from nine runs using leaded gasoline
showed 1.7 to 8.6 percent benzene solubles. In this discussion,
the benzene soluble fraction is defined as that portion which was
also soluble in methanol. Seven samples from four lead-free fuel
runs ranged from 13.4 to 70 percent solubles. Run 34 is exceptional
in showing 20.9 percent benzene solubles with a leaded gasoline;
Run 34 was the only run employing a high performance, high octane
requirement vehicle. Run 44 shows 2.4 percent benzene solubles
when non-leaded gasoline was used; Run 44 was the only run utilizing
non-leaded Fuel Type B.
The amounts insoluble in methanol ranged from 10 to 30 percent of
the amount initially soluble in benzene. In some cases, the methanol
insoluble material appeared to be an oil (i.e. Runs 22, 23, 34),
having IR characteristics of an aliphatic hydrocarbon. In several
other cases, the methanol insoluble fraction was soluble in acetone,
producing a yellow coloration similar to the methanol soluble
fraction, and is believed to be organic. The methanol insoluble
fraction was generally insufficient for routine analysis.
Particulate samples of runs utilizing leaded fuels showed an
acidity of 0.02 to 0.83 percent calculated as benzoic acid; the
average was 0.37 percent for 21 samples excluding one exception
-------
-196-
of 7.8 percent. Five samples from runs without lead in the fuel
ranged from 0.34 to 4.5 percent acidity, with the median value
C\-3]
at 1.0 percent. Sawicki and Hauserv °' have shown that carboxylic
acids are present in the benzene soluble fraction of air-borne
particulates. The acidities of benzene and methanol soluble fractions
ranged from 2 to 24 percent with the exception of the Type B fuel
sample (Run 44) which showed 42 percent.
The phenolics of 28 pertinent particulate samples (17 runs)
ranged from 0.01 to 1.8 percent calculated as p-phenylphenol.
Samples Range, %
20 0.01 - 0.12
6 0.20 - 0.44
2 1.1 - 1.8
No distinction could be made based on the presence or absence
of lead (TEL) or additives. The phenolics of the benzene and methanol
soluble fractions range from 0.4 to 3.7 percent with the exception
of the Type B fuel sample which was 17 percent. Gross^ ' reports
increased phenolic emissions in direct relation to fuel aromatics,
which our studies tend to confirm.
The ultraviolet absorptivity of the benzene soluble fraction
is. considered to be a measure of aromatic but not aliphatic organic
chemicals. Absorptivities can be related to the published knowledge
of the ultraviolet absorbance characteristics of organic compounds.
Absorptivity, earlier called extinction coefficient or specific
extinction, is discussed in books by Scott^ ' and by Friedel and
/ -I c \
Orchin^ '. When the amount of benzene soluble fraction is too small
for accurate measurement, the related values such as the relative
ultravjolet absorbance/mg particulate or the ultraviolet absorbance
of_ the total , col lected particulate may be useful for comparative
evaluations. The absorptivities of the benzene (and methanol)
soluble fractions range from 3.5 to 53. Two possible correlations
are observed. The aromaticity of the benzene solubles was lower
(1) when Andersen samplers were employed in contrast to glass
fiber filters, and (2) when lead (TEL) was omitted in the fuel
used.
-------
-197-
Thus with the Andersen post filters, samples from runs containing
leaded fuels showed values of 12 to 42 (Runs 23 and 31) whereas
samples from non-leaded fuels showed values of 3.9-7.2 (Run 29).
With glass filters, the corresponding values with lead were 21
to 53 (Runs 19, 20, 23, 24, 25, 28, 31, 34, 40, with 15 excepted).
Corresponding values without lead were 16 to 29 (Runs 22, 29, 53,
with 44 excepted).
Runs 24 and 25 are the only duplicate engine runs listed in the
tables. Runs 22, 24, and 25 were the only runs for which replicate
particulate samples were collected during the run and subsequently
analyzed. An indication of reproducibi1ity, maximum deviations,
expressed as percent of the mean (average), were calculated for
the duplicates as follows:
TABLE 55
ENGINE RUN AND ANALYTICAL METHOD REPRODUCIBILITY
ANALYSIS OF FIBERGLASS FILTER PAPERS
EXPRESSED AS PERCENT OF THE MEAN
Engine Run Filter Paper
Repeatabili ty Repeatabi1i ty
In particulates, benzene solubles 14% 6%
acidity 46% 41%
phenolics 20% 33%
In benzene soluble fractions,
absorptivity 5% 3%
acidity 37% . 39%
phenolics 20% 20%
The deviations indicate that the acidity measurements are less
precise than the others, possibly because trace acid contamination
is more likely. The precision is best for the percent benzene
solubles and absorptivity because milligram amounts are utilized;
the analyses of phenolics and acidity utilize microgram amounts.
-------
-198-
Hangebrauck et. al. analyzed for polynuclear aromatics in exhaust
participates, and calculated reproducibi 1 i ty as 42-55 percent as
percentage of the mean^ '.
If the experiments and analyses are conducted to help attain a more
desirable ecology, then the precision is deemed adequate to
detect significant changes (i.e. two-fold and greater). Precision
can be improved by processing larger samples, or by using averages of
multiple determinations.
The Gelman, Type A, glass fiber filter (61698, pure grade, 0.3y,
142 mm) is considered the best of those studied for the analysis
of organics. The residues obtained via benzene extraction of the
blank filters amounted to 0.4 ± 0.25 mg with absorptivities of
2.1 ± 1 at 255 nm.
The results obtained using the Millipore filter AAWP, 0.8y are
unsatisfactory because the benzene soluble residues of blank filters
ranged from 25 to 30 mg, often exceeding the weights of the residues
obtained by benzene extraction of filters containing particulates.
The blank residues had absorptivities ranging from 0.6 to 0.8 at
25 nm, attributed to a tailing effect of an intense absorbance
doublet at 275 and 285 nm.
The UV absorbance and fluorescence values tend to give similar
variations on all the samples. In general, the smaller particles
have the highest concentration of detectable organic material present.
The concentration also increases when non-additive gasolines are
used; however, the total particulate is also decreasing and, therefore,
the total detectable organics in a given size range do not vary
significantly with additive. The tube sweeping samples indicate
an increase in organics at a further distance down the tube from
the engine, while the slit samples contain very low organic
levels, which may be due to the low contact with exhaust fumes.
The fluorescence curves may be the most useful in the future in
-------
-199-
correlating to actual percentage amounts of various classes of
organic compounds, since spectra have been obtained at excitation
wavelengths of 290, 330, and 353my.
The Relative UV Fluorescence (RF) value was assumed to be
proportional to the poly-nuclear content (i.e. anthracene
and higher); however, this point has not been established
experimentally in this series.
Samples from six Andersen impingement filter plates of Runs 21
and six from Run 22 were analyzed according to the UV procedure
described earlier but modified to measure only those dilutions
when the ultraviolet absorbance at 255 nm is less than 0.4 to minimize
fluorescence quenching. The RF must be compared to particulate
weight, benzene soluble fraction, or the Relative Ultraviolet (RU)
value for correlation and other uses of the analyses. The concept
of the RF and RU values was devised for small amounts (i.e. <10 mg)
of collected particulates.
The RU value is considered a relative measure of aromatics in particulate
extracts; absorbance values are proportional to concentration. The
RF value is considered a relative measure of poly-nuclear aromatics
(PNA). The ratio RF/RU could be a relative measure of the ratio
of PNA to total aromatics. If both RU and RF values are proportional
to concentration, then the ratios RF/RU and RU/RF will be constant
at different dilutions.
Plotting data for Runs 19 and 20 as shown in Figures 79 and 80
illustrate two points: 1) The ratios of RU/RF changed markedly
upon further dilution of the extracts of Plates 1 and 6, Run 20.
2) The ratio RU/RF of all extracts decreases proportionally with
the dilution as measured by absorbance. These results can be explained
by fluorescence quenching at higher concentrations. The established
technique for minimizing quenching is to make measurements in solutions
of greater dilutions.
-------
-200-
Figure 79
Ratio RU/RF as Function of A255
Run #20
Extracts of Andersen Plate
2.0
Lr>
m
(X
2. .O
O
PLATE
0
E I
*l LWT6 t
o
8
»o
-------
-201-
Figure 80
Ratio RU/RF as Function of A255
Run #19
Extracts of Andersen Plate
_ *
in
.
c?
RUN
PLME
6
PLATE 5
0
L.
-------
-202-
Figures 81 and 82 illustrate the corresponding ratios for Runs 21
and 22 when the absorbance at 255 nm of the solutions measured
was kept below 0.4. In each run, with the exception of Andersen
stage 1, the ratios are considered to be constant (i.e., 2.6 ±0.4
and 2.9 ±0.2).
The ratios were plotted as RU/RF in the figures to emphasize quenching;
the ratios are given as RF/RU in Table 56 to be proportional to
fluorescence content.
Assuming that the ratios of RF/RU listed in Table 56 are meaningful,
the following conclusions can be made:
a) The largest particulates (Plate 1) contain a smaller
ratio of PNA's to total .aromatics present.
b) No significant differences in the ratios for
particulate sizes represented on Plates 2 through 6.
c) The differences in the ratios observed between
i
Runs 21 and 22 are considered insignificant.
The levels of carbonyl compounds, calculated as benzophenone equi-
valents, were less than 5 percent in all particulate samples examined.
Comparisons and correlations with engine operating conditions could
not be made with confidence below this level. Accuracy is limited
because of the high solvent and filter blanks. Reducible chemicals
other than carbonyls are potential interferences.
Time did not permit checking the polarographic analyses using established
methods. The polarographic responses are based on measurement
of reducible, chemical species and are characterized by specific,
half-wave potentials. Aliphatic carbonyls and aromatic aldehydes
in general give useful responses only after conversion to the hydrazones
by addition of hydrazine. Lead salts and aromatic ketones such
as acetophenone and benzophenone give measurable responses without
hydrazi ne.
-------
1.2,
-In
(^
C<
ILJ
^
- Z
IT.
U
H
h
-203-
Figure 81
Ratio RU/RF as Function of A255
Run #21
Extracts of Andersen Plate
2.1
CS>
JZL
O Z, 4 6 * 10
Figure 82
Ratio RU/RF as Function of A255
Run #22
Extracts of Andersen Plate Filters
PL/VYE \
i
o
0 2. ' ' 4 6 8
-------
-204-
TABLE 56
ANALYSES OF RUNS 21 AND 22
Andersen
Run Plate
21 1
2
3
4
5
6
22 1
2
3
4
5
6
Sample Wt.
(mg)
2.12
2.00
1.39
1.10
0.44
0.61
0.62
0.40
1 .00
0.95
1 .16
0.90
Relative
Ultraviolet (RU)
Value
1330
850
719
1000
1909
3607
6242
3175
1730
1684
2250
3591
Relative
Fluorescence (RF)
Value
375
295
332
442
805
1631
1484
1105
611
608
824
1139
Ratio
RF/RU
0.28
0.35
0.46
0.44
0.42
0.45
0.24
0.35
0.35
0.36
0.37
0.32
Note
Fluorescence determined with solutions diluted so that the
ultraviolet absorbance at 255 nm <0.4.
-------
-205-
In this work a maximum of 2 ml of methanol solutions of the benzene
soluble residue was available for polarographic analyses. The
results are expressed in amounts of representative compounds for
each class rather than mole percentiles. Thus aliphatic carbonyls
are calculated as acetaldehyde, even though this volatile compound
is not expected in particulate samples. Responses for aliphatic
ketones (limit, 25 yg/ml calculated as acetone) and zinc salts
(limit, 10 yg/ml) were not observed in the samples examined.
The response for formaldehyde is fairly specific; its presence in
some particulate samples could be accounted by the oxidation of
micro amounts of the methanol solvent. Benzophenone was chosen
as a calibration standard because prior spectroscopic work after
formation of the 2,4-dinitrophenylhydrazones indicated the carbonyls
to be more similar to the aromatic rather than aliphatic ketones.
At lower levels, zinc salts could interfere in the determination of
benzophenone.
An unsuspected finding was the presence of lead compounds in the
methanol solutions of the benzene soluble fraction when leaded
fuel was used. Thus the benzene soluble fraction of Run 40 showed
10.1 percent Pb by emission spectroscopy and 13.9 percent via
polarography. The benzene solubles from eight out of nine runs
utilizing leaded gasoline showed polarographic responses equivalent
to 2-14 percent lead; the limit of detection in the ninth run was
1.5 percent. Corresponding analyses of Runs 22 and 44 (non-leaded)
showed a 0.9 percent (polarography) and 0.4 percent (emission
spectroscopy) respectively.
Polarographic analysis of the sample collected during Run 44
indicated the presence of an interfering material equivalent to
56 percent Pb. Thus the high lead content of Run 31 is questionable,
The values for lead via polarography should be considered maximal.
Emission spectroscopy is superior when only the lead content is
desi red .
-------
-206-
Lead was not detected in the blanks from unused filters and the
benzene solvent. The lead response could not be measured polaro-
graphically when Millipore filters were used because an excessive
background signal was observed. The percent Pb in the benzene
solubles was calculated as follows:
V x W
% Pb =
Ws x 10
where
WDK is the response for Pb calcualted as yg/ml
Pb
s
V is the amount of.methanol in ml used to dissolve W
W is the amount of benzene soluble residue, mg
Values of percent Pb were not calculated for samples containing less
than 1 mg/5 ml benzene solubles because the detection limit in these
cases would be 3 percent.
It has been suggested that the UV absorptivity at 255 nm of the
benzene soluble residue can be used as a measure of aromaticity.
PbBr2 has an absorptivity of 16.6 at 255 nm. Thus the presence
of lead compounds can alter the absorptivity and produce an erroneous
measure of aromaticity. Measurement of the absorptivity at 300
rather than 255 nm would minimize the interference of lead compounds
in measuring aromaticity.
It should be readily apparent at this point, that detailed in-depth
analysis of particulate material collected from each and every
experimental run was not conducted. Experimental runs and subsequent
analyses were designed consistent with attempts to ascertain signi-
ficant factors and detailed analysis of selected samples, as much as
to develop and critique the analytical procedure. Complete analysis
of a single vehicular cycled run would be literally impossible
because of lack of sufficient sample, even when using leaded fuels.
The report, does, however, provide meaningful general examination
-------
-207-
and details of particulate emissions with sufficient and appropriate
examination of key variables, as they become apparent, to warrant
its use as the basis for detailed future studies.
-------
-208-
VI. FUTURE
This research program has attempted to quantify the key factors
associated with the generation, collection, and analysis of
exhaust particulate as related to fuel factors and additives
therein. As is usual in ventures of this nature, research
generates many more questions than it answers. It is obvious that
much additional time and money can be spent analyzing exhaust
particulates and, indeed, such may be necessary in the future.
A key factor, however, before meaningful work can be conducted
by various groups is the examination of the effects of the generating
and collection procedures on exhaust particulate. Real-world
exhaust particulate assessment is nearly impossible and certainly
impractical. On the other hand, examination of tailpipe particulate
emissions is clearly misleading.
Further efforts must be directed toward defining key generation and
collection aspects of the exhaust particulate problem so that
nearly-real assessments of fuel factors, additives, and devices
can be made.
Such efforts will, simultaneously, provide the appropriate technical
review necessary for the meaningful application of an exhaust
particulate emission standard from motor vehicles, if such is
employed in the future.
-------
-209-
REFERENCES
T. Habibi, K. , Kunz, W. 6., Jacobs, E. S., Pastell, D. L.,
Characterization and Control of Vehicle Gaseous and
Participate Exhaust Emissions," Fifth Technical Meeting,
Air Pollution Control Association, West Coast Section,
Oct. 8-9, 1970.
2. Medi-Comp Research and Development Corp., Salt Lake City,
Utah.
3. Olin, J. G., and Sem, G. J., "Piezoelectric Aerosol Mass
Concentration Monitor," presented at Symposium on Advances
in Instrumentation for Air Pollution Control, Cincinnati,
Ohio (May 1969).
4. Chaun, R. L., "An Instrument for the Direct Measurement of
Particulate Mass," Aerosol Science 1, p 111 (1970).
5. Olin, J. G., Sem, G. J., and Christenson, D. L., "Development
of a Piezoelectric Microbalance for Continuous Measurement
of Aerosol Mass Concentration," Final Report, Contract
No. CPA 22-69-83, Thermo-Systems, Inc., (May 1970).
6. Nader, J. S., and Allen, D. R.* "A Mass Loading and
Radioactivity Analyzer for Atmospheric Particulates,"
presented at the 52nd Annual Meeting Air Pollution Control
Association, Paper No. 59-28 (June 1959).
7. Baldecker, P. A., Anal. Chem. 4_3_, 405 (1971).
8. Hess, T. M., Owens, J. S., and Reinhardt, L. G., Ind. Eng.
Chem. Anal. Ed.. 11, 646 (1939).
9. American Society for Testing Materials, 1916 Race Street,
Philadelphia, Pa., "Recommended Practice of Photographic
Photometry in Spectrochemical Analysis," ASTM Designation
E116 (1964).
10. Valori, P., Melchiorri, C., Grella, A., and Alimenti, G.
Nuovi Ann. Ig. Microbiol. 17(4). 311-24 (1966); C.A. 67.,
14651h (1967).
11. Environmental Protection Agency, Office of Air Programs,
5 Research Drive, Ann Arbor, Mich.
-------
-210-
12. Manary, 0. J., Moran, J. B., Herling, R. H., Karches, W. E.,
and Wagman, J., "A Comparison of Automotive Particle Mass
Emission Measurement Techniques," paper presented at Combustion
Institute 1971 Technical Session, Ann Arbor, Mich.,
March 23-24, 1971.
13. Sawicki, Hauser, and Stanley, Anal. Chem. 31, 2063-65 (1959).
14. Gross, G. P., "Effect of Fuel and Vehicle Variables on
Polynuclear Aromatic Hydrocarbon and Phenol Emissions,"
paper presented at the SAE Meeting, Detroit, Mich.,
Jan. 10-14, 1972.
15. Scott, A. I., Ultraviolet Spectra of Natural Products,
MacMillian Company,New York (1964).
16. Friedel, R. A., and Orchin, M., Ultraviolet Spectra of
Aromatic Compounds, John Wiley & Sons, Inc., New York (1951).
17. Hangebrauck, R. P., Lauch, R. P., and Meeker, J.,
Amer. Indust. Hyg. Assoc. J., pages 47-56 (Jan.-Feb. 1966).
18. Bergman, W., "Characterizing and Measuring Automotive
Particulate Emission With Two Improved Sampling Techniques,"
paper presented at the Combustion Institute, Ann Arbor,
Mich. , March 23-24, 1971.
19. Esso Research and Engineering Company, Development of an
Automotive Particulate Sampling Device Compatible with the
CVS System, 72nd National Meeting of AIChE, St. Louis,
Mo., May 22, 1972.
-------
PART 2
-------
-211-
I. CONCLUSIONS
1. Exhaust particulate mass emission rates are a function of
mode of vehicle operation. They increased with test mode
in the following order: 60 mph steady state < 41 minute
cold start LA-4 cycle < 23 minute cold start LA-4 cycle.
2. Low-leaded fuel consistently afforded higher particulate
mass emission rates than did non-leaded fuel.
3. The mass median equivalent diameter of exhaust particulate
is a function of vehicle operation mode. It increased with
test mode in the following order: 60 mph steady state < 41
minute cold start LA-4 cycle < 23 minute cold start LA-4
cycle over the range of 0.54-9.0 microns.
4. Of the particulate filtering systems employed, the highest
mass emission rates were detected by an Andersen Impactor with
back-up 142 mm Millipore filter operating at 1 cfm. Successively
lower mass emission rates were obtained by use of parallel
142 mm Gelman glass fiber filters operating at 1 cfm and
4 cfm.
5. An increase in dilution tube flow rate from 350 to 500 cfm
did not result in any significant trend in observed particulate
mass emission rate. However, it did effect an overall increase
in the mass median equivalent diameter of collected particulate
and in the concentration of trace metals associated with the
collected exhaust particulate (500 cfm rates being the higher).
6. Cooling of air ahead of the dilution tube inlet resulted in an
increase in both the observed particulate mass emission rates
and the concentration of particulate associated benzo-a-pyrene.
A corresponding decrease in particule MMED for non-leaded fuel
was observed. In general, this cooling also resulted in a
lower concentration of particulate associated trace metals.
-------
-212-
Cooling of the air diluted exhaust effluent by means of
a heat exchanger within the dilution tube resulted in a
decrease in the observed mass emission rates for particulate
matter. No significant trends were obvious for the effect
of this variable on particulate concentrations of either
benzo-a-pyrene or trace metals.
-------
-213-
II. EXPERIMENTAL PROCEDURE
A. FUEL CHARACTERIZATION
Samples of some 30 different commercially available gasolines
were procured from three different geographic areas of the
United States. These areas'- New Jersey, Los Angeles, and
Detroit - were selected in order to afford samples of gasoline which
had been refined from at least two different base stocks.
The samples were collected in 5 gallon mild steel cans which were
rinsed with 1 gallon of the specific fuel to be analyzed prior
to filling. In order to assure that metal pick-up from the cans
was not contributing to the trace metal analyses which were
performed on each sample, research grade fuel was stored in one
of the cans for a period of one week and then subjected to analysis
for trace metal content as a control.
A list of the fuels procured, their geographical origin, advertisied
RON and lead content is shown in Table 57.
Each sample was subjected to analysis for RVP, distillation, RON,
MON, and FIA composition using standard ASTM Procedures*. In
addition each gasoline was analyzed for trace metals, lead,
.sulfur, phosphorus, aldehydes, chlorine and bromine, carbon
and hydrogen, and benzo-a-pyrene using the standard analytical
methods which have been described earlier in this report.
B. EVALUATION OF DILUTION TUBE VARIABLES ON THE COLLECTION OF
EXHAUST PARTICULATE HATTER
Using the Dow dilution tunnel described in detail on page 18 of
this report, a series of tests were conducted to evaluate the
effects of several dilution tube variables on the collection and
nature of automotive exhaust particulate.
*ASTM Procedures D323, D86, D908, D357, D1319
-------
-214-
TABLE 57
GASOLINE SAMPLES IDENTIFICATION
Sample
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
Location
Detroit
Detroi t
Detroi t
Detroit
New Jersey
New Jersey
New Jersey
New Jersey
Los Angeles
Los Angeles
Los Angeles
Los Angeles
Detroit
Detroit
Detroit
New Jersey
New Jersey
New Jersey
Los Angeles
Los Angeles
Los Angeles
New Jersey
Los Angeles
Detroit
New Jersey
Los Angeles
Detroi t
Detroi t
New Jersey
Los Angeles
Stated RON
Stated Lead Content
94 '
94
94
94
94
94
94
94
94
94
94
94
100
100
100
100
100
100
100
100
100
94
94
91
91
91
91
91
91
91
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
3 cc/gal
No lead
3 cc/gal
3 cc/gal
3 cc/gal
0.5 cc/gal
0.5 cc/gal
0.5 cc/gal
0.5 cc/gal
0.5 cc/gal
No lead
No lead
No lead
No lead
-------
-215-
Exhaust particulate matter was generated using two 1971 Chevrolet
Impalas operating on the chassis dynamometer, each fitted with
identical 350 CIO V-8 engines. These vehicles had been utilized
in the earlier part of the contract effort. One vehicle was
operated on Indolene 0 91 RON non-leaded fuel, and the other on
Indolene 5 91 RON fuel containing 0.5 cc TEL/gallon in combination
with 0.2 theoretical equivalents of EDC and 0.07 theoretical
equivalents of EDB.
Each test vehicle was operated on the Clayton chassis dynamometer
and the total exhaust fed into the Dow dilution tube described in
detail in Phase I of this report.
Air diluted exhaust particulate was collected identically utilizing
sample probes located at the end of the exhaust inlet and connected
to two parallel 142 mm Gelman glass fiber filters operating at 1 cfm,
one 142 mm Gelman glass fiber filter operating at 4 cfm, and an
Andersen 6-stage impactor with back-up 142 mm Millipore filter
operating at 1 cfm. This type of collection system has been
described in detail earlier in this report (see page 21).
A series of baseline tests were performed on each vehicle. Particulate
matter was generated and collected under the following vehicle
operating sequences:
a) 60 mph road-load, steady state - 2 hours
b) 23 minute LA-4 cycle (cold start)
c) 41 minute modified LA-4 cycle (cold start)
The total flow rate through the dilution tube was adjusted to
350 cfm prior to each test run being initiated with the vehicle
shut down. In each test the following particulate characteristics
were determined: mass emission rate (gm/mile), mass size distribution,
and polynuclear aromatic content determined as benzo-a-pyrene. Attempts
to determine the organic content of the collected particulate matter
-------
-216-
by carbon and hydrogen analysis failed because insufficient
sample was available to afford meaningful data. In all test
runs trace metal analyses were also performed on the particulate
matter collected on the 142 mm Millipore filter used as a back-up
to the Andersen impactor. In those runs utilizing low lead fuel,
a lead determination was made on the particulate matter collected
on the various stages of the Andersen impactor. The above
analytical scheme was used throughout this investigation of
particulate sampling parameters. The analytical procedures
utilized have been described in detail in Phase I of this report.
On completion of the baseline testing, the following series of
tests were conducted:
1 . Variation of Dilution Tube Flow Rate
Tests b) and c) above were repeated with the total flow rate
through the tube adjusted to 500 cfm for both the leaded and
non-leaded vehicles. Again this flow rate was established prior
to each test sequence with the vehicle shut down.
2. Effect of Dilution Air Cooling
A series of experiments were performed to determine the influence
of dilution air cooling on collected exhaust particulate matter.
Three approaches were utilized; cooling within the dilution
tube, cooling of diluent air ahead of the dilution tube, and use
of diluent air when the ambient temperature was less than 40°F.
In order to effect cooling of the air-diluted exhaust effluent
within the dilution tunnel, a heat exchanger was designed in
such a way that it offered a maximum surface area for cooling
yet provided the least opportunity for particle trapping by
impingement. To accomplish this, two 48" x 29" x 1/16" mild
steel plates were fitted each with 40 feet of 1/4" ID copper
tubing which was looped back and forth over their surface.
The tubes were welded to the plates at intervals of approximately
-------
-217-
1 inch along their length (see Figure 83). The plates were
then bent along their width to form two concentric cylinders
which were separated by 2-inch metal spacers. This assembly
was mounted in the dilution tube at a point 4 feet downstream
of the exhaust inlet and held in position by a second set of
2-inch spacers fitted to the inside wall of the dilution tube.
A schematic of the heat exchanger is shown in Figure 84. This
arrangement assured a minimum interference with the flow
pattern of diluted exhaust effluent within the dilution tube.
The effect of this device on collected particulate matter was
determined with both air and water passing through the cooling
coils during 60 mph steady state and 23 minute LA-4 cycle
(cold start) vehicle operation. Runs were conducted with the
total air flow through the dilution tube adjusted to both
350 cfm and 500 cfm prior to vehicle start-up.
In a second set of experiments, the heat exchanger was removed
and an automotive radiator attached to the dilution tunnel
immediately ahead of the air inlet filter. Passage of water
through this device permitted cooling of inlet air prior to
its entry into the dilution tube. The effect of cooling the
dilution air in this manner on the collected particulate
matter was investigated with the test vehicles operating at
60 mph steady state (2 hours), in the 23 minute LA-4 cycle
(cold start), and in the 41 minute modified LA-4 cycle (cold
start). These tests were also run with the total dilution
tube flow rate adjusted to both 350 cfm and 500 cfm prior to
vehicle operation.
A final series of tests intended to ascertain the effect of
dilution air temperature on collected exhaust particulate
was conducted in the absence of a heat exchanger by drawing
dilution air from outside the dynamometer facility, which had
an ambient temperature of less than 40°F just before the
-------
48"
A
29"
10 - 1/4" ID Copper Tubing
£T>
C
50
00
co
i
ro
O3
DILUTION TUBE COOLING BAFFLE
-------
10-48 inch 1/4 inch ID Copper
Tube Coil on Each Sleeve
CUT-AWAY VIEW OF COOLING SLEEVE
INSIDE OF DILUTION TUBE
Coolant Inlet to
Outer Sleeve Coil
FIGURE 84
Outer Cool ing
Baffle Sleeve
Coolant Outlet From
Innter Sleeve Coil
Dilution Tube
Coolant Outlet From Outer
Sleeve Coil
ro
vo
Coolant Inlet to
Inner Sleeve Coil
Spacers (8)
-------
-220-
Dri-Pak filter. These latter experiments were run with the
vehicles operating at 60 mph steady state (2 hours), in the
23 minute LA-4 cycle (cold start), and in the 41 minute
modified LA-4 cycle (cold start). The total flow rate through
the tube was adjusted to 350 cfm prior to each test run.
Figure 85 shows a complete test matrix for the above set of
experiments.
C. EVALUATION OF A BETA-GAUGE PARTICIPATE MASS MEASURING DEVICE
A series of test runs were performed to correlate the exhaust
particulate mass measuring efficiency of a prototype Beta-gauge
compared with the conventional collection techniques utilized
throughout the major part of this contract effort.
The Beta-gauge device evaluated was developed by the Industrial
Nucleonics Corporation of Columbus, Ohio, under Environmental
Protection Agency Contract No. 68-02-0210. A detailed description
of the device can be found in the Final Report published under
this Contract in February 1972. Collection of exhaust particulate
within the device was accomplished by drawing a proportional
sample of air-diluted exhaust effluent from the Dow dilution tube
through a Pallflex E70/2075W filter pad having a cross-sectional
area of 3 sq cm. The sample probe for the Beta-gauge was located
at the end of the dilution tube remote from the exhaust inlet
and adjacent to the probes used to feed the conventional
filtering equipment (see Figure 2).
The following three vehicles operating on a chassis dynamometer
were used to generate the exhaust particulate:
-------
-221-
FIGURE 85
EVALUATION OF DILUENT AIR TEMPERATURE ON THE COLLECTION
OF EXHAUST PARTICULATE MATTER
TEST MATRIX
Dilution Tube
Cooling Mechanism Flow Rate Test Conditions*
Internal Heat Exchanger:
Air cooled 350 A, B
Water cooled 350 A, B
Water cooled 500 A, B
External Heat Exchanger:
Water cooled 350 A, B, C
Water cooled 500 A, B, C
Ambient Air <40°F 350 A, B, C
*A = 60 mph steady state
B = 23 minute LA-4 cycle (cold start)
C = 41 minute modified LA-4 cycle (cold start)
-------
-222-
1971 Chevrolet Impala - 350 CID V-8 - Indolene 0 fuel
1971 Chevrolet Impala - 350 CID V-8 - 0.5 cc/gallon leaded fuel
1971 Chevrolet Impala - 350 CID V-8 - 3.0 cc/gallon leaded fuel A*
These were operated under a variety of steady state conditions on
the chassis dynamometer and were also tested in the 23 minute LA-4
cycle (cold and hot start) and in the California 7 mode cycle.
For comparison purposes, two parallel proportional filters were
employed in this part of the program: a 142 mm Gelman glass fiber
filter operated at 4 cfm, and a 47 mm Gelman glass fiber filter
operated at 3.29 cfm. In one run (see Results Section) the Beta-
gauge unit was operated in such a way that the face velocity of
air diluted exhaust through it was equivalent to that in the
47 mm filter. This approach then allowed a direct comparison of
particulate mass emission rates as detected by both the Beta-gauge
and proportional filters for a variety of different fuels and vehicle
operating sequences.
*See page 85 of Phase I.
-------
-223-
III. EXPERIMENTAL RESULTS
A. FUEL CHARACTERIZATION
Physical and chemical analyses of the thirty commercial gasoline
samples procured are shown in Tables 58, 59, 60, and 61.
B. EVALUATION OF DILUTION TUBE VARIABLES ON THE COLLECTION OF
EXHAUST PARTICULATE MATTER
Tables 62 and 63 show the mass emission data obtained during those
test runs intended to determine the effects of dilution air cooling
and dilution tube flow rate on the physical and chemical character
of exhaust particulate matter. Also included is temperature data
obtained in each run for the raw exhaust immediately ahead of the
dilution tube, dilution air immediately prior to exhaust mixing,
diluted exhaust at the sampling zone and in the 1 cfm filter. The
latter temperature was measured a few millimeters above the filter
pad surface. In the steady state runs the dew point within the
filter units is also presented. This was determined by direct
measurement of the relative humidity and temperature of the air
diluted exhaust effluent at the sampling zone of the dilution tube
and subsequent use of psychrometric tables. Data generated by Dow
under Environmental Protection Agency Contract EHS-70-101 suggests
that a filter temperature of less than 20°F above the dew point
can lead to condensation of water within the filters and erroneous
mass emission data.
Tables 64 and 65 present data for the lead and benzo-a-pyrene (BaP)
content of the particulate matter collected.
Finally, Tables 66 and 67 show trace metal analyses for the
particulate matter collected on the back-up Millipore filter used
in each of the test runs.
-------
TABLE 58
PHYSICAL ANALYSES OF GASOLINE SAMPLES
API Gravity
Distillation:
IBP
5
10
20
30
40
50
60
70
80
90
95
EP
% Recovery
% Residue
% Loss
RON
MON
RVP
FIA:
% Saturates
% Olefins
% Aromatics
Stated RON
Stated Lead Content
(cc/galIon)
Source*
i
63.8
88
104
106
140
150
192
214
238
264
300
350
362
378
95.0
0.4
4.6
92.8
84.2
13.2
66.5
16.0
17.5
94
3
D
i
65.5
74
86
95
114
138
163
184
212
240
276
336
386
401
97.0
0.8
2.2
91.2
87.2
14.0
78.9
7.1
14.0
94
3
D
1
62.2
88
100
110
136
160
186
216
252
288
306
342
385
424
95.0
0.6
4.4
92.0
86.3
13.0
70.7
7.4
21.9
94
3
D
i.
60.7
84
100
111
136
166
190
216
246
276
302
352
392
420
96.0
0.5
3.5
93.1
87.0
12.9
70.7
7.4
21.9
94
3
D
5_
64.0
94
106
116
140
162
190
210
242
274
320
342
378
412
95.5
0.8
3.7
91.7
85.7
12.6
70.7
11.7
17.6
94
3
N
i.
61.2
78
93
104
128
153
182
216
244
282
311
356
382
414
96.0
0.8
3.2
93.8
86.0
13.5
60.8
13.7
25.5
94
3
N
7.
64.1
84
98
111
128
150
169
192
224
261
300
344
385
408
97.0
0.8
2.2
93.5
85.6
12.8
64.8
16.0
19.2
94
3
N
8.
63.0
88
112
120
148
176
200
222
248
172
304
340
362
390
95.0
1.0
4.0
91.9
85.6
12.3
69.1
10.6
20.3
94 '
3
N
i
59.1
88
108
118
146
172
194
212
236
262
290
346
398
414
97.5
0.6
1.9
93.3
84.4
11.3
71.7
5.2
23.1
94
3
L
15.
58.3
96
102
124
148
169
200
232
262
298
340
380
400
422
95.5
0.6
3.9
91.5
83.7
11.1
64.3
6.7
29.0
94
3
L
TJ_
60.1
80
98
110
138
169
192
222
264
290
324
360
381
412
96.0
0.8
3.2
91.2
84.7
12.6
71.0
8.6
20.4
94
3
L
li
60.4
96
112
122
144
162
184
202
228
266
300
362
388
424
95.5
0.8
2.7
93.6
85.0
10.1
72.2
8.1
19.7
94
3
L
ro
ro
*D = Detroit N = New Jersey L = Los Angeles
-------
TABLE 59
PHYSICAL ANALYSES OF GASOLINE SAMPLES
API Gravity
Distillation:
IBP
5
10
20
30
40
50
60
70
80
90
95
EP
% Recovery
% Residue
% Loss
RON
MON
RVP
FIA:
% Saturates
% Olefins
% Aromatics
Stated RON
Stated Lead
Content (cc/gal)
Source*
11
60.5
81
96
112
150 .
190
210
220
246
274
304
362
384
410
95.5
0.6
3.9
99.9
92.4
13.1
65.9
4.4
29.7
100
3
D
11
65.9
78
92
99
120
144
170
194
215
232
252
290
338
370
98.0
0.6
1.4
99.6
90.6
14.9
72.7
9.9
17.4
100
3
D
11
59.9
82
100
116
150
184
210
228
252
272
300
338
360
398
95.0
0.4
4.6
99.4
91.5
13.0
69.4
2.6
28.0
100
3
0
11
59.2
80
94
104
124
150
182
220
232
282
318
340
376
406
97.0
0.6
2.4
99.1
92.2
12.9
64.8
3.0
32.2
100
3
N
IT
65.4
86
96
102
122
140
162
188
210
240
272
312
356
394
96.0
1.0
3.0
100.2
91.1
14.1
64.2
14.8
21.0
100
3
N
i§.
56.3
84
104
116
144
180
206
220
236
240
276
316
358
386
97.0
0.6
2.4
99.6
85.9
12.5
49.2
8.4
42.4
100
0
N
li
56.7
86
108
122
152
188
212
232
254
270
310
338
382
412
97.0
0.6
2.4
99.6
91.9
11.3
64.5
5.0
30.5
100
3
L
20.
55.4
96
111
124
146
170
192
220
243
268
294
340
356
386
98.0
1.0
1.0
100.0
90.6
9.2
57.2
6.0
36.8
100
3
L
21
58.3
88
103
118
142
168
198
216
238
264
292
328
368
420
98.0
0.6
1.4
99.6
90.9
11.4
66.0
6.4
27.6
100
3
L
ro
t>o
en
*D = Detroit N = New Jersey L = Los Angeles
-------
TABLE 60
PHYSICAL ANALYSES OF GASOLINE SAMPLES
API Gravity
Distillation:
IBP
5
10
20
30
40
50
60
70
80
90
95
EP
% Recovery
% Residue
% Loss
RON
MON
RVP
FIA:
% Saturates
% Olefins
"% Aromatics
State RON
Stated Lead
Content (cc/gal)
Source*
22.
61.9
86
98
110
126
148.
170
196
222
252
290
348
378
398
95.0
0.8
4.2
95.3
84.1
12.8
54.0
16.6
29.4
94
0.5
N
23.
59.1
92
106
116
132
150
168
199
218
250
280
310
340
389
98.5
0.8
0.7
92.1
82.9
10.0
64.0
8.1
27.9
94
0.5
L
24.
60.0
102
122
138
160
176
204
222
240
260
288
328
342
390
95.0
0.6
4.4
88.4
80.6
9.6
67.9
7.5
24.6
91
0.5
D
25_
60.3
90
101
132
158
184
203
222
238
256
278
310
346
388
98.0
0.5
1.5
90.4
84.2
10.1
70.1
7.5
22.4
91
0.5
N
26.
54.9
99
118
134
163
196
224
252
280
290
304
359
382
408
95.0
1.0
4.0
91.8
83.2
9.7
63.7
3.0
33.3
91
0.5
L
27.
60.8
92
110
126
. 146
172
194
216
236
256
294
328
366
400
96.0
0.5
3.5
88.4
80.6
10.4
67.9
7.5
24.6
91
0.:
D
28.
62.5
84
108
110
132
160
190
212
236
260
292
342
370
400
96.0
0.4
3.6
89.9
83.7
12.0
75.5
2.1
22.4
91
0
D
2!
67.5
94
110
118
134
150
177
200
216
236
260
300
335
368
95.5
0.6
3.9
90.3
82.8
10.1
75.4
12.6
12.0
91
0
N
30.
60.0
106
118
134
154
175
192
216
236
252
283
314
340
394
99.0
0.5
0.5
89.8
81.1
7.5
66.2
7.9
25.9
91
0
L
ro
ro
*D = Detroit N = New Jersey
Los Angeles
-------
TABLE 61
CHEMICAL ANALYSIS OF GASOLINE SAMPLES
Fuel
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
Parts per Million (Wt.) q/qal
Fe Ni Cu Al Ca
<0.5 <0.5 <0.1 <0.5 <0.5
II It H II II
H II II II M
II II II II II
II II II II II
II M II II II
II II II II II
II II II II II
II It II II II
II II II II It
II II II II II
II II II II II
II II II II II
II II II II Qfg
" " " " 0.8
1.0 " " " <0.5
<0.5 ' 0.7
ii ii ii ii n c
II II II M II
M n n M <0>8
" " " " <0 . 5
ii n M n n
0.5 0.5
0.8 <0.5
<0.5
II II It II II
II II II II II
II II II II II
0.5 " " " 0.9
0.5 " " " <0.5
Mg Mn Cr Sn Zn Ti Pb
<2 <0.2 <0.5 <0.5 <2 <0.5 3
" " 3
1
n ii n n n ii -
II II M II II II _
II II II II It II ,
II II II II II II _
II II II II II II -
II II II II II II -
It II II II II II _
II M II II II M .
II II II II II It -
ii ii ii ii ii n -
n n n n n n -
it n n n n n -
n n it n n n _
n n n n n n _
n n n n n n
ii n n n n n
ii n n n n n
o
II II II II II II
II II II II II II
O ll ll II II II
-------
TABLE 62
EFFECT OF DILUTION VARIABLE ON PARTICULATE MASS .EMISSION RATES
NON-LEADED FUEL
Dilution Tube
Particulate Collected Thermal Profile
(gin/mile) (°F)
o
c
a a>
•a
I/I O
•c- y
VI
VI +J
03 VI
-C 01
o 03
•r- ce
4_>
3 3:
r— O
•9— r—
0 U-
350
500
350
350
500
350
500
350
350
500
350
350
500
350
500
350
350
500
350
500
350
0.
X 3 0
LU i— S-
•r- Q
+•> Q
03 LL.
01 C 0
1C ••-• — •
-
-
Air-5°F
H20-10°F
H20-25°F
-
-
-
_
-
Air-5°F
H20-10°F
H20-25°F
-
-
-
_
-
-
-
.
a>
+-> 3
03 Ol 1—
S- 03 c
o •*•* o ^— *
4-> C -r- LL.
03 >-> +J 0
•1- 3 O
•o *. r— «3-
O3 "r~ »r- V
o£ *z a—'
-
-
-
-
-
Yes
Yes
Yes
_
-
-
-
-
Yes
Yes
Yes
.. _
-
Yes
Yes
Yes
c
0) i-
t/l 0)
i- r—
01 a.
•o E
C R}
< CO
.0024
.0026
.0017
.0015
.0026
.0021
.0023
.0029
.0466
.1133
.0886
.0746
.0733
.0605
.1000
.0653
.0243
.0869
.0365
.0608
.0578
Ol
S-
o
0- i.
•r- Ol
i— 4J
r— i—
•r- •!—
S U.
.0071
.0060
.0012
.0074
.0079
.0131
.0182
.0062
.1073
.0333
.0280
.0373
.0933
.1120
.0666
.0746
.0882
.0304
.0973
.0913
.0608
Ol
C i-
Ol O
V) O.
t- T-
01 i—
•a + •—
C i-
en
re >
<— 03
eg *-^*
i- B
CU4-
X) U
•c-
U_ i—
.0046
.0116
.0055
.0055
.0075
.0057
.0066
.0096
.0793
.0466
.0466
.0303
.0533
.0466
.0533
.0770
.0365
.0347
.0395
.0652
.0700
4->
VI
3
03
JC
X
UJ
518
518
500
500
482
500 .
525
530
300
302
302
302
300
302
302
302
302
302
300
302
300
*t.
c
o
•t—
4^
3
w—
•r-
o
65
75
80
75
85
60
55
38
85
80
80
75
85
55
' 60
32
85
75
58
60
30
c
o
IV!
at
r—
a.
E
03
00
155
120
140
125
121
124
no
145
90
85
95
80
80
75
75
75
90
85
75
75
70
0
i.
3 r—
03 U_
S-
Oi E
E U
01
1— f—
115
100
103
100
98
100
92
no
85
80
80
77
75
70
72
68
83
80
72
70
68
c
•t-
o
a_
2
Ol
a
82
66
77
77
65
76
67
78
ro
ro
00
i
-------
TABLE 63
EFFECT OF DILUTION VARIABLE ON PARTICULATE MASS EMISSION RATES
0.5 LEADED FUEL
Particulate Collected
(gm/mi1e)
Dilution Tube
Thermal Profile
o
c
<"^ O
•Q
in o
••-S
(/)
in +•*
to in
J= (U
01-
60 mph
SS
LA-4
23 min
CS
Mod.
LA-4
41 min
CS
.
o
z
c
3
a:
127B
118B
149B
144B
1486
133B
137B
174C
127A
118C
149A
144A
148A
133C
137C
174A
124A
118A
133A
137A
174B
E
1 1
350
500
350
350
500
350
500
350
350
500
350
350
500
350
500
350
350
500
350
500
350
3
pa o 0. i. 10 C
X 3 O O +-> O'—
Ul r— S- J-> C -r- U.
•f- O (O •— ' +•> O
+•> O •>- 3 O
CL
TO E
C flB
<: <^
.0026
.0154
.0030
.0058
.0055
.0064
.0108
.0034
.1680
.2200
.1400
.1726
.2000
.2426
.3400
.0793
.0761
.0652
.1552
.0739
.0793
OJ
t.
o
CL i.
•r* O>
r— +•>
i— r—
•r* *r—
SLJL.
.0213
.0191
.0213
.0305
.0245
.0286
.0345
.0186
.2660
.1533
.0513
.0840
.0333
.2380
.2600
.0933
.1025
.1174
.1735
.1782
.0933
d
C i-
01 O
t/1 OL
i. -r-
0) + •—
^ r—
C '^
«£ S
.0239
.0345-
.0243
.0363
.0300
.0350
.0454
.0220
.4340
.3733
.1913
.2566
.2333
.4806
.6000
.1726
.1796
.1826
.3286
.2521
.1726
CM
•4-
O
in •
in en
03 >
r— (O
O— '
>- E
«U •*-
JD U
•r-
U-r—
.0166
.0212
.0189
.0214
.0208
.0221
.0229
.0138
.1120
.1266
.0420
.0630
.0533
.1446
.1133
.1166
.0517
.1130
.0608
.0391
.1166
+j
in
3
03
.C
X
Ul
482
464
518
554
518
464
472
644
302
305
305
290
305
300
302
300
305
302
305
302
300
•s.
c
o
•r
4_>
3
9—
•r-
0
65
85
75
70
95
52
52
36
65
85
75
70
83
52
52
37
60
78
52
52
37
Ol
c
o
tvl
O>
^
CL
E
>o
to
135
130
145
139
128
114
103
180
100
95
95
75
78
78
75
75
105
95
75
75
70
o
Ol CO
L. •"->
3 r—
4-> 'r-
03 Lu
i.
oi E
CLV-
E U
01
1— F-
99
104
108
108
103
89
88
135
95
80
75
75
75
70
68
75
88
82
72
70
70
c
•r»
O
Q.
S
Ol
o
64
68
80
79
i
76 rv>
ro
68 us
54
85
-------
TABLE 64
LEAD AND BENZO-a-PYRENE ANALYSIS
0.5 LEADED FUEL
Dilution Tube
Chassis Dyno Flow Rate
Test Mode Run No. (cfm)
60 mph
SS
LA-4
23 min
CS
Mod.
LA-4
41 min
CS
127B
118B
149B
144B
1486
133B
137B
174C
127A
118C
149A
144A
148A
133C
137C
174A
124A
118A
133A
174B
350
500
350
350
500
350
500
350
350
500
350
350
500
350
500
350
350
500
350
350
Wt. Percent Lead by
Heat Exchgr. in Radiator Atomic Absorption
Dilution Tube at Air Dilution Air on Andersen Plate No.
(°F Drop) Intake (<40°F) 1 + 2
3.00
0.27
Air-5°F - 1.33
H20-20°F - - 0.56
H20-15°F - - 0.53
Yes - 2.40
Yes - 0.42
Yes 0.35
0.69
0.82
Air-5°F - - 0.97
H20-20°F - - 0.62
H20-15°F - - 0.00
Yes
Yes - 0.75
1.06
0.88
1.60
Yes - 0.24
Yes 1.05
3 + 4
3.12
0.08
1.50
0.38
0.53
2.18
0.19
0.40
1.00
0.76
1.00
0.54
0.00
0.92
2.86
0.60
1.93
0.22
1.05
5 + 6
3.62
0.35
2.83
2.43
1.66
2.09
0.85
1.00
0.75
0.79
1.77
0.30
0.10
0.71
1.20
0.92
1.46
0.19
0.94
BaP ppm
Based on
Total
Particulate*
30
280
90
15
85
80 ™
105 £
60
440
30
35
345
160
95
60
60
90
1025
345
120
*From 1 cfm fiIter
-------
Chassis Dyno
Test Mode
60 mph
SS
LA-4
23 min
CS
Mod.
LA-4
41 min
CS
Run No.
164A
. 169B
152B
153B
154B
157B
159B
172B
164C
169C
152A
153A
154A
157C
159C
172C
164B
169A
157A
159A
172A
Dilution Tube
Flow Rate
(cfm)
350
500
350
350
500
350
500
350
350
500 .
350
350
500
350
500
350
350
500
350
500
350
TABLE 65
BENZO-o-PYRENE ANALYSIS
NON-LEADED FUEL
Heat Exchgr. in
Dilution Tube
(°F Drop)
Air-5°F
H20-10°F
H20-25°F
Radiator
at Air
Intake
Dilution Air
(<40°F)
Air-5°F
H20-10°F
H20-25°F
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
BaP ppm
Based on
Total
Parti culate*
Mass
170
30
15
115
95
165
60
5
215
85
10
50
120
85
105
85
170
185
270
295
530
ro
co
*From 1 cfm filter
-------
TABLE 66
PARTICULATE TRACE METAL ANALYSIS - MILLIPORE FILTER PAPERS - LEADED FUEL
Chassis dyno
Test Mode
60 MPH S.S.
-
LA- 4 23 win
cold start
Modified LA-4
41 minute
cold start
Run
No.
127b
118b
149b
144b
14 8b
133b
137b
174c
127a
118c
149a
144a
148a
133c
137c
174a
124a
118a
133a
137a
174b
Diln Tube
Flow rate
(cfm)
350
500
350
350
500
350
500
350
350
500
350
350
500
350
500
350
350
500
350
500
350
Heat Exch
in Dl tube
(°F drop)
-
Air-5°F
H,0-20°F
H,0-15°F
^
-
~
_
-
Air-5°F
H,0"-20°F
H,0-15°F
ft
-
—
' _
- .
-
-
-
Radiator at Dilution
..air. inlet air. 40°F
-
-
-
_
Yes
Yes
Yes
— ••
-
-
_.
- -
Yes
Yes
Yes
— —
-
Yes
Yes
Yes
Weight Percent
Fe Ni
,108<
.13 <
.02
.034<
.03 <
.04 <
.072<
.31 <
.42 <
.74 <
.182
.222
1.2 <
.157<
.103<
1.30
.235<
.222<
.14 <
.146<
.38 <
.027
.04
.011
.01
.015
.02
.024
.013
.035
.086
.091
.056
..20
.04
.051
.27
.058
.07
.035
.049
.04
Cu Al
.095
.13
.047
.05
.076
.061
.108
.11
.158
.26
.223
.28
1.0
.176
.154
.59
.088<
1.44
.158
.195
.23
.041
.065
.02
.04
.045
.031
.036
.064
.21
.13
.182
.167
.60
.08
.051
.16
.058
.148
.05
.073
.12
Ca Mg Mn Cr Sn
.77
1.54
.376<
.425
.80
.408
.75
.59
2.31
3.08
3.82
2.89
9.80
1.19
.949
1.70
1.32
2.29
1.10
1.05
1.70
.162<
.30 <
.035<
.059<
.106<
.091<
.132<
.16 <
.386<
.56 <
.364<
.28 <
.80 <
.235<
.21 <
.38 <
.294<
.48 <
.193<
.27 <
.43 <
.014<
.02 <
.005<
.004
.10
.01 <
.012<
.013
.017<
.04 <
.045<
.028
.10 <
.02 <
.026<
.05 <
.029<
.037<
.017<
.024<
.04
.014<
.04 <
.012<
.01 <
.015<
.02 <
.024<
.013
.035<
.08 <
.09K
.056<
.20 <
.02 <
.05K
.05 <
.058<
.07 <
.035<
.049<
.048<
.014<
.04
.012<
.01
.015
.02
.072<
.012
.035<
.08 <
.09K
.056<
.20 <
.02 <
.05K
.05
.058<
.07 <
.035<
.049<
.04
Zn Ti
.08K
.15 <
.035<
.05 <
.06 <
.07 <
.024<
.27 <
.105<
.26 <
.27 <
,167<
.60 <
.117<
.154<
.77 <
.176<
.22 <
.015<
.146<
.16 <
.'014
.04
.012
.01
.015
.02
.024
.013
.035
.08
.091
.056
.20
.02
.051
.05
.058
.07
.035
.049
.04
*
Pb
13.1
12.78
15.4
19.8
15.4
13.57
9.18
29.0
7.4 i
4.87 £
30.6 £
13.2 i
14.1
26.9
15.29
8.9
13.2
8.88
8.33
11.11
5.4
* by Atomic Absorption Analysis
-------
TABLE 67
TRACE METAL ANALYSIS - MILLIPORE FILTER PAPERS
NON-LEADED FUEL
o
c
O 0)
•o .
I/I 0
in *J
to v>
-C O
0 1—
60 mph
SS
LA-4
23 min
CS
Mod.
41 min
CS
0
c
3
CtL
164A
169B
152B
153B
154B
157B
159B
172B
164C
169C
152A
153A
154A
157C
159C
172C
164B
169A
157A
159A
172A
0)
•"•"*• -Q
E S- 3
O ••-> O_ i. O--^
•i— a; uj i — L. •*-> c -r- u-
•!-> -i- Q — ' +J 0
3 S 4J Q -i- 3 O
i — O (OU. "O i- i — ^
•r- ^— 01 C O (O ••- 't— V
on. z ••- «-* o;< Q«--
350 -
500 - -
350 Air-5°F
350 H20-10°F
500 H20-25°F -
350 - Yes
500 - Yes
350 - - Yes
350 - -
500 - -
350 Air-5°F
350 H20-10°F
500 H20-25°F
350 - Yes
500 - Yes
350 - - Yes
350 - -
500 -
350 - Yes
500 - Yes
350 - - Yes
Weight Percent
Fe
.31
.25
.6
.107
.143
.04
.11
.23
.167
.8
.5
.222
.21
.125
.40
.31
.21
.71
.094
.14
.30
Ni
.03
.06
.20
.036
.048
.02
.02
.038
.042
.20
.167
.111
.07
.04
.10
.06
.03
.14
.031
.048
.05
Cu
.31
.31
1.0
.178
.286
..08
.11
.19
.25
.8
.83
.555
.28
.16
.50
.25
.24
1.14
.125
.14
.20
Al
.14
.25
.6
.07
.095
.06
.06
.15
.13
.6
.5
.222
.14
.08
.30
.188
.10
.86
.063
.096
.15
Ca
3.00
4.56
11.2
2.11
2.86
.92
1.32
2.57
2.88
14.2
8.33
7.00
3.71
2.29
7.0
4.94
2.76
12.43
1.78
2.05
3.65
Mg
.35
.56
1.4
.214
.286
.10
.13
.27
.29
1.2
1.0
.67
.42
.25
.70
.56
.276
1.28
.156
.19
.35
Mn
.017
.03
.10
.10
.024
.01
.01
.019
.02
.10
.083
.056
.035
.02
.05
.03
.017
.07
.015
.024
.025
Cr
.03
.06
.20
.036
.048
.02
.02
.038
.042
.20
.167
.111
.07
.04
.10
.06
.03
.143
.031
.048
.05
Sn
.03
.06
.20
.036
.048
.02
.02
.038
.042
.20
.167
.111
.07
.04
.10
.06
.03
.143
.031
.048
.05
Zn
.10
.187
1.0
.107
.143
.06
.06
,115
.12
.60
.5
.333
.21
.125
.30
.188
.10
.43
.094
.14
.15
Ti
.03
.06
.6
.036
.048
.02
.02
.038
.042
.20
.167
.036
.07
.04
.10
.06
.03
.143
.031
.048
.05
Pb*
1.4
11.3
11.5
1.0
1.8
.1
.2 '
ro
18.9 "
to
i
.7
17.1
1.3
.4
2.5
1.7
1.4
15.0
2.7
7.2
1.0
1.4
7.6
*by Atomic Absorption
-------
-234-
C. EVALUATION OF BETA-GAUGE
Tables 68, 69, and 70 present mass emission data for exhaust
participate matter as measured by the Industrial Nucleonics
Beta-gauge and conventional proportional filtering devices.
-------
Test Vehicle: 1971 Chevrolet - 350 CID V8 Engine
TABLE 60
EVALUATION OF INDUSTRIAL NUCLEONICS BETA GAUGE
Test Fuel: A (2.66 TEL/gallon)
Deviation
Run No.
2
3
A
5
6
7
8
9,10
11
12
13
14
15
Driving
Condition
30 nph SS
30 mph SS
30 mph SS
60 nph SS
60 mph SS
LA-A CS
LA-A HS
LA-A HS
60 mph SS
60 mph SS
60 mph SS
30 mph SS
15 mph SS
Sampling
Time
(min)
20
20
20
20
20
23
10
23
10
10
10
15
15
Beta
Mass
Gain
(u gm)
2980
2A91
2A85
Abort
2366
3230
2151
Abort
3627
3870
1929
1502
1A37
Integrated
Flow
(liters)
2135
1935
18AO
87A
1022
- 787
A53
795
A17
118A
1382
1A2 mm
Filter
Wgt. Gain
(TOE)
3.65
3.85
3.60
13.2
1A.O
A. 05
9.15
5.80
5.75
2.40
.1.75
Avg . Beta
Flow Rate
(1/min)
10A.2
87.1
82.8
A1.4
41.1
72.9
45.3
79.5
41.7
78.9
92.1
Beta
Emission
Rate
(mR/min)
18.21
18.22
19.11
38.31
34.4
41.7
113.3
68.9
65.4
18.0
14. 7
142 mm
Emission
Rate
(rag/min)
22.8
24.1
22.5
82.5
76.1
50.6
114.4
72.5
71.9
20.0
14.8
Beta
vs .
142 mm
(%)
-20.1
-2A.2
-15.1
-53.6
-5A.8
-17.8
-1.0
-5.0
-8.9
-10.3
-0.6
Notes
A,B
A,B
A,B
C
A,B
A.B
A.B
C
D
D
D
D
D
ro
CO
CJl
i
Notes: A - Swirlmeter downstream of pump; standing wave in flow meter causing error in flow
measurement
B - Average flow rate corrected for elevated pump exhaust temperature
C - Test aborted due to computer cycling malfunction
D - Swirlmeter relocated to inlet upstream of filter; temperature correction
not required
-------
TABLE 69
EVALUATION OF INDUSTRIAL NUCLEONICS BETA GAUGE
Test Vehicle: 1971 Chevrolet - 350 CID V8 Engine
Test Fuel: 0.5 cc TEL/gallon, 91 RON
Run
22
23
24
25
26
27
28
29
30
31
32
33
Nntf
Driving
Condition
LA-4 CS
LA-4 HS
LA-4 HS
LA-4 HS
LA-4 HS
60 mph SS
30 mph SS
15 mph SS
Idle
30 mph SS
60 mph SS
60 mph SS
><; • n - ^ui rl r
Sampling
Time
(min)
23
10
23
23
23
15
15
15
15
15
5
5
na tai* rial
Beta Mass
Gain (pgm)
2796
960
251
298
959
4119
350
332
248
510
2308
1605
nratoH in "in
Integratec
Flow
(liters)
1784
1222
506
506
1840
993
966
1469
1488
1472
496
495
Tat fnncfrrp;
1 Filter Wt. Gain
(mg)
142 mm
7.1
1.6
2.3
2.4
2.5
7.0
1.2
0.7
0.5
1.5
3.0
2.2
»m of filti
47 mm
8.2
0.9
1.3
1.4
1.4
4.6
0.4
0.3
0.2
0.5
1.6
1.2
*r}
Avg.
Beta
Flow
(1/min)
77.6
122.2
22.0
22.0
80.0
66.2
64.4
97.9
99.2
98.1
99.2
99.0
Emission Rate
(mg/min)
Beta
22.1
11.1
7.0
8.3
7.4
58.7
5.5
3.2
2.4
4.9
65.5
45.7
142 mm
38.6
20.0
12.5
13.0
13.6
70.9
12.2
7.1
5.1
12.5
75.0
55.0
47 mm
54.2
13.7
8.6
9.3
9.3
52.5
4.1
3.0
2.0
5.2
48.6
36.5
Deviation^!)
B-
142 mm
-42.4
-44.0
-43.0
-36.3
-45.7
-17.2
-58.0
-55.0
-53.4
-60.8
-12.7
-16.8
B-
47 mm
-59.0
-18.7
-18.4
-10.3
-20.3
12.0
26.0
5..0
16.4
-3.2
34.6
25.4
47 mm-
142 mm
54.1
-31.7
-31.3
-29.1
-31.9
-26.0
-66.7
-57.1
-60.0
-59.5
-35.1
-33.7
Notes
D.E.J
D.E
D.E.H
D.E.F.H
D,E
D.E.G.J
D.E.G
D.E.G
D.E.G
D,E
D.E
D,E
ro
CO
E - 47 mm parallel filter used in addition to 142 mm filter (47 mm flow
F - Gelman Type A filter used in cassette
G - Flow through parallel filters identical (3.29 cfm)
H - Face velocity through 47 mm and cassette equal
0 - 47 mm filter plugged, AP excessive
Flow rate for 142 mm filter = 4 cfm except under footnote G.
3.29 cfm)
-------
TABLE 70
EVALUATION OF INDUSTRIAL NUCLEONICS BETA GAUGE
Test Vehicle: 1971 Chevrolet - 350 CID V8 Engine
Test Fuel: Indolene 0 (No lead)
Run
16
17
18
19
20
21
Notes
Driving
Condi tion
LA-4
LA-4
LA-4
LA-4
LA-4
CS
HS
HS
HS
HS
Cal ifornia
: D -
E -
K -
Sampling Integrated
Time Beta Mass- Flow
(miri) Gain (ugm) (liters)
23
10
23
23
23
47.5
Swirlmeter rel
47 mm
Test
paral lei
1049
156
33
230
. 197
359
ocated to inlet
filter used in
aborted because of brake
2454
1208
736
2075
2378
4750
(upstream
addition
Filter Wt. Gain
(rag)
142 mm 47 mm
4.05
1.35
1.4 -
1.40
1.40 0.2 .
2.20 0.6
of filter)
to 142 mm filter
Avg.
Beta
Flow
(1/min)
106
120
32
90
103
100
.7
.8
.0
.2
.4
.0
Emission R
(mg/minl
Beta 142 mm
6.1 22.0
1.8 16.9
0.64 7.6
1.6 7.6
1.2 7.6
1.1 5.8
ate Deviation (%)
B- 6- 47 mm-
47 mm 142 mm 47 mm 142 mm
-72.5
-89.1
-91.6
-79.4
1.3 -84.6 -11.3 -82.5
1.9 -81.0 -43.8 -66.8
failure on car
Notes
D
D
D
D
D,E
D.E.K
.', --
i
ro
CO
Flow rate for 142 mm filter = 4 cfm
Flow rate for 47 mm filter = 3.3 cfm (showed 6.5" Hg pressure differential)
-------
-238-
IV. DISCUSSION OF RESULTS
A. EVALUATION OF DILUTION TUBE VARIABLES ON THE COLLECTION OF
EXHAUST PARTICULATE MATTER
Prior to a discussion of the effects of dilution air flow rate and
dilution air cooling on the observed mass emission rates of exhaust
particulate matter, consideration will be given to the influence
of fuel and vehicle operating sequence on this parameter.
The use of low-lead gasoline resulted in the emission of higher
levels of exhaust particulate than were observed for non-leaded
gasoline. This result was not unexpected and corroborates the
similar finding in Phase I of this contract effort.
Of the three vehicle operating sequences employed, the two cold
start cyclic sequences afforded higher particulate mass emission
rates than did 60 mph steady state operation. This is to be
expected, since during the early modes of the cold start test
cycles, the vehicle is operating in a choked condition. Higher
particulate mass emission rates were generally observed for the
cold start 23 minute LA-4 cycle than for the 41 minute LA-4 sequence,
This was again anticipated, since even though the actual collected
mass of particulate generally increased with the longer cycle,
the grams per mile declined because of the relatively shorter
period of cold start operation. In order to prove that volatile
organic particulate was not being lost from the filtering devices
during the ten minute engine shut down period of the 41 minute
cycle, an experiment was performed in which a 1 cfm glass fiber
filter was exposed during the course of a 23 minute cold start
LA-4 cycle. The filter was weighed upon completion of the test
run and replaced in the system. Dilution air alone was passed
through the filter at 1 cfm for ten minutes and the filter
reweighed. No loss in weight was observed.
-------
-239-
An examination of the relative weights of participate matter
collected on the plates of the Andersen impactor versus the
back-up Millipore filter for the three vehicle modes studied,
suggests that there is an overall increase in particle size as
one moves from 60 mph steady state operation to the 41 minute
cycle, and a further increase in size for the 23 minute LA-4 cycle.
This is confirmed by an examination of the particulate mass
distribution profiles shown in Appendix D. It is suggested that
these data result from the relatively high concentrations of
exhaust products which occur during the choked or partially choked
conditions found in the early stages of the cold start cycle
and from the relatively low temperatures present throughout the
exhaust system and dilution tunnel during this same period.
Such conditions would favor the formation or growth of large
exhaust particulate matter.
In general, the concentrations of benzo-a-pyrene associated with
the collected particulate matter were higher in the cyclic modes
of vehicle operation. This again is believed to result from
the relatively inefficient combustion which occurs during the
early stages of a cold start test sequence.
Examination of the mass distribution profiles for leaded particulate
matter collected during the test series performed with low lead
fuel, indicates a general decrease in particle size when one
compares steady state to cyclic operation.
A comparison of the efficiencies of the various collection devices
employed in this phase of the program indicates that the Andersen
sampler and back-up 142 mm Millipore filter, operated at 1 cfm,
afforded higher levels of particulate matter than did a 142 mm
glass fiber filter operating at the same flow rate. This
observation corroborates the findings in Phase I of this contract
effort.
-------
-240-
Comparison of the particulate mass emission rates at dilution
tube flow rates of 350 and 500 cfm shows no apparent trend in
results. However, an examination of the relevant mass distribution
profiles in Appendix D indicates an overall increase in particle
size at the higher dilution tube flow rate. This conclusion is
supported by analysis of the relative weights of particulate
matter collected on the plates of the Andersen sampler versus
the back-up Millipore filter. This increase in particle size is
believed to result from entrainment of larger particles in the
diluted exhaust stream at the higher dilution tube flow rate.
Such particles might be expected to suffer gravitational fall out
at lower diluent air velocities.
Increasing the dilution tube flow rate to 500 cfm afforded no
significant trends in either the concentrations of lead or
benzo-a-pyrene in the collected exhaust particulate. However,
an increase in the trace metal content of the material on the
Millipore filter was evident for both fuels studied.
Use of a water cooled automotive radiator ahead of the dilution
tube air intake gave a temperature drop of 15-30°F for the
diluent air. With this device in position, an increase in the
mass emission rates for particulate matter was generally observed.
Presumably this increase is the result of the condensation of
organic matter accelerated by the lower temperatures of the dilution
air. This hypothesis is supported by the observed increase in
the particulate concentration of benzo-a-pyrene, and by a decrease
in the concentration of trace metals associated with particulate
collected on the Millipore filter. Cooling of the dilution air
also resulted in the collection of particulate matter having a
smaller MMED for non-leaded gasoline. No such effect was evident
for 1ow-1eaded fuel.
-------
-241-
The use of a water-cooled heat exchanger within the dilution
tunnel generally afforded a reduction in the observed particulate
mass emission rates. This was particularly pronounced during
23 minute LA-4 cold start cyclic operation. It should be noted
that the temperature drop across the heat exchanger was only
15-25°F but that this was nevertheless sufficient to affect
the measured emission rates for particulate matter. This decrease
in observed particulate emissions is believed to result from
condensation onto the surface of the heat exchanger. Physical
trapping of particulate matter by direct impingement on the device
should be minimal because of its design and mode of introduction
into the dilution tube. The above trend was observed for both
non-leaded and low lead fuels.
Examination of the relevant particulate mass distribution profiles
indicates that use of the cooling coil under 60 mph steady state
vehicle operating conditions resulted in a shift in the MMED of
collected particulate matter to a smaller size for low lead fuel
and to a larger size for non-leaded fuel. Under the operating
conditions of the cold start 23 minute LA-4 cycle, the converse
was true. .
No significant trends are obvious for either the particulate
concentrations of benzo-ct-pyrene or trace metals as a function of
diluted exhaust effluent cooling.
Throughout the above test program, filter temperature and dew point
determinations (Tables 62 and 63) indicated that there was sufficient
spread between these two sets of data to minimize problems
associated with condensation of moisture on filter surfaces.
-------
-242-
B. EVALUATION OF BETA-GAUGE PARTICULATE MASS MEASURING DEVICE
A study of the data collected during the evaluation of the
Industrial Nucleonics particulate emission Beta-gauge indicates
that there was close correlation between the mass emission rates
measured by this device and via a 142 mm glass fiber filter,
operated at 4 cfm, when the particulate matter was generated by
a vehicle running under steady state conditions on gasoline
containing 3 cc TEL/gallon. After initial operational problems
with the device were corrected, the deviation between the mass
emission rates measured above was from 0.6-10.3 percent. In all
cases the conventional filter afforded the higher values (Table 68)
A similar series of tests were made on a vehicle operating on
low-leaded fuel (0.5 cc TEL/gallon). Under the conditions of both
hot and cold start 23 minute LA-4 cycles, the deviation between the
Beta-gauge and 142 mm (4 cfm) filter ranged from 36.3-45.7 percent.
The corresponding deviation between the Beta-gauge and the 47 mm
filter (3.29 cfm) ranged from 10.3-18.7 percent. Again the conven-
tional filters afforded the higher mass emission rates. Under
steady state vehicle operation, the deviation in mass emission
rates between the Beta-gauge and 142 mm filter ranged from 12.7
to 60.8 percent. The corresponding deviation between the 47 mm
filter and Beta-gauge was 5-34 percent. However, in this latter
instance, the Beta-gauge afforded the higher mass emission rates.
In a final set of experiments, the measuring capabilities of the
Beta-gauge and conventional filters were compared using a vehicle
running on non-leaded fuel. In a series of cyclic runs, there was
considerable deviation (79-91 percent) between the mass emission
rates afforded by the Beta-gauge and 142 mm filters.
Thus the ability of the Beta-gauge to correlate well with glass
fiber filter measurements became less reliable as the level of
tetraethyl lead in the test fuel was reduced. Two factors are
believed to contribute to the observed discrepancies.
-------
-243-
The face velocity of air diluted exhaust effluent through the
filter membrane of the Beta-gauge was in general much higher than
that through the regular filters. With non-leaded fuel specially,
this could result in the more rapid volatilization of organic
particulate from the filter medium, thus yielding a lower observed
mass emission rate.
Further, although the glass fiber filters utilized are relatively
insensitive to air-borne moisture, the Pallflex filter medium
used in the Beta-gauge is more sensitive in this regard. Thus,
this factor may also be responsible in part for the observed
deviations.
-------
-244-
APPENDIX A
Total unburned hydrocarbon emissions (ppm Mole %) as a
function of engine or vehicle operating hours for all
test fuel runs. Vehicle emissions determined during
cruise mode operation only (60 mph - road load).
Legend:
Code Cycle No.*
© 2
0 3
x 4
A 5
SS Steady State (cruise mode 60 mph road load)
*See Table 2, page 13.
-------
-245-
30 40 50
.,..,. t ...
lits-LS t e a d yl-St a t e
; n i i j i | ; ; i • I : ! : ; i i i ;
TOTAL'HypROCARBbNiys'.i H
-------
-246-
mm
-------
-247-
ETr^miTiTrnnTE
4HYDROCARBON vsJ HpURS
:444.i44J.RUN
-TRf ' '
MftrTi
-Cycle
2
3
4
5
SS
-------
-248-
-------
-249-
s
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-------
-250-
TOTAL HYDROCARBON vs. HOURS ENGINE OPERATION
Run No. 16
tlxLJJ.Lt.aJ. ill:
-------
-251-
!!!!'! M
BON,vs.!H
i_|.RUN;N6..
1. .Jju..
-------
-252-
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-------
-253-
::xj:. i|t.tt::-::i:4i"-"ij: TOTAL HYDROCARBON vs.
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SATURATED HYDROCARBON vs. HOURS ENGINE OPERATION
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TOTAL HYDROCARBON vs. HOURS ENGINE OPERATION
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-256-
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-------
-257-
HYDROCARBONS vs. HOURS ENGINE OPERATION
Run No. 24
-------
-258-
HYDROCARBONS vs. HOURS ENGINE OPERATION
Run No. 25
HYOROCARBOHS vs. HOURS ENGINE OPERATION
-------
-259-
HYDROCARBOIIS vs. HOURS ENGINE OPERATION
Run No. 28
-------
-260-
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Run No. 31
-------
-261-
-------
-262-
SATURATED HYDROCARBON vs. HOURS ENGINE OPERATION
Run No. 32
HYDROCARBONS vs. HOURS ENGINE
Run No. 33
-------
-263-
HYOROCARBOMS vs. HOURS EIIGINE OPERATION--;
Run No. 34
HYDROCARBONS vs. HOURS ENGINE
Run No. 37
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TOTAL HYDROCARBON vs. HOURS ENGINE OPERATION
Run No. 40
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-265-
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HYDROCARBONS vs. HOURS ENGINE OPERATION
Run No. 43
Hours of Operation
-------
-267-
TOTAL HYDROCARBON vs. HOURS
Run No. 44
: • • Bpi-iTi>n- 11
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SATURATED HYDROCARBON vs.' HOURS ENGINE OPERATION
Run No. 44
-------
-268-
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HYDROCARBONS vs. HOURS ENGINE OPERATION;
Run No. 45 I
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-270-
HYDROCARBONS vs. HOURS ENGINE OPERATION
Run No. 52D
Hours of Operation -
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HYDROCARBONS vs. HOURS ENGINE OPERATION
Run No. 55A
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-------
-271-
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HYDROCARBONS vs. HOURS ENGINE
Run No. 55C
-------
-272-
HYDROCARBONS vs. HOURS ENGINE
Run Mo. 55C
-------
-273-
-------
-274-
HYDROCARBONS vs. HOURS ENGINE OPERATION
Run No. 56B
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HYDROCARBONS vs. HOURS ENGINE OPERATION --
Run No. 56C
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-------
-275-
HYDROCARBONS vs. HOURS EIIGINE OPERATION
Run No. 58 • \ '•
TOTAL HYDROCARBON vs. HOURS
Run No. 59
-------
-276-
ENGINE OPERATION ft:til
SATURATED HYDROCARBON
-------
-277-
HYDROCARBONS vs. HOURS ENGINE OPERATION
Run No. 63
HYDROCARBONS vs; HOURS ENGINE OPERATION
Run No. 67
tfa
-------
-279-
l.ert-ri'l
Hun
Huri 1 1 x
Hun 12
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run Nos. 4, 11, 12
Weight % Particles of Diameter <0
0.01 0.01 O.I 0.2 O.S I 2 5 10 20 30 40 50 60 70 80 90 OS
fl 95 90 SO 70 60 • SO 40 30 .20 10 5 ? I n
; I I; • i: I - -rfe |=Jr.M.J -fa i I-.U iit -• j-4=fci=Lta I i; j.rtm bk-Ur
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run Nos. 6, 11, 16
- Run
; Run 11 \
Run 16 A
1 I .
Particles of DlameW
0.01 0.03 0.1 0.2
».l 999 M.M
-------
0,5 O.f O.I 0.06 001
„ _1 CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run Nos. 13 and 14
Height % Particles of Diameter
-------
It.M 99.9 M.I
f 1 O.S 0.7 O.I 005 0.01
to ia to u to K
Leend '~^
Run
Run 8 D
S CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run Nos. 7. 8. 9. 11
—' ' •——•—-—-)•'••
height % Particles of Diameter « M «0 » 80 MM
n.8 99.1 M.N
-------
n.N f3.« It.l M 91
10 M » 20 10 I I I U O.t O.I 0» 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 18
J.lHelflht X Particles of Diameter
-------
-283-
fc*"
CUMULATIVE PARTICLE
"" M • ° 'Y si . , '-^o-^11^^^
» ra S is ^
-------
,g C3.C3 CJ.O C3.0
CUMULATIVE PARTICLE SIZE DISTRIBUTION
.Height 2 Partlclos of Dlamotar
-------
«.« M.9 M.O
t I 0.9 0,2 O.I 0,01 001
CUMULATIVE PARTICLE SIZE DISTRIBUTION i?
..Weight * Particles of Diameter
-------
-286-
M.M M.t n.i 99 9i
W 60 70 60 50 40 M 20 10 1 i I 0.9 O.I O.I Oft 001
CUMULATIVE PARTICLE SIZE DISTRIBUTION H
Run No. 28
Weight * Particles of Diameter
-------
-287-
2 1 0.5 0.2 O.I O.OS 001
CUMULATIVE PARTICLE SIZE DISTRIBUTION i»
Run No. 31
-J..: Height % Particles of Diameter
-------
-288-
SO 70 eO M> 40 30 20
1 0.5 07 O.I 001 OQI
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 33
i Plates 3 and 6 assumed at lH
a weight of .0001 gms.
Particles of Diameter
0.01 O.OS 0.1 0.1 O.S 1
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 34
Weight % Particles of Diameter
-------
-289-
80 70 60 SO 40 30 70
t 0.5 O.Z O.I O.C5 001
CUMULATIVE PARTICLE SIZE DISTRIBUTION :,;••.
Run No. 37
j Weight % Particles of Diameter
-------
It H.l fOJ 99 II MM 10 70
' 30 20 105 21 0.5 0.2 0.1 O.C5 0 01
CUMULATIVE PARTICLE SIZE DISTRIBUTION ;-I
.0-1-4. M f
_._,...4 JTi-TcTflJ
( .„(_.....
Weight X Particles of Diameter <0
0.01 0.01 0.1 O.I 0.9 I I
10 It 10 40 U M n to
CUMULATIVE PARTICLE SIZE DISTRIBUTION i£;
Weight % Particles of Diameter
-------
99.99 99.9 9S.« f> 9fl 95 90 80 70 60 SO 40 30 20 10 5 II. 0.5 07 O.I 004 001
CUMULATIVE PARTICLE SIZE DISTRIBUTION H
Run No. 42
Plates 4, 5, and 6
Pl.a
! Weight % Particles of Diameter
-------
4. e043 -292-
99.99 M9 99.8
V> 18 (5 M »0 70 60 90 10 10 20 10 5 1 I 0.3 0? 01 005 001
CUMULATIVE PARTICLE SIZE DISTRIBUTION HV-
Run No. 44
...: Weight % Particles of Diameter
-------
CUMULATIVE PARTICLE
Run No
Weight % Particles of Diameter
IV
o
. 7.
V
O ••••
Weight % Particles of Diameter
-------
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Weight X Particles of Diameter
-------
9999 99.9 998 90 9
-295-
10 70 CO 50
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 59 fflr
ffi
Weight % Particles of Diameter
-------
70 60 50 40 30 20 10 5 ? I OS 07 O.I O.Ci 001
99.9f M.> 99.1 99 »« 9! 90
CUMULATIVE PARTICLE SIZE DISTRIBUTION H1J:
Run No. 63
_M Weight X Particles of Diameter
-------
-297-
V) 98 S5 90
CUMULATIVE PARTICLE SIZE DISTRIBUTION H>i
Run No. 52
1200 RPM
Weight X Particles of Diameter
-------
99,99 99.B 90.< 99 98 95 »
-298-
70 60 ' 50 in 30 70
10 S ! I 0.5 0!
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 55
Catalyst Muffler
Particles of Diameter 0 15 US 99
90.8 99.9 99.99
9999 99.9 90.8 91 98
;0 50 10 30 '/(I
2 1 0.5 0.2 0.1 0.05 0,01
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 55
Catalyst Muffler
"J I W«1g'ht"it'pa'rtic'leV'o'f Diameter
-------
-299-
'9.SS 99.9 99.8 99 98 95 90 80 70 60 50 40 30 JO 10 5
I O.S 0.? 0.1 0.05 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 56
Chevrolet V-8
% Particles of Diameter
-------
-300-
APPENDIX C
Mass Distribution for Lead, Chlorine, Bromine, and Organics
-------
= MASS DISTRIBUTION FOR
feLEAD, CHLORINE, AND BROMINE •
Run No. 4
^Organic ^-^-
D -:£ :~
% Total 1n Particles of Diameter
-------
tM> 99.9 M.I
91 9! 90 10 70 10 SO 40 30 20
( Legend
Pb
ganic
MASS DISTRIBUTION FOR -'
E LEAD, CHLORINE. AND BROMINE =
Run No.7
* Total 1n Particles of Diameter
-------
-303-
Legend
Cl °
Organic A
= MASS.DISTRIBUTION FOR
= LEAD, CHLORINE. AND BROMINE
^i Run 9
% Total in Particles of Diameter >9
-------
-304-
tl» HJ Ml
tl II H U 10 70 10 80 40 M ;o
O.S O.g Q.I 0.03 0.01
MASS DISTRIBUTION FOR
LEAD. CHLORINE, AND BROMINE
Run 12
% Total 1n Particles of Diameter
-------
-305-
W.M 99.» «.» M »» ii V} K> 1 «,,»,, i ,",
,0 5 '___ ' "•' "' "•'
MASS DISTRIBUTION FOR
LEAD, CHLORINE. AND BROMINE
Run No. 14
% Total 1n Particles of Diameter
-------
-306-
99.W ».< M.8 » 98 95
80 70 60
0,3 0.? O.I 0.0$ 0.01
MASS DISTRIBUTION F
LEAD. CHLORINE, AND BROMINE
% Total 1n Particles of Diameter
-------
-307-
1 0.5 O.J 0.1 0.04 0.01
^~t;~ri~\ . -.:! ~J . ..-rtri. . :.f J":_r*j r-::
4rfH- .---I—;--;^-••- r*r|-'i
MASS DISTRIBUTION FOR
LEAD. CHLORINE. AND BROMINE i^
Run No. 20
:f=uOrgani c fe;r-
I Tube sweepings and slits = 6.17%
= of total weight. Not included in
i. this graph.
% Total 1n Particles of Diameter
-------
= MASS DISTRIBUTION FOR
= LEAD, CHLORINE, AMD BROMINE i=
Br
Organic Isp
Tube sweepings and slits = 12.9%
of total weight. Not Included In
this graph.
Total 1n Particles of Diameter
-------
aO 70 60 60 40 30 20 10 5 21 0.6 0.2 O.I O.OS 0.01
'"-
a^M?^m-m
= MASS OISTRIDUTION FOR
= LEAD, CHLORIHE, AND BROMINE .i=
Legend
Organic
No Pb, Cl . or ...
Br analysis.
Tube sweepings and slits ° 4.16t
of total weight. Not Included In
this graph.
_ _ * Total 1n Particles of Diameter
-------
-310-
« MM «0 70 M 50 40 K 20 10 « 71 0.5 07 0.1 0.0> 001
*%$^^.*\-^#. •••)•#'&
13- Legend".
MASS DISTRIBUTION FOR
LEAD, CHLORINE. AND BROMINE
Run llo. 28
-1. ' % Total 1n Particles of Diameter
-------
-311-
Hit HI M.I n »t n «o to ro to so 40 10 10 10 «
MASS DISTRIBUTION FOR
~ LEAD, CHLORINE, AND BROMINE
Tube sweepings and slits • 13.835!
of total weight. Not Included 1n
% Total 1n Particles of Diameter
-------
-312-
M 70 60 50 40 30 iO
Legend
Organic ® r==
No Pb, Cl, or ^
Br analysi s.
MASS DISTRIBUTION FOR
LEAD, CHLORINE, AND BROMINE
Run Ho. 40 I
Total in Particles of Diameter
-------
•313-
0.9 OJ O.I 0.06 0.01
Hi MASS DISTRIBUTION FOR
= LEAD, CHLORINE, AND BROMINE ~
Run No. 45
Tube sweepings and slits = 0.526X
of total weight. Hot Included 1n
this graph.
' • • , i •'
,4 . .- I ..If .-I..-,
:.ulfUJ
X Total 1n Particl
es of Diameter
-------
-314-
APPENDIX D
Cumulative Particle Size Distribution
of Particulate and of Lead
-------
-315-
•I 91 «! 90
10 70 60 M 40 80 20
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 164A (Non-leaded fuel)
Mode: 60 mph, SS
Dilution Tube Flow: 350 cfn
Weight % Particles of Diameter
-------
-316-
OOS 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION :
Run No. 152B (Non-leaded fuel)
Mode: 60 mph, SS
Dilution Tube Flow: 350 cfm
1 Weight % Particles of Diameter
-------
-317-
99 98 95 90
80 70 60 50 40 30 70
CUMULATIVE PARTICLE SIZE DISTRIBUTION in
Run No. 154B (Non-leaded fuel
Mode: 60 niph, SS
Dilution Tube Flow: 500 cfm
! ; |1 Weight % Particles of Diameter
-------
-318-
DISTRIBUTION
leaded fuel)
Weight % Particles of Diameter
,-• i i -I • • •-* I i ' 1
DISTRIBUTION
Mode
s_..|i Dilution
Weight * Particles of Diameter
-------
-319-
99,99 99.9 99.6 99 98 95 90
70 60 50 40 30 20 10 5 2 1 0.5 11.2 0.1 OOS 0.01.
nm oot o i 0
-------
-320-
10
"•' •¥•
DISTRIBUTION
leaded fuel)
particles of Diameter
LdJJLu-J--ir-^™ -zr- -«
,. - ... 1KOfl (Non-leaded fuel) ![R!iJii|M
ounui.ni*¥** .
Run No. 159A (Non-leaded fuel)
KU M i»" •
Mode: LA-" "1 Minutes
SSllffl ! r
f weight * Particles of Diameter
-------
99 » 99.9 99.8
99 98 95 90 80 70 gO SO 40 SO 20 10 ft II 0.5 07 O.I OOi i)0t
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 172A (Non-leaded fuel)
Mode: LA-4 41 Minutes
Dilution Tube Flow: 350 cfm
~-t-
-r
-y
H
11
Trt
: : : 3E& : :
i
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"-B
HP
m
Weight % Particles of Diameter
-------
-322-
CUMULATIVE PARTICLE SIZE DISTRIBUTION Ig
Run No. 169C (Non-leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 500 cfm
Weight X Particles of Diameter
-------
-323-
2 1 O.S 0,7 0,1 0.« 0,0]
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 153A (Non-leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 350 cfm
p Weight % Particles of Diameter
itili1TrtiiiiiTiTTmrrrnTiTnTiirnrnTinn;ni!iirnH
20 30 40 50 «0 70
80 70 60 90 40 30
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 154A(Non-leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 500 cfm
Weight % Particles of
iiiiiinrmimniirinii
001 0.0ft 0
-------
-324-
0,4 O.J 0.1 Q Oi 0,01
CUMULATIVE-PARTICLE SIZE DISTRIBUTION
Run No. 157C (Non-leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 350 cfm
I Weight % Particles of Diameter
-------
O.S 0.7 0 I O.lrt
CUMULATIVE PARTICLE SIZE DISTRIBUTION ?nt
Run No. 172C (Non-leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 350 cfm
Weight % Particles of Diameter
-------
-326-
99 98 95 90
1 O.S 07 0.1 0.06 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION l
Run No. 118B (Leaded fuel)
Mode: 60 mph, SS
Dilution Tube Flow: 500 cfm
Weight % Particles of Diameter
-------
: CUMULATIVE PARTICLE SIZE DISTRIBUTION
I Run No. 144B (Leaded fuel)
Mode: 60 mph, SS
Dilution Tube Flow: 350 cfn
Weight X Particles of Diameter
-------
CUMULATIVE PARTICLE SI2E DISTRIBUTION
Run No. 133B (Leaded fuel)
Mode:• 60 mph
Dilution Tube Flow: 350 cfm
Weight % Particles of Diameter
-------
O.S 0.2 O.I 0.05 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 174C (Leaded fuel)
Mode: 60 mph , SS
Dilution Tube Flow: 350 cfm
Particles of Diameter
-------
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 118C (Leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 500 cfm
Weight % Particles of Diameter
2 I 0.5 (U O.I 0.05 0j» .
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 149A (Leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 350 cfm
Weight % Particles of Diameter
-------
0,1 o.» o.oi..
70 60 SO 40 90
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 144A (Leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 350 cfm
Tin Weight * Particles of Diameter
-------
».M M.9 M t 99 91 99
-332-
90 90 70 80 BO 40 10 20
10 5 2 I 0.5 0.2 O.I O.OS 0.01.
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 133C (Leaded fuel)
Mode: LA-4 23 Minutes
Dilution Tube Flow: 350 cfm
Weight % Particles of Diameter • »99
-------
-333-
2 1 0.5 03 O.I 0.05 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION H
Run No. 174A (Leaded fuel)
Mode: LA-4 23 Minutes .
Dilution Tube Fiow: 350 cfm
Height X Particles of Diameter
-------
-334-
1 0.5 0.? 0 ] 0,OS 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Run No. 118A (Leaded fuel)
Mode: LA-4 41 Minutes
Dilution Tube Flow: 500 cfn
Weight % Particles of Diameter
-------
-335-
99 98 95 90
I 0.5 0? 0.1 COS 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION Hz
Run No. 137A (Leaded fuel)
Mode: LA-4 41 Minutes
Dilution Tube Flow: 500 cfm
Weight % Particles of Diameter
-------
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 1278
Mode: 60 ">ph,
Dilution Tube Flow:
Weight X Particles of Diameter
-------
S9.99 99.9 99.1
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 149B
Mode: 60 mph, SS
Dilution Tube Flow:
Height % Particles of Diameter
-------
-338-
99 9j gi 90
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 1486
D1lu 1on Tube Flow:
•m- ritr "ti r
. tn .(.:•-•
. Height % Particles of Diameter 60 70 80 90 95
99.99 99.9 99 I
99 91 9S 90 80 70 60 SO 10 30 20 10 5 21 O.S 0.2 O.I 005 0.01
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 133B
Mode: 60 mph , SS
Dilution Tube Flow:
Weight % Particles of Diameter 0 60 70 80 90
-------
-339-
MM M.I »e
n »« 8» m m in 10 so 10 10 20 10 5 ' i o.s o; 01 001 001
CUMULATIVE PARTICLE SIZE DISTRIBUTION "'":;
Lead on Andersen Plates
Run No. 137B
Mode: 60 mph, SS
Dilution Tube Flow:
Height % Particles of Diameter
-------
-340-
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
- Run No. 124A
[ Mode: LA-4 (41 minutes)
. Dilution Tube Flow:
! Height % Particles of Diameter <0
0.01 0.05 0.1 O.t 0.3
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 118A
Mode: LA-4 (41 minutes)
Dilution Tube Flow:
Height % Particles
Diameter <0 : I ;
i|l
0.01 0.0) 0.1 0.2
.8 99.9 9?-99
-------
-341-
: CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 133A
Mode: LA-4 (41 minutes) '
Dilution Tube Flow:
u 2-
i
70 60 SO
0 ?
-------
-342-
s n ? o i o.os 001
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 174B
Mode: LA-4 (41 minutes)
Dilution Tube Flow:
Weight % Particles of Diameter 0 60 70 80 SO 9&
-------
99 98 95 90
-343-
80 70 tO 50 40
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 118C
Mode: LA-4 (23 minutes
Dilution Tube Flow:
I/eight % Particles of Diameter
-------
-344-
SO 70 60 50 10 30 20
O.S 0 J •: 1 005 001
-' i: --: ^sfeg^^^^h^^^^gt^^feamiij^a^jtafeii-i *&*&>
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 144A
Mode: LA-4 (23 minutes)
Dilution Tube Flow:
HE
i! Height % Particles of Diameter
'C 4
4i
•4 (23 minutes) jj|
e Flow: =1
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;!•!.! " ' : !• K-!f vhptTt'
.';;: !f ---_^Tf!3'!|iiir
•.;;: j- | •JijJi.iLiiji
•j l • • i j( •
.:. |.k.
1 ! 1 : ' 1 • : . ••:.:':•• f = i .-"• i"^'
r ! : F -r-.i-.i . • '" : ::;-i -:":- ::'
.. !- .•-'.'•:?•• . .:." ":-..:: \ r: :it ^7
cL^iLi ""'-'.-. r"; .]:'" Im- " ;•.?
X . . T . -..-•- __ r . : . ^ ^ • '- - ^ j -. .' . ; . r J
U J •• .-.-• = • :• = ;; = = : = .:;• - FT - : : TT
ill-!: '? :---. -:|- :=-:i = L.--: T .. .'•• . ••
:: |!j •(.-:• i S = ;;!;:;:-. f ; i
: . > : , -. •-. -L- ~ ; _i| - • f ? - • j
•;ii a;|! ' "' TT ' :ll MJ
i 1 1 i i i i 1 • I ' i
, :{ j;- ; j| | . j j!
: j l|. ! L'. j .1 il Jl4ii4ll.
i! i; | Height Si Part
"• ''' : il il Ulli'lli 1 1
fiSj^^-l^ififtlrttei-..^
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'j ; 3Jt ; "ids :''''fe- -hp' 'L: fjs ii1- J; JsjJ-' '-'I' •
'-. ' Si tiS ttp' = =p== -ft ft^ ; 3- :iti • ' 1
i' "
; n-!'.| TJ-'fij: .ipB :frl£ |; Sh; B*t.= --I-. •-
\& ii-ir-hSl^ifvii; B!.;.!3'i/"r •
- If} M ! r -j*'- ; ^ =f 1 ' : ja":. ; iS - ^ -^i •:
;: "f |; J|p:a" !-i; fl|l !•{&;"!'- ;
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!; • -j;. ^FT^j ^ji ~^\ '
•hjl ;i!j_!:lji ;M-!; i ;--
/i' ' ill 1 Mil M-
; j • J .j-i: : • ^ ; : ;};^fc : •.-. }•. ir .(•• : i. • ;••
: rl t-V • j'-;"ff = I • t- 1 ' -•' ' '•'• \j/
• .': '!•• : -I'^ii: -f yj'j': • ^ •
! . i ' :..'! vi''' \ \\ '•• 'j/s' • t '
F - T • , ' - • ., j • = -• - =• • . - |; - • ; f •*• • - ---
.}:•.•• L • !"|! ::••...•-• :j' >«=. . H-.
-
: ^' 4. :| ' : p' j- " . ' -. / j I: : t. . f. /Lv . '. • J .
•.H t- • ,!n .••• : 'f; .:i ^ ;•-=-)
•'•.•il : i{ -l! .t "'7 •'" ::J' t|i : '1 "i "
)..-..!' ^ l..i T , { . J .. ,-| . ..
"ijr 4+1 ' -'' ul t'i-: '!.':"
3 ' • !'!i )• ! IJl i-t ' i;" • i
l " i i ' M ; ii HI. -iJ 4
i i . j . i i II | p . J .
.llilLilULiii.!'
icles of Diameter
-------
-345-
CUMULATIVE PARTICLE SIZE DISTRIBUTION
Lead on Andersen Plates
Run No. 174A ' '
Mode: LA-4 (23 minutes)
Weight % Particles of Diameter
------- |