EPA-600/3-75-010C
September 1975
Ecological Research Series
ANNUAL CATALYST RESEARCH PROGRAM REPORT
APPENDICES
Volume II
Health Effects Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. Environmental Protection Agency, have been grouped into
five series. These five broad categories were established to
facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL RESEARCH series.
This series describes research on the effects of pollution on
humans, plant and animal species, and materials. Problems are
assessed for their long- and short-term influences. Investigations
include formation, transport, and pathway studies to determine the
fate of pollutants and their effects. This work provides the
technical basis for setting standards to minimize undesirable
changes in living organisms in the aquatic, terrestrial and
atmospheric environments.
This document is available to the public through the National
Technical Information Service, Springfield, Virginia 22161.
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EPA-600/3-75-010 C
September 1975
ANNUAL CATALYST RESEARCH PROGRAM REPORT APPENDICES
Volume II
by
Criteria and Special Studies Office
Health Effects Research Laboratory
Research Triangle Park, North Carolina 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AMD DEVELOPMENT
HEALTH EFFECTS RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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CONTENTS
Page
CATALYST RESEARCH PROGRAM ANNUAL REPORT
EXECUTIVE SUMMARY 1
INTRODUCTION 5
PROGRAM SUMMARY 7
TECHNICAL CONCLUSIONS 17
DISCUSSION 22
REFERENCES 45
APPENDICES TO CATALYST RESEARCH PROGRAM ANNUAL REPORT
VOLUME 1
A. OFFICE OF AIR AND WASTE MANAGEMENT
A1. AUTOMOTIVE SULFATE EMISSIONS 1
A2. GASOLINE DE-SULFURIZATION - SUMMARY 53
A2.1 Control of Automotive Sulfate Emissions
through Fuel Modifications 55
A2.2 Production of Low-sulfur Gasoline 90
VOLUME 2
B. OFFICE OF RESEARCH AND DEVELOPMENT
Bl. FUEL SURVEILLANCE
B1.1 Fuel Surveillance and Analysis 1
B1.2 The EPA National Fuels Surveillance
Network. I. Trace Constituents in Gasoline
and Commercial Gasoline Fuel Additives ... 19
B2. EMISSIONS CHARACTERIZATION
B2.1 Emissions Characterization Summary .... 44
B2.2 Sulfate Emissions from Catalyst- and Non-
catalyst-equipped Automobiles 45
B2.3 Status Report: Characterize Paniculate
Emissions - Prototype Catalyst Cars 68
B2.4 Status Report: Characterize Particulate
Emissions from Production Catalyst Cars . . 132
B2.5 Status Report: Survey Gaseous and Particu-
late Emissions - California 1975 Model Year
Vehicles 133
B2.6 Status Report: Characterization and Meas-
urement of Regulated, Sulfate, and Particu-
late Emissions from In-use Catalyst Vehicles -
1975 National Standard 134
B2.7 Gaseous Emissions Associated with Gasoline
Additives - Reciprocating Engines. Progress
Reports and Draft Final Report - "Effect of
Gasoline Additives on Gaseous Emissions" • • 135
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VOLUME 3
Page
B2.8 Characterization of Caseous Emissions from
Rotary Engines using Additive Fuel -
Progress Reports 220
B2.9 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Oxygen- and Sulfur-
containing Additives 232
B2.10 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Various Nitrogen-
containing Additives 233
B2.11 Status Report: Characterize Diesel Gaseous
and Particulate Emissions v, ith Paper Vight-
duty Diesel Exhaust Emissions" 234
B2.12 Status Report: Characterize Rotary Emissions
as a Function of Lubricant Composition and
Fuel/Lubricant Interaction 242
B2.13 Status Report. Characterize Particulate
Emissions - Alternate Power Systems (Rotary) . . 243
B.3 Emissions Measurement Methodology
B3.1 Emissions Measurement Methodology Summary. . . 1
B3.2 Status Report: Develop Methods for Total
Sulfur, Sulfate, and other Sulfur Compounds
in Particulate Emissions from Mobile Sources ... 2
B3.3 Status Report: Adapt Methods for S02 and S03
to Mobile Source Emissions Measurements 3
B3.4 Evaluation of the Adaption to Mobile Source
SOj and Sulfate Emission Measurements of
Stationary Source Manual Methods 4
B3.5 Sulfate Method Comparison Study. CRC APRAC
Project CAPI-8-74 17
B3.6 Determination of Soluble Sulfates in CVS
Diluted Exhausts: An Automated Method 19
B3.7 Engine Room Dilution Tube Flow Characteristics. • 41
B3.8 An EPA Automobile Emissions Laboratory 52
B3.9 Status Report: Protocol to Characterize Caseous
Emissions as a Function of Fuel and Additive
Composition - Prototype Vehicles 89
B3.10 Status Report: Protocol to Characterize Particu-
late Emissions as a Function of Fuel and Additive
Composition 90
B3.11 Interim Report and Subsequent Progress Reports:
Development of a Methodology for Determination
of the Effects of Diesel Fuel and Fuel Additives
on Particulate Emissions 192
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Page
B3.12 Monthly Progress Report #7: Protocol to
Characterize Gaseous Emissions as a Function. . .
of Fuel and Additive Composition 200
B3.13 Status Report: Validate Engine Dynomometer Test
Protocol for Control System Performance 218
B3.14 Fuel Additive Protocol Development 221
B3.15 Proposed EPA Protocol: Control System
Performance 231
VOLUME 4
B3.16 The Effect of Fuels and Fuel Additives on Mobile
Source Exhaust Particulate Emissions 1
VOLUME 5
B3.17 Development of Methodology to Determine the
Effect of Fuels and Fuel Additives on the Perform-
ance of Emission Control Devices 1
B3.18 Status of Mobile Source and Quality Assurance
Programs 260
VOLUME 6
B4. Toxicology
B4.1 Toxicology: Overview and Summary 1
B4.2 Sulfuric Acid Effect on Deposition of Radioactive
Aerosol in the Respiratory Tract of Guinea Pigs,
October 1974 38
B4.3 Sulfuric Acid Aerosol Effects on Clearance of
Streptococci from the Respiratory Tract of Mice.
July 1974 63
B4.4 Ammonium and Sulfate Ion Release of Histamine
from Lung Fragments 89
B4.5 Toxicity of Palladium, Platinum and their
Compounds 105
B4.6 Method Development and Subsequent Survey
Analysis of Experimental Rat Tissue for PT, Mn,
and Pb Content, March 1974 128
B4.7 Assessment of Fuel Additives Emissions Toxicity
via Selected Assays of Nucleic Acid and Protein
Synthesis 157
B4.8 Determination of No-effect Levels of Pt-group
Base Metal Compounds Using Mouse Infectivity
Model, August 1974 and November 1974 (2
quarterly reports) 220
B4.9 Status Report: "Exposure of Tissue Culture
Systems to Air Pollutants under Conditions
Simulating Physiologic States of Lung and
Conjunctiva" 239
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Page
B4.10 A Comparative Study of the Effect of Inhalation of
Platinum, Lead, and other Base Metal Compounds
Utilizing the Pulmonary Macrophage as an Indicator
of Toxicity 256
B4.11 Status Report: "Compare Pulmonary Carcinogenesis
of Platinum Group Metal Compounds and Lead Com-
pounds in Association with Polynuclear Aromatics
Using ir^ vivo Hamster System 258
B4.12 Status Report: Methylation Chemistry of Platinum,
Palladium, Lead, and Manganese 263
VOLUME 7
B.5 Inhalation Toxicology
B5.1 Studies on Catalytic Components and Exhaust
Emissions 1
B.6 Meteorological Modelling
B6.1 Meteorological Modelling - Summary 149
B6.2 HIWAY: A Highway Air Pollution Model 151
B6.3 Line Source Modelling 209
B.7 Atmospheric Chemistry
B7.1 Status Report: A Development of Methodology to
Determine the Effects of Fuel and Additives on
Atmospheric Visibility 233
Monthly Progress Report: October 1974 255
B7.2 Status Report: Develop Laboratory Method for Collec-
tion and Analysis of Sulfuric Acid and Sulfates . . • .259
B7.3 Status Report: Develop Portable Device for Collection
of Sulfate and Sulfuric Acid 260
B7.4 Status Report: Personal Exposure Meters for
Suspended Sulfates 261
B7.5 Status Report. Smog Chamber Study of SO.
Photo-oxidation to SO. under Roadway
Condition 262
B7.6 Status Report: Study of Scavenging of SO_ and
Sulfates by Surfaces near Roadways 263
B7.7 Status Report: Characterization of Roadside
Aerosols: St. Louis Roadway Sulfate Study 264
B7.8 Status Report: Characterization of Roadside
Aerosols: Los Angeles Roadway Sulfate Study . . . .269
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Page
VOLUME 8
B.8 Monitoring
B8.1 Los Angeles Catalyst Study. Background Pre-
liminary Report 1
B8.2 Los Angeles Catalyst Study; Summary of Back-
ground Period (June, July, August 1974) 13
B8.3 Los Angeles Catalyst Study Operations Manual
(June 1974, amended August 1974) 33
B8.4 Collection and Analysis of Airborne Suspended
Particulate Matter Respirable to Humans for
Sulfates and Polycyclic Organics (October 8, 1974). . 194
VOLUME 9
B.9 Human Studies
B9.1 Update of Health Effects of Sulfates, August 28, 1974 1
B9.2 Development of Analytic Techniques to Measure
Human Exposure to Fuel Additives, March 1974 7
89.3 Design of Procedures for Monitoring Platinum
and Palladium, April 1974 . 166
B9.4 Trace Metals in Occupational and Non-occupation-
ally Exposed Individuals, April 1974 178
B9.5 Evaluation of Analytic Methods for Platinum and
Palladium 199
B9.6 Literature Search on the Use of Platinum and
Palladium 209
B9.7 Work Plan for Obtaining Baseline Levels of Pt
and Pd in Human Tissue 254
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Appendix B1.1
Fuel Surveillance and Analysis
A national fuel and fuel additive sample collection network has
been established. Commercial samples of fuels, consumer-purchased
additive packages, and crankcase lubricants are collected at the retail
outlets. These samples are shipped to NERC-RTP for detailed analysis.
This program, of necessity, has devoted considerable effort toward
development of advanced analytical procedures and standardized reference
materials which will assure an appropriate and accurate analytical
data base. Analysis has focused on lead, phosphorus, sulfur, trace
metals, and fuel distillations.
It is the intent of this activity to provide actual commercial
product analysis for comparison with registration information. In the
case of lead and phosphorus analysis, such information provides a basis
for assessing compliance with the two EPA regulations regarding the
special fuel for catalyst vehicles (FR, January 10, 1973) and the lead
phase-down regulations (RF, Dec. 6, 1973).
In addition, the data gathered through this network and from other
sources, regarding the sulfur levels in the unleaded fuel required for
catalyst vehicles permits a more realistic estimate of the impact of catalyst
generated sulfuric acid on human exposures. This, of course, is due to the
fact that the sulfur content of the fuel is a determinant of the sulfuric
acid emission rate.
Analysis of gasolines collected in Los Angeles and San Francisco areas,
consumer purchased additive packages, motor vehicle crankcase lubricants,
and distillate fuel oils are shown on the following pages. Gasoline
sulfur levels, by grade, are summarized from the EPA Surveillance Network
and U.S. Bureau of Mines Survey in the final table.
-------
Gasoline Analysis
Sample No.
F73-000-504
F73-000-505
F73-Ot>0-517
F73-000-519
F73-000-523
F73-000-501
F73-000-506
F73-000-508
F73-000-515
F73-000-419*
F73-000-518
F73-000-509
F73-000-511
F73-000-514
F73-000-522
F73-000-502
F73-000-507
F73-000-510
F73-000-513
F73-000-516
F73-000-520
F73-000-521
Los
Grade
No Lead
No Lead
No Lead
No Lead
No Lead
Low Lead
Low Lead
Low Lead
Low Lead
Low Lead
Low Lead
Regular
Regular
Regular
Regular
Premium
Premium
Premium
Premium
Premium
Premium
Premium
Anqolcs Metropolitan
Sulfur
0.005
0.006
0.071
0.073
0.070
0.025
0.078
0.075
0.051
0.062
0.068
0.073
0.100
0.090
0.021
0.020
0.070
0.021
0.023
0.041
0.026
0.017
Lead
0.015
0.011
0.019
0.019
0.015
0.462
0.385
0.418
0.451
0.836
0.473
0.92
1.17
1.53
3.72**
2.86
2.09
2.50
1.79
2.86
2.04
1.87
Area
IBP
107
103
105
98
108
96
100
101
93
92
92
89
95
95
102
98
99
94
92
90
101
106
Distillation «F
10% 50% 90%
152
144
140
135
144
122
133
132
122
128
124
129
128
128
148
131
126
126
130
117
170
170
230
228
218
217
217
238
228
229
204
230
218
241
227
207
215
237
219
223
231
245
246
263
300
305
318
323
321
328
350
3-19
311
364
320
350
361
367
?77
339
344
339
333
323
337
335
* Sample taken in San Diego, Ca.
** Run in duplicate.
-------
Gasoline Analysis
Sample No.
F73-000-414
F73-000-423
F73-00'0-401
F73-000-405
F73-000-407
F73-000-A08
F73-000-411
F73-000-412
F73-000-415
F73-000-402
F73-000-406
F73-000-410
F73-000-416
F73-000-417
F73-000-422
F73-000-421
F73-000-403
F73-000-404
F73-000-409
F73-000-413
F73-000-418
F73-000-420
San
P'rnncisco
Metrooolitan Area
Distillation °F
Grade
No Lead
No Lead
Low Lead
Low Lead
Low Lead
Low Lead
Low Lead
Low Lead
Low Lead
Regular
Regular
Regular
Regular
Regular
Regular
Blend
Premium
Premium
Premium
Premium
Premium
Premium
Sulfur
%
0.007
0.007
0.012
0.005
0.009
0.029
0.030
0.021
0.008
0.019
0.012
0.077
0.004
0.005
0.013
0.028
0.004
0.004
f
0.027
0.010
0.006
0.005
Lead
gin/gal
0.015
0.013
0.484
0.462
0.561
0.594
0.539
0.550
0.495
2.19
1.53
1.53
1.38
0.816
2.04
1.53
1.68
2.50
2.75
2.75
0.969
1.79
IBP
100
106
47
100
98
103
102
105
100
98
102
103
98
1Q4
91
100
100
100
100
105
104
97
10%
137
140
134
132
134
138
137
133
130
136
135
132
136
138
128
139
140
129
136
132
145
143
50%
216
217
205
207
209
228
230
202
201
238
220
213
229
230
228
229
225
206
233
193
255
234
90%
324
328
31?
325
331
330
333
325
320
355
326
345
326
323
355
325
320
339
343
310
329
340
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ADDITIVE IDENTIFICATION
RTP, N. C. AREA
SamP1e Description
F73-000-006 Wynns Engine Tune Up
F73-000-013 Prestone Carb Tune Up
F73-000-016 Dupont Gas Booster
F73-000-477 Preston Carburetor and Fuel
System Cleaner
F73-000-478 Marvel Mystery Oil
F73-000-479 STP Oil Treatment
F73-000-480 Rislone Engine Treatment
F73-000-481 Prestone Prime Gas Dryer
F73-000-482 STP Double Power Gas Treatment
F73-000-483 Wynn's Engine Tune Up
F73-000-484 Wynn's Concentrated Supreme
Oil Supplement
F73-000-485 Wynn's Gasoline Treatment
F73-000-486 Wynn's Carburetor Cleaner
F73-000-487 Gumout Carburetor Cleaner
F73-000-488 Alemite CD-2 Oil Detergent
F73-000-489 Dupont Oil Treatment
F73-000-490 Dupont Gas Guard
F73-000-491 Casite Motor Honey
F73-000-492 Casite Tune-Up
-------
EPA FUEL ADDITIVES
SAMPLE
F-n-ox
«
ft
tf
H
n
n
t. 1
tl
n
H
M
**
"
»•
* ' M.
. n
H
n
it
M
M
NO.
1-006
•006*
-Oli
•Oli*
-016
-016*
•477
•478
-479
-480
-481
-482
-483
-484
-485
-486
-487
-488
•489
-490
-491
-492
Mj
i
2
-------
EPA FUEL ADDITIVES
SAMPLE NO.
F-73-000-006
" -006*
" -013
#• " -013»
X* " -016
• -016*
11 -4n
• K* " -478
•* " -479
" -480
" -481 j
" -482
" -483
•jtf* " -484
" -485
" -486
11 -487
" -488
*•* " .-489
" -490
" -491
ft " -492
Ag
laooi
2
-------
MOTOR OIL IDENTIFICATION
Sample No Description Region
F73-000-255 Gulf, SAE 10-20-40 3
F73-000-258 Texaco, SAE 10W-40 3
F73-000-374 Shell, SAE 10W-40 7
F73-000-375 Standard, SAE 10W-40 7
F72-009-572 Gulf, 10W 20W-40 1
F72-009-573 Texaco, 10W-40 1
F72-009-574 Mobil, 10W-40 1
F72-009-620 Texaco, 10W-40 3
F72-009-660 Mobil, 10W-40 4
F72-009-665 Exxon, 10W-40 4
F72-009-707 Texaco, 10W-40 5
F72-009-712 Enco, 10W-40 5
F72-009-7S2 Mobil, 10W-40 6
F72-009-767 Gulf, 10W-40 6
F72-009-848 Standard, 10W-40 7
F72-009-8SO Texaco, 10W-40 7
F72-009-864 Exxon, 10W-40 8
F72-009-870 Texaco, 10W-40 8
F72-009-920 Enco, 10W-20W-40 9
F72-009-922 Gulf, 10W-40 9
-------
Sample Number
Region
Identification
72-009-609
72-009-658
72-009-722
72-009-751
72-009-768
72-009-847
72-009-858
72-009-878
72-009-921
72-009-923
72-009-953
•72-009-961
72-009-964
72-009-971
72-009-994
73-000-320
73-000-323
73-000-391
73-000-392
73-000-424
73-000-425
73-000-464
73-000-465
III
IV
V
VI
VI
VII
VIII
VIII
IX
IX
X
X
X
X
X
V
V
VIII
VIII
IX
IX
I
I
Gulf, 10W-40
Texaco, 10W-40
Gulf, 10W- 40
ENCO, 10W- 40
Texaco, 10W-40
Gulf, 10W-40
Mobil, 10W- 40
Gulf, 10W-40
Texaco, 10W-40
Mooil, 10W-40
Texaco, 10W-40
Shell, 10W-40
Mobil, 10W-40
Gulf, 10W-40
Texaco, 10W-40
Gulf, 10W-40
Texaco, 10W-40
Gulf, 10W-40
Texaco, 10W-40
Gulf, 10W-40
Texaco, 10W-40
Texaco, 10W-40
Gulf, 10W-40
-------
EPA MOTOR OILS
SAMPLE NO.
r-n-coo-255
" -258
" -374
" -375
F-72-009-57Z
" -573
" -574
- -574*
" -620
" -«0
" -665 j
11 -70T
" -712
" -712*
" -752
" -767
" -767 *
" -MS
". -850 •
" -864
" -870
11 -920
" -922
Ag
<0.07
7
aozs
-------
EPA MOTOR OILS
SAMPLE NO.
F-I3-ODO-25S
11 -25S
11 -374
11 -375
f -72-009-572
" -573
" -574
11 -574"
" -620
11 -660
" -665
" -707
11 -712
" -712*
11 -752
- -767
" -767 •
11 -848
" -850
" '-864
" -870
" -920
" -9Z2
460
<20
<20
1160
410
<20
16110
2017
<20
SOtlO
<60
<20
<60
8*4
40110
670
770
1170
<20
<20
<20
<20
390
Mn
018
023
025
0 101 0.03
0141002
0,22
021
019
030
022
a 08 1 003
016
0.081002
010
019
01010.02
-------
EL£,-Z;;TAL ANALYSIS CF E.P.A. KQT33 CII.S U3/m!
SAMPLE i
72-C:-?-G39
72-C35-J53
72-C:?-722
72-OC3-751
72-CC9-763
72-c;?-:-:?
72-C39-S53
72-C39-S78
72-OC9-921
72-0:9-73
72-C37-5J3
72-C:9-951
72-039-561
72-0:9-<571
72-CJ9-9T4
73-G30-320
73-0:0-323
73-0:3-391
73-C:0-392
73-CC3-424
73-::C"£25
73-C:3-454
73*0:0-465
Ag
<2
<0.005 <1
-------
ELEMENTAL ANALYSIS OPE.P.A. MOTOR OILS ug/ml (cont)
s ••.;••.?<.£ §
72-C:9-S09
72-C9-55S
.72-C-:?-722
72-C09-751
72-C:9-763
72-039-E47
72-C3=-£3S
72-C35-378
72-C39-921
72-C39-CZ3
72-G:?-rJ3
72-009-951
72-009-564
72-G9-S71
72-03?-9«
73-GCO-320
73-COO-3Z3
75-CO391
73-COO-392
73-C:XK24
73-0^-425
73-C33-454
73-C:->455
TJ_Q.->JJ^7A
Eu
<0.0333
-------
ELE?.iE:3TAL ANALYSIS 07 E.P.A. MGTGR OILS fJg/ir.I (coat)
u>
SAiV3LE *
72-'.:r-639
72-C:9-05S
72-C39-722
72-039-751
72-CC9-7C3
72-CJ7-S47
72-CG9-Q58
72-CG9-S78
72-CG9-921
72"-C:?-9Z3
72-C39-953
72-C09-951
72-C09-954
72-CG9-971
72-CC9-994
73-GCO-320
73-G33-323
73-CIO-391
73-OCO-392
73-c:-;K24
73-00-25
73-CC3-MJJ
73-CCD-463
Sc
-------
FUEL OIL ANALYSIS
Sample Number
72-009-622
72-009-623
72-009-726
72-009-727
72-009-735
72-009-746
72-009-747
72-009-748
72-009-749
72-009-750
72-009-790
72-009-791
72-009-792
72-009-833
72-009-938
72-009-972
72-009-979
Region
III
III
V
V
V
V
V
V
V
V
VI
VI
VI
VII
IX
X
X
Brand Identification
Texaco, No. 2
Shell, No. 2
ARCO, No. 2
Texaco, No. 2
Mobil, No. 2
ARCO, No. 6
Hartney Oil Co. No. 6
Allied Oil, No. 6
Allied Oil, No. 6
Ap:,x Oil
Fort Worth
Refinery, No. 5
Fort Worth
Refinery, No. 5
Fort Worth
Refinery, No. 5
Phillips, No. 2
Navy Fuel Depot
Pacific, Mixture
Shell, No. 2
-------
ISiTAL ANALYSIS OF E.P.A. DISTILLATE FUEL GILS ug/rr.I
SA.V.PLE 9
72-C:?-522
72-C09-OZ3
72-C09-726
72-C09-727
72-CC9-735
72-C09-746
72-C09-747
72-CC9-7-53
72-C09-749
72-CC9-750
72-C:9-7?0
72-C09-791
72-C09-792
72-CQ9-S33
72-C09-93S
72-009-972
72-CC9-979
Ag
-------
ELEKEBTAL ANALYSIS OF E.P.A. DISTILLATE FUEL OILS ng/ml [cont]
SAf/.PLE «
72-CJ9-&22
72-CC9-5Z3
72-OC9-726
72-009-727
7.2-CC9-735
72-039-746
72-C39-747
72-OC9-74S
72-C79-749
72-009-750
72-CG?-790
72-CC9-791
72-CG9-792
72-C09-S33
72-C37-93S
72-C09-972
72-C09-979
Eu
-------
ELEMEHTAL ANALYSIS OF E.P.A. DISTILLATE FUEL OILS u*/m! [contj
SAMPLE!
72-009-622
72-CC9-623
72-CG9-726
72-009-727
72-009-735
72-059-746
72-009-747
72-009-743
72-C09-749
72-009-750
72-009-790
72-009-791
72-C09-792
72-009-333
72-CG9-533
72-009-972
72-009-979
Sc
-------
GASOLINE SULFUR CONTENT*
00
A. N AT I 0 N W I D E FIGURES
1. REGULAR
2. P R E JM I U N
3. NON-LEADED
B. SOUTHERN CALIFORNIA
1. REGULAR
2. P P. E M- I U M
3. N 0 N - L E A D E D**
T. g S U L F U R
A V G M A X
0.038 G.069
0.023 0.045
0.023 0.060
0.069 0.116
0.042 0.056
0.023 0.037
W T. % S U L F U R***
A V G
.034
.015
.035
M A X
.119
.067
.133
*SOURCE-U. S. BUREAU OF MINES MINERAL INNDUSTRY SURVEY
: CO, J U M E 1 9 7 3
**ONLY 19 SAMPLES WERE TESTED
*** E' P A FUEL SURVEILLANCE NETWORK-! 20 COMMERCIAL GASOLI K"E
SAMPLES
-------
Appendix B1.2
The EPA National Fuels Surveillance Network
I. Trace Constituents in Gasoline and Commercial
Gasoline Fuel Additives
by
Robert H. Jungers
Robert E. Lee, Jr.
and
Darryl J. von Lehmden
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, North Carolina 27711
For presentation at the Annual ACS Meeting, August 1973
For publication in Environmental Science and Technology
19
-------
Sulfur Results on Regional Gasoline Sariples
(Results Reported in Tercents)
Total Sa-nples • 111
34 Pre.oiim w/avg of 0.019 SS
40 Regular w/avg of 0.032 »S
37 Low Lead w/avg of 0.021 %S
REGION I (Boston)
Preriun
6
Regular
5
Low Lead
8
Hi
0.037
Hi
0.033
Hi
0.057
Lo
0.011
Lo
0.007
Lo
0.007
Avera<»e
0.016
Average
0.022
Average
0.040
REGION III (Oiarlottesville, Va.)
Pre:u.ui.\
6
Regular
7
Low Lead
5
Hi
0.025
Hi
0.049
Hi
0.042
Lo
0.011
Lo
0.023
•Lo
0.007
Average
0.017
Average
0.040
Average
0.027
REGION IV (Atlanta)
Preriiira
2
Regular
4
Low Lead
5
Hi.
0.035
Hi
0.028
Hi
0.10
Lo
0.024
Lo
0.059
Lo
0.055
Average
0.030
Average
0.033
Average
0.018
20
-------
ABSTRACT
A National Fuels Surveillance Network has been established to
collect gasoline and other fuels through the 10 Regional Offices
of the Environmental Protection Agency. Physical, chemical, and trace
element analytical determinations are made on the collected fuel samples
to detect components which may present an air pollution hazard or poison
exhaust catalytic control devices now under development.
A summary of trace elemental constituents in over 50 gasoline
samples and 18 commercially marketed consumer purchased gasoline
additives is presented. Quantities of Mn, Ni, Cr, Zn, Cu, Fe, Sb, B,
Mg, Pb and S were found in most regular and premium gasoline. Environ-
mental implications of trace constituents in gasoline are discussed.
21
-------
INTRODUCTION
The combustion of petroleum based fuel in'motor vehicles represents
an important emission source of both participate and gaseous pollutants
to the environment. The potential health, hazard associated with the
combustion products from fuels and fuel additives was recognized in the
Clean Air Act as amended in 1970, Section 211, which empowers the Environ-
mental Protection Agency (EPA) to require manufactuvers of fue1^ and
fuel additives to register their products. As an integral part of this
program, EPA established a National Fuels Surveillance Network (MFSN)
in 1972 for the collection and analysis of fuels and fuel additives
throughout the country.
In addition to providing data for validating information provided
by fuel and fuel additive manufacturers, the NFSN should also serve as
a source of information for a variety of other uses including: (a) the
detection of constituents in motor vehicle fuel which could poison exhaust
catalytic control systems now under development to meet statutory standards,
(b) detection of toxic components in fuel, especially heavy metal con-
taminants introduced during transport and storage processes, (c) the
development of accurate emission factors for assessing the contribution
of trace metals and other fuel components to the atmosphere, (d) the
enforcement of federal regulations on fuel additives such as the regulated
limits on lead and phosphorus in gasoline (Federal Register, Part II,
Jan. 10, 1973), and (e) the design of studies to identify emission con-
stituents.
22
-------
This is the" first in a series of reports on the NFSN, and is
limited to a description of the network operation, chemical analytical
methods used, and a summary of results of trace constituents in gasoline
and commercially marketed consumer purchased gasoline additives.
EXPERIMENTAL
The Operation of the National Fuels Surveillance Network
Fuel samples are generally collected by the ten EPA regional offices
in accordance with specific requests from EPA's National Environmental
Research Center (NERC) located in Research Triangle Park, North Carolina.
NFSN was established in 1972 during which 200 gasoline samples were
collected. It is anticipated that approximately 1000 samples will be
collected annually thereafter and sent to the NERC for in-depth chemical
and physical analysis. During the early phases of the network, the
collection of gasoline and consumer purchased gasoline fuel additives
was emphasized, however, proportionately larger quantities of other
fuels will be collected in subsequent years to include aviation gasoline,
jet fuel, diesel fuel, distillate and residual fuel oil, and motor oil
samples.
Generally, fuel samples are collected at the last point in the dis-
tribution system, i.e., the retail outlet such as service stations and
heating oil distributors, although selected samples from refineries and
pipelines will also be collected. Samples are collected in a metal-
jacketed 500 ml Wheaton* hard-glass container (Wheaton Glass Co.) with a
*Mention of commercial products does not constitute endorsement by the EPA.
23
-------
teflon*-lined cap. The Wheaton bottle is cleaned by soaking 24 hours in
1:1 nitric acid, rinsing with distilled water and soaking for an additional
24 hours in distilled water. This procedure has been found to remove
detectable levels of trace metal contaminants from the container.
In sampling gasoline, at least one gallon is discarded from the pump
before filling the container completely, discarding the gasoline, refilling
the container to the shoulder, capping tightly, and marking the level on the
bottle. The collected sample is placed inside another metal can which is
filled with an absorbant, sealed, labeled and sent to the NERC Fuels
Laboratory by ground transportation in accordance with Title 49, Code
of Federal Regulations (Code of Federal Regulations, 1968). In the
laboratory, the samples are ordinarily stored at room temperature in
subdued light although refrigeration is suggested for long term storage.
CHEMICAL ANALYSIS
Procedures outlined by the American Society for Testing and Materials
(ASTM) are followed from gasoline, diesel fuel, distillate and residual
fuel oil, crankcase oil and consumer purchased fuel additives to determine
ash content (ASTM, D-482, 1971), viscosity (ASTM, D-445, 1971), thermal
value (ASTM, D-240, 1971), API gravity (ASTM, D-287, 1971), and saturates
non aromatic olefins and aromatics (ASTM, D-1319, 1971). Ordinarily these
determinations are made only on selected samples and are not part of the
routine analysis carried out.
Sulfur is determined by combustion iii an oxygen enriched atmosphere
or by burning in an artificial atmosphere of 70?! carbon dioxide and 30«
*Mention of commercial products does not constitute endorsement by the EPA.
24
-------
oxygen (ASTM, D-1266 and D-129, 1971); phosphorus in gasoline by
ignition with zinc oxide, dissolution in sulfuric acid followed by spec-
trophotonjetric analysis using ammonium molybdate-hydrazine sulfate; and
carbon, hydrogen, and nitrogen by pyrolysis at 975° C over platinized
carbon utilizing a Perkin-Elmer 240 elemental analyzer in accordance
"with the manufacturer's instructions.
Lead in gasoline in the range of 0.01 to 0.10 gm/gal. is determined
by atomic absorption (ASTM, 1973). The lead in the sample is extracted
into methyl isobutyl ketone with a quaternary ammonium salt (tricapyl
methyl ammonium chloride) after the organic lead has been converted to
inorganic lead with iodine. The lead content of the sample is determined
o
by atomic absorption flame spectrometry at 2833 A using standards prepared
from reagent grade lead chloride. By the use of this treatment, all
alkyl lead compounds give identical response.
Two multi-element techniques that were intensively investigated
for obtaining elemental data on gasoline and other fuels in the trace
concentration (ppm-ppb) range were neutron activation analysis and spark
source mass spectrometry. Studies to evaluate the accuracy and precision
of these methods are reported elsewhere. (vonLehmden, Jungers and Lee, 1973)
Neutron activation analysis was limited for the analysis of gasoline because
of the possible explosion of the volatile sample in the nuclear reactor
and the masking effect of bromine which swamps the radioactive signal of
elements having similar half-lifes.
On the other hand, spark source mass spectrometry was applicable for
the analysis of over 20 elements in gasoline including Be, Cd, As, V, Mn,
25
-------
N1, Sb, Cr, Zn, Oi, Se, B, Ag, Al, Fe, Mg, Cl, P, Pb; and Ca. A gasoline
sample -is oxidized with bromine followed by freeze drying to remove the
liquid and final drying to remove the odor of gasoline. The remaining
residue, including the trace elements, is mixed with graphite until homo-
genous and is pressed into an electrode for analysis with an AEI MS 702R
spark source mass spectrometer equipped with photograph plate output
(Carter, 1973).
In the study reported here, over 40 gasoline samples were collected
for trace element analysis which included at least two regular grades in
each of the following cities: Boston, New York, Philadelphia, Atlanta,
Chicago, Kansas City, Denver, Dallas, San Francisco, and Seattle. In
addition, a total of 6 no-lead or lov.'-lead gasoline samples were collected
•in'Seattle, Boston,'Philadelphia and, Kansas'City. Six oil companies
were represented in the study including Texaco, Mobil, Shell, American,
Exxon, and Gulf.
Eighteen samples of commercially available consumer purchased
gasoline additives were purchased at retail outlets in the Raleigh-Durham,
North Carolina area and analyzed by neutron activation. The brands
i
sampled included: STP Gas Treatment; Gumout, Fuel Mix Tune Up; Wynn's
Engine Tune up: Wynn's Spitfire Gas Power Booster; K-Mart Gas Treatment;
Zerex Gasoline Antifreeze; Prestone Carb Tune up; Dupont Gas Booster; and
Max S-E-T Gas Booster.
RESULTS AND DISCUSSION
Trace Elements in Gasoline
Table I presents a sunimary of the concentration range of trace
constituents in 50 gasoline samples collected for the NFSN. Except for
26
-------
Pb and S, all determinations were made by spark source mass spectrometry
(Carter, 1973). In premium grade gasoline measureable concentrations of
Cd, As, V, Hn, Ni, Sb, Cr, Zn, Cu, B, Ca, Ag, Al, Fe, Mg, Cl, P as well
as Pb and S were found. .Trace amounts of the same elements were also
found in regular grade gasoline except for Cd, V, Ag, Al and P. In low
lead or no lead gasoline, trace amounts of Mn, Ni, Cr, Zn, Cu, Fe,,Cl,
Ca, Pb and S were detected.
No association was apparent in the levels of trace constituent
found in gasoline and the sampling location. It seems, therefore,
that the ele-r,.ents detected were (a) native to the crude oil before
refining, (b) introducted as a fuel additive or as a contaminant of
a fuel additive, or (c) extracted during the transfer and storage
process, e.g., pipelines and service station tanks. In both imported
and domestic crude oils, Se, As, Ni, S, and V are known to be present
(Anderson, 1973), however, it is likely that the levels of these elements
are reduced or even removed in the gasoline fractions during the
refining process. On the other hand, B, Ca, Cu, Mn, Zn, P, Pb, Cl and
S are known to be components in some organic fuel additives reported
to EPA (Bridbord, 1972) although not all are necessarily associated
with an individual fuel manufacturer.
It appears that a portion of the trace constituents found in gasoline
is introduced in fuel additives or is extracted from the transport and
storage system. Hydrocarbon soluble metal compounds can form by reaction
of phenols, mercaptans and other acidic materials in gasoline with metals
in contact with the gasoline between the refinery and the automobile.
27
-------
(Polss, 1973). Metals can deteriorate antioxidant addivites such as
phenylcnediamines and hindered phenols which prevent gum formation.
To reduce oxidative deterioration in gasoline, a metal deactivator
such as N, N-disalicylidene-1,2-propanediamine is used to chelate Cu and
other metals. Although ir.etal deactivators are effective suppressors of
oxidative deterioration, the chclated metal contaminants will be com-
busted thereby acting as potential poisons of exhaust catalytic devices
now under development or the metals may be emitted into the air as
pollutants. Indeed, most of these elements have been identified in
auto exh?.ust participate (Moran, Baldwin, ,'lanary and Valenta, 1372).
Table II presents concentration ranges of lead and phosphorus for
197 premium, regular and low lead gasoline samples collected during 1972
in ten designated cities. A review of this table shows that the lead
concentration range in New York is well below 2.0 grams Pb/gallon as
required by NYC regulations. The Federal standard for lead and phos-
phorus as published in the Federal Register (Part II, 1973) defines "lead
free" gasoline as containing not more than 0.05 g/gal. and "phosphorus
free" as containing not more than 0.005 g/gal. This 91 minimum octane
gasoline must be made available after July 1, 1974 in a substantial
percentage of gasoline retail stations to provide a fuel which can be
used with exhaust catalytic system. Of further interest the proposed
standard (Federal Regulation, Part III, 1973) specifies a decreasing
amount of lead which will be allowed in all gasoline dispensed by either
the refiner, distributor or retailer. This decrease- is January 1, 1975 -
2.0g Pb/gnl; January 1, 197G - 1.7g Pb/gal.; January 1, 1977 - 1.5g Pb/gal.;
28
-------
January 1, 1978 - 1.25g Pb/gas. In non-lead manufacturing areas, the
reduction in lead should result in a definite decrease in atmospheric
lead.
Trace Constituents in Corrniercial Consumer Purchased Fuel Additives
Eighteen commercially marketed gasoline additives were analyzed
by neutron activation analysis (Rancitelli, 1973). Results, summarized in
Table III show that measureable levels of Hg, As, V, Mn, Sb, Cr, Zn, Co,
Se, Sn, Ag, Al, Fe, and Sr were found. Additives of this type are multi-
functional acting as antioxidants, metal deactivators, corrosion inhibitors,
anti-icers, and carburetor and valve deposit detergents. Ordinarily,
these additives are used to supplement the additives already present in
fuol and may not necessarily be representative of additives blended at
the refinery.
Examination of Table III reveals the presence of comparative high
levels of Sn (up to 140 yg/ml). Apparently the predominant source of the
Sn and possible other elements such as Fe in the fuel additives may have
been the metal packaging container, especially from the soldered connection.
Intensive use of commercially-marketed additives can add to the environ-
mental trace metal burden and increase the potential for poisoning exhaust
catalytic control devices.
Environmental Implications
The presence of metallic elements in gasoline, especially those
which have suspected biological toxicity such as Cd, As, V, Ni, and Cr
29
-------
is of concern to environmentalists because of the potential widespread
dissemination of these constituents, most in the respirable range, at
ground level. Several studies of the particle size of trace metal com-
ponents in ambient air have shown that Pb, V, and In are associated with
particles predominantly of a sub'micron aerodynamic size (Lee, Goranson,
Enrione, and Morgan, 1972; Lee, Patterson, and Wagman, 1968). Particles
in this size range can remain suspended in air for long periods of time
and can penetrate deep into the human respiratory system (Morrow, 1964).
Furthermore, many of the metals found in gasoline, notably Fe and Pb
(Urone, Lutsep, Noyes, and Parcher, 1968) can act as catalysts in the
transformation of primary atmospheric pollutants to secondary pollutants,
e.g. S02 to SO.. Although gasoline combustion may not necessarily be
the major source of these constituents, the-fact that over 100 billion
gallons are consumed annually indicates that gasoline combustion should
be considered in estimates of environmental emissions of these metals.
Another environmental concern, mentioned earlier is the presence
of constituents such as S, which may poison exhaust catalytic devices
now under development thereby reducing their effective operating life.
Coupled with this concern is the distinct possibility that fine metal
particles may be produced from the exhaust catalysts themselves as
recently reported by Balgord (1963). It becomes important, therefore
to characterize the trace constituents in the fuel in order to assess
the amount of trace metals emitted by exhaust catalytic devices. The
widespread use of consumer purchased gasoline additives which contain
trace elements that can effect catalytic performance also presents a
serious problem.
30
-------
As more information becomes available through the National Fuels
Surveillance Network, it may be necessary to institute some type of
control at the refinery or distributor outlet to remove trace con-
taminants from fuel before it is combusted in the motor vehicle.
31
-------
ACKNOWLEDGEMENT
The authors thank Jack Hein, Kathy MacLeod and Allan Riley from this
laboratory for the chemical analysis. The authors also thank EPA Regional
personnel who participated in the planning, sampling and shipping of the
gasoline samples.
32
-------
LITERATURE CITED
American Society for Testing and Materials, Book of ASTM Standard Methods,
Method D-432, Part 17, p. 187 (1971).
American Society for Testing and Materials, Book of ASTM Standard Methods,
Method D-445, Part 17, p. 178 (1971).
American Society for Testing and Materials, Book of ASTM Standard Methods,
Method D-240, Part 17, p. 124, (1971).
American Society for Testing and Materials, Book of ASTM Standard Methods,
Method D-2S7, Part 17, p. 131, (1971).
American Society for Testing and Materials, Book of ASTM Standard Methods,
Method D-1319, Part 17, p. 474 (1971).
Amercian Society for Testing and Materials, Book of ASTM Standard Methods,
Method D-1266, Part 17, p. 431 (1971). and D-129, Part"!/, p. 74, "(1971)
American Society for Testing and Materials (ASTM), "Determination of
Low Lead Concentration in Gasoline by Atomic Absorption Spectrometry,"
Tentative Method, in press (1973).
Anderson, D. L. "A Limited Program for Analysis of Foreign Crude and
Kesidjal Oils," CPA Internal. Report, National Environmental Research
Center, RTP, N. C. (1973).
Balgord, W. D., Science 180. 1168 (1963).
Bridbord, K. personal communication, EPA National Environmental Research,
Center, RTP, N. C. (1972).
Carter, J. A. "Matrix Evaluation and Quality Control Analysis of Fuel and
Fuel Additive Samples," EPA No. AS0971, Oak Ridge National Laboratory, Oak
Ridge, Tennessee (1973).
Code of Federal Regulations. Title 49 - Transportation, part 172.5, p. 58,
including exemptions part T73.118 and 173.119 p. 143-148 January 1, 1968.
Federal Register, "Regulations of Fuels and Fuel Additives" Part II, .38
January 10, 1973.
Federal Register, "Regulations of Fuel and Fuel Additives, Notice of Pro-
posed Rule Making," Part III, JJ8 January 10, 1973.
Lee, R. E., Jr., Goranson, S. S., Enrione, R. E., and Morgan, G. B.,
Envrion. Sci. Techno!. 6. 1025 (1972).
Lee,^R. E., Jr., Patterson, R. K., and Uaginan, J. Environ. Sci. Techno!.
2, 2C3 (1963).
33
-------
Moran, J. B., Baldwin, M. J., Manary, 0. 0., and Valenta, J. C. "Effect of
Fuel Additives on the Chemical and Physical Characteristics of Particulate
Emissions in Automotive Exhaust," EPA-R2-72-066 performed by Dow Chemical
under contract CPA-22-69-145, December 1972.
Morrow, P. E., Am. Ind. Hyg. Ass. J. 25. 213 (1964).
Polss, P. "What Additives Do for Gasoline," Hydrocarbon Processing,
61, (1973).
Rancitelli, L. "Neutron Activation Analysis of Fuel and Fuel Additive
Samples," EPA Contract fio. AS0161, Battelle Laboratories, Richland, Washington
(1973).
Urone, P., Lutsep, H., Noyes, C. M., and Parcher, J. F., Environ. Sci. Techno!.,
2., 611 (19G8).
von Lehniden, D. J., Jungers, R. H., and Lee, R. E., Jr., Anal. Chem., in
press (1973).
34
-------
Table I
Trace fleir.ants in Gasoline
Premium (22 Sc.r.;;)lcr.)
Element
Be
Cd
As
V
Mn
Mi
Sb
Cr
Zn
Cu -
Se
B
Ag
Al
Fe
Mg
Cl
P
Pb**
s***
Ca
Range
<0.001
<0.001 - 0.03
<0.001 - O.C:'2
0.001 -
0.002 -
0.003 -
<0.003 -
-------
Table II
loncentraticn Ranges of Lead and Phosphorus in Gasoline Samples Collected during 1972 in Ten EPA Regions
ot
: , :y^
Lccd
Prc:::iu'.n
, ;.•:,-, (9)
, ,'e.-:; (9)
: . : :l;.,-a (f)
.. '--..La (6)
:. -. ..,0 (11
.-,-.:.s (5)
' . .5 City (E)
: ..- (£)
:. "Varicisco (S)
: .112 (4)
* i
0
1.
1.
)1.
2.
1.
1.
1.
1.
.49-2.85
.85-1.31
31 -2.77
78 -2.5G
03 -2.72
10-2.89
21 - 2.65
C4-2.72
48-3.52
CO -2.65
(qrar'S/U.S
Regular
(5) 1.23-2
(11)0 72-1
(9) 1.19-2
(7) 0.90-2
(7) 0.33-2
(5) 1.39-2
(5) 1.42-2
(5) 1.14-1
(5) 1.28-2
(7) 1.62-3
. Gal
.84
.08
.70
.36
.43
.72
.20
.94
.32
.40
Ion)
(11
(5)
(8)
(6)
(7)
(5)
(5)
(4)
(6)
(3)
Low
) o
0.
0.
0.
0.
0.
0.
0.
0.
0.
Lead
.009-0
018-0
010 -3
016 -3
003 - 1
032 -3
Oil -1
022-1
037 -0
.68
.29
.60
.48
.70
.44
.46
.20
.63
020 -0.50
Phosphorus (nrii.-:s/U.S. Ssll
Prciinirn Rscjior
(9)<0. 0001-0. 006 (5)<0.0~JUL~0.004 (1
(9).O.CC01-0.0002 (11)<0. 0001-0. OOC1 (
(«)<0. 0001-0. 0003 (9)<0. 0001-0. 0001 (
(6)<0. 0001-0. 004 (7)<0. 0001-0. 0001 (
(11)<0. 0001-0. 0003 (7)all <0.0001 (
(5)<0.0001-C.0002 (5)<0. 0001-0. 0001 (
(5)-O.OG01-0.0(J01 (5)all «-0.0001 (
(5)-O.OC01-0.0001 (5)all<0.0001 (
(9/all ^0.0001 (5)all <0.0001 (
(4}-0-0001-0.0001 (>)<0. 0001-0. 0001 (
on)
Low Le;d
1)'-.O.C031-0
5)
-------
Table III
Trace Elements in Consumer Purchased Fuel Additives*
Concentration Rcnge (ug/:r.l) Avg
Hg <0.0002 • 0.002
Cd <0.02 - 0.20
As
-------
LI i . I I i >j i . i I i.S> Ll i k In*. ..... V. I I >L • ' •,. I .Ui'J ' ' »
. . , Ir - ., .
M.i'Lus oi i.,>:>- ..... I Ci-rr is iCiiLion i'L»Y,iMn tor
.-ji>j:Ci 'iriicc i.JU'..^:ii:."> in Coal i;ly A:,h, ik'.siuual i'ui'.l DATE February 19, 197'*
Oil and Gasoline
IYO'-1 tfarryl 'J. von LciundiMi, Ciiicf, IDS, QCB/QAiIMlT^/ ^/. .
TO Sec Below
The status of tins LPA-NBS funded profjr.Tn for the certification of 15
trace clciwnrs (Hj, )Jc, 1'b, Cd, V, Iln, Nl, Cr, As, Sc, Zn, S, P, F, and U)
in coal,if]y .ish, fuc] oil, and gasoline is as follows:
^A. Coal and fly ,ish will be issued by March 1, 1974.
^ B. lic-oidiuil fuel oil will be issued by June 30, 1974, for
selected cJeiucnts.
\C. Gasoline certification is under way with no set date
for issuance.
The following information is required to order the NBS-SRM:
Coal, SRI-i // 1632. Cost - $73.00 (75 gm)
F.ly ..sh, Sl'ol ,'/ 3633. Cost - $73.00 (75 gin)
Fuel oil, SWI // 1634. Cost - $75.00 (100 ml)
Attached is a copy of the latest report on the certification progress.
One item is of particular significance in the report. The lead content
i n <".i«.ni i PI> ''^TP^sos- ^'jr-'n0 "Lor""*1? "hon i-«o i.Tolinr*. is r»*?cc"d to
prevent Jcad decomposition and that saicp]es stored for IS Months at
iifcr atuie in Jari.nc&s sho.; no si^is of decomposition.
The implication of this finding to the enforcement program for
unleaded gasoline is that all samples collected by mobile van operators
which beconc chain of custody samples by nature of being a violation or
a border line case, and r.ll samples used as quality control test
samples must be stored in such a manner to prevent exposure to light.
Attachment
Addresses: /
On/QAi.iiL (D. Shearer, T. Hauser)/
RJ/CSL (C. Crai£, J. Dorsey)
Dnfi/CSL (U. K,i.v.;cbrnuck, 1C. Janes)
FJ.J/.i'Si^D (C. Freed, J. SJakofosky)
ACii/QALiil, (U. Thompson, il. J lingers)
QAD (C. riosL)
QCJJ/ yAZin, (S. liochhciscr, T. Clark, S. Bronibcrg)
r;'A I ."ill 1 i/O-u 111-711
-------
File Number
NBS-ePA-1AG-Oir:,
CHAKACTIEKJ2ATION OF STANDARD RCFEKCNCE MATERIALS FOH
DETERMINATION Of TF7ACE ELEMENTS IN FUELS
Division of Aimoa'phoric Surveillance
ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park, N.C.
/ V \
IIB /
U.S. Department of Commerce
National Bureau of Standards
Washington. D.C. 2O234
39
-------
Date:
To
From
u.'.;. n^-vya.T'.-^JT o.- COMMEHCC
i'J -'.;c:r.,.i K.uru.iii u. L
»".-• !-n,jL:iii. DC ,'OAV,
February 1, 1974
James R. McNesby, Manaf>!<5r
Measures for Air Quality^
Through: Philip D. LaFJlcur/ Acting Chi
An a 1 y t i c a 1 C h o.rc-vs try P ^" ^ c ^ "VIT-
Via: John K. Taylor, Manager T..,
Environmental Analysis Progranl/^Division 310
Donald A. Becker, Acting Chief"
Activation Analysis Section
First Half FY 197/1 Progress Report on the Determination
of Trace Elements in Fuel Oil and Gasoline
Progress lias been made in several arras in tho determination
of trace elements in fuel oil and gas'linc. These
specific areas include storage condition, sample
handling techniques, and analytical methodology. Both
standards are currently undergoing analysis, and the
present status of each is discussed separately below.
Trace Elements in Gasoline
Initial testing of the gasoline stability with time on
the open shelf indicated definite decomposition was
occurring, most likely of the lead tetracthyl. This
was obvious through the deposition of a coating on
the glass surface, a scum on the top of the gasoline
still inside the original bottle, and a definite increase
in participate matter in the liquid itself. Thus, much
of the work on this material was held up until definitive
storage conditions could be determined. It lias now
been established that storage in the dark will prevent this
decomposition, and samples stored for 18 months at
ambient temperatures in. the dark show no signs of decomposition
Therefore, work on the sample-handling and analysis of
of gasoline is being continued.
-------
Sampling handling aspects of the gasoline arc very
difficult, since considerable evaporation occurs during
sampling and analysis causing significant decreases in
analytical precision and accuracy. A number of methods
of sampling and sample handling arc being evaluated,
including direct evaporation techniques, direct solvent
extraction techniques, and direct aspiration of the
gasoline into a flame type atomic absorption spectrometer.
The determination of some elements may also be possible
using non-destructive ne.utron activation analysis, however
the high bromine content of the gasoline will make this
analysis difficult.
In order to determine what trace elements are actually
present in the gasoline in measurable quantities, a.
general scan using optical emission spcctroscopy was
made. Due to sample handling problems, this technique
cannot be quantitative for gasoline, but detectable
quantities of Pb, Si, P, Mg, Sn, Fe, Al, Cu, Ag, Zn,
Ti, Ba, Ca, Sc and Cr were seen. The methods used
included slow evaporation of 100 ml of gasoline down
to 'v/SO mg of tar-like material. This procedure
probably loses some of the trace elements, especially
ones like Ni (probably present as the carbonyl), but
is valuable for obtaining a "more than" figure for
quantitative evaluation by other analytical techniques.
Trace Elements in Fuel Oil
Significant progress has been made in the analysis of
trace elements in the fuel oil. The present status is
shown in Table 1, and reveals that four elements (Ni,
Pb, V, Fe) have been determined by two or more methods
which agree, and can be certified when necessary. One
element (Zn), has been determined by txvo methods which
disagree (NAA and ATA), so additional work is necessary
to resolve this discrepancy.
Three more elements (Hg, Mn, Se) have been determined
by one method, and have a second method in process or
being examined for feasibility. Another three elements
(Cr, Cd, Be) are currently undergoing analysis, two of
which (Cr, Cd) should be feasible by at least two
methods. Arsenic and beryllium can be determined by only
one analytical method at present, with arsenic already
determined and beryllium currently undergoing analysis.
The fuel oil used was originally certified for sulfur
-------
content, but is undergoing rcanalysis by NAA in order
to verify that the sulfur content- is still the same as
previously. Finally, two elements (U, Th) have been
determined by IDMS and found to be extremely ]ow. A
second method is probably possible (NAA) but is not felt
to be justified for this material.
Thus, it is apparent that the analysis of the fuel oils
is progressing satisfactorily, and .-most of the stated
elements of interest (arsenic through zinc in Table 1)
should be able to be certified by the end of FY 1974.
-------
Table 1. Trace Elements in Fuel Oil Standard
Element
Arsenic
Beryllium
Cadmium
Chromium
Mercury
Manganese
Nickel*
Lead*
Sulfur
Selenium
Vanadium*
Zinc**
Method 1
NAA - Determined
SPEC - In process
NAA - In process
NAA - In process
NAA - Determined
NAA - Determined
IDMS - Determined
IDMS - Determined
Previously certified
NAA - Determined
NAA - Determined
NAA - Determined**
Method 2
POL - In process
ATA or IDSSMA - Feasible
ATA - Feasible
SPEC - Feasible
POL and ATA - Determined
POL - Determined
NAA - In process
IDSSMS - Feasible
ATA - Determined
ATA - Determined**
Iron*
Thorium
Uranium
POL - Determined
IDMS - Determined
IDMS - Determined
ATA - Determined
*Have two methods which agree
**Methods disagree
IDMS = Isotope Dilution Mass Spectrometry; IDSSMS = ID Spark
Source MS; POL = Polarography; SPEC = Spectrophotometry;
ATA = Atomic Absorption; NAA = Neutron Activation Analysis; MICRO
Microcalorimetry (Bomb.)
-------
Appendix B2.1
EMISSIONS CHARACTERIZATION
SUMMARY
The major effort in the ORD Fuel and Fuel Additive, Catalyst, and
Mobile Source Emissions Research Prog.ains has involved detailed charac-
terization of non-regulated emissions from mobile sources and the
effect fuel additives and control devices might have on such emissions.
Past efforts focused upon characterization of parti oil ate emissions
and the related development of a particulate measurement method (Appen-
dix B3). This has been an extremely difficult and complex task but is
reflective of the problems involved in the characterization and subsequent
development of new measurement and analytical technology. This broad
and advanced capability within the ORD research otaff, spec.fie to mobile
source particulate measurement methodology has been a positive critical
factor in our ability to ascertain the magnitude of sulfuric acid
emissions from both catalyst- and non-catalyst-equipped vehicles.
Detailed analysis of gaseous emissions products have also been conducted
within the control of these programs.
The effects sought in this research are really twofold: (1) determi-
nation of the change in relative ratios of identified non-regulated gaseous
and particulate emission species as a result of fuel, fuel additive, or
control device changes, and (2) determination of new exhaust species which
may result from fuel, fuel additives, or control device changes. Once
an emission product of concern or interest has been identified, the program
emphasis shifts to one of development of a detailed, specific measurement
methodology. Measurement methodology development is covered in detail in
the following Appendix B3.
Contained within this Appendix are those ORD programs which focus
upon the characterization of non-regulated gaseous and particulate exhaust
products from both catalyst and non-catalyst-equipped motor vehicles.
-------
Appendix U2.2
S'JLFATE EMISSIONS FROM CATALYST AND'WON-CATALYST EQUIPPED AUTOMOBILES
Chemistry and Physics Laboratory
NERC-RTP
INTRODUCTION
Recent observe)tion of unusually high particulate emissions
from catalyst-equipped automobiles has revived interest in sulfate,
platinum and obher condensed phase substances which may be present
in the exhaust of catalyst-equipped automobiles (1). Since full-
scale production of such cars is in progress, it is extremely
important to assess the impact of such substances on the roadway
air quality. Recent calculations from roadway dispersion models
suggest that automotive sulfate accumulation could cause localized
problems if the emission rate is as high as 0.05 grams/mile (3).
In the past several months abundant data has emerged to show
that sulfate emission rates at least that high can be expected
with either pelleted or monolithic catalysts (4-10). Additionally,
some estimates of non-catalyst automobile emission rates have bet-n
made, this latter with considerable attcndent controversy over
experimental methods. A numbe>- of EPA and industrial investigators,
usino filtration or condensation procedjres, contend that sulfate;
emissions from conventional non-catalyst cars ia minimal (4-8).
Other groups, using a bubbler collection method, feel thesis
substantial sulface emission from non-catalyst cars (9,10). It seems
possible that nt Ic.ist some of this bubbler-found sulfate could be
-------
an arLifact of the chemical reaction with some of the many reactive
compounds present in exhaust (6,7).
'II iu purpose of this paper is to presenb additional
data on thir. topic, to compare the sulfate emissions values
from other groups, and to suggest avenues for future research.
Recognition of a new environmental problem associated with
catalyst-equipped automobiles in the months immediately preceding
thei r production by the millions points as clearly as any event
of recc-rit years to the continuing need for high quality scientific
research into the overall economic, environmental, and energy
conservation consequences of automotive technology.
EXPERiMlONTAL
All automotive testing was carried out on a water-brake
chasc.i-3 dynamometer, qualified and calibrated according to the
Federal Register procedures. Exhaust gas sampling was also
carried out, usinq Constant Volume Sampling equipment and
procedures as prescribed in the 1975 Federal Test Procedure (11),
i.e. a six-bag CVS gas handling system.
-------
Filter samples of condensed phase substances occurring in
the exhaust were obtained, using a 5 meter-long, 0.5 meter diameter
cylindrical stainless steel tunnel, interposed between the dilution
air box and the CVS. Auto exhaust was injected into the center
of this tube through a 5 cm. O.D. downstream facing tube terminating
in the plane of a baffle-plate orifice which restricts the dilution
air flow to a diameter of 25 cm. The tunnel design is similar to
that used by Moran and Manary (12) and by Habibi (13), except for
its greatly reduced length. A diagram of the apparatus is shown
in Figure 1, and photographs of both floor- and over-mounted
installations are shown in Figures 2 and 3. By placing the CVS
system toward the front of the automobile and the floow mounted
tunnel along side, a fairly compact chassis dynamometer test stand
can be achieved. While the bulk of the dilution tunnel system
is ungainly, a reasonably satisfactory particulate handling system
can be achieved without undue cost of impact on auto exhaust gas
analysis facilities.
Under the conditions of the experiments reported herein,
the combined exhaust-dilution air flow rate was the maximum rate
available with the 4 speed CVS, 11.5 m3/min. (406.9 SCFM),
-------
corresponding to a linear flow rate r>f approximately 1 meter/sec.
(3.2 ft/^cc) and a Reynolds number of about 60,000. The baffJe-
orifice plate functions as a mixing device, forcing the gas to
high renter-tube velocities and intense mixing with inimal wall
conUu.t. While no studies of recirculation patterns in the
mixing zone have as yet been made, rather extensive flow and
aerosol concentration profiles have been determined and w.ll and
sampling system loss experiments have been made. Results of
these experiments arc being presented-in detail in other publications
(14); the results to date indicate the flow profile to be unifoim
within - ID'S and the aerosol concentration to be uniform with
- 15%. Aerosol loss experiments were conducted by operating
several 1975 Federal test procedures with a catalyst-equipped
automobile after thorough steam and solvent cleaning of the tunnel.
Following the vehicle experiments, the tunnel was then disassembled
and thoroughly washed with a measured volume of distilled
water. Measurement of sulfate in the washings indicated
less than 1% of the sulfate handled by the tunnel was lost
to the walls. A similar experiment with non-catalyst cars
indicated about 3*i of the organic aerosol handled was recovered
in the methylene chloride wall washings.
-------
Samples of ^articulate matter were obtained through a
rake of four 2.5 cm (1 in.) stainless steel probes at the
isokinctic flow rate of 28 liters/min (1CFM). The probe
centerlines are located on the corners of a 15 cm. diameter square,
the center of which is located on the tunnel centerline. Rerosol
is ducted through tubing and filter holders to 47mm, 0.45 micron
fluorocarbon filters. The sample handling and filtering system
was designed and constructed with smooth continuous walls, long
radius bends, no restrictions and only gradual (20°) increases
in diameter in the filter holder. Experiments with both organic
and sulfate aerosols indicate that insignificant aerosol handling
losses were incurred wjth this apparatus (14).
Automobiles used in these studies included two full size
sedans, one equipped with a 400 CID V-8 engine, air-pump
and monolithic platinum catalyst and the other with a 455 CID
V-8 engine with pelleted catalyst and no air pump. For the
monolithic catalyst car, the oxygen content was approximately
4% in the pre-catalyst cjases and the overall engine air-fuel ratio
was approximately 16/1 (4). For the pelleted-catalyst equipped
car, the exhaust oxygen content was about 2 vol.?.. Both cars
-------
were conditioned and tested according to the provisions of the
1975 Federal Test Procedure, except that the heat-build and
evaporative loss sections of the test were omitted. Some recent
experiments have been carried out with the Highway Fuel Economy
test. Base fuel used for all the tests was the same reference
gasoline being used throughout the EPA contract fuel additive
programs. It has been described previously (4).
Methods of analysis for sulfate (15) , SC>2 (16) , and
individual hydrocarbons (17) have also been described previously.
Sulfate is analyzed by an automated colorimetric procedure involving
barium chloranilate as the colorimetric reagent. SC^ is determined
by an adaptation of the method of West and Gaeke, and detailed
hydrocarbons by an automated gas chromatographic procedure. Bubbler
samples for SO2 determination were obtained using a gas handling
manifold, equipped with solenoid valves which switch the bubbler
vacuum. Valve operation is controlled by relays switched by the
CVS logic. The CVS bag samples and bubblers, in turn, are switched
by a clock-timer sequencing mechanism initiated by the cycle driver
at his station. No special sequencing of filter samples was used
and, consequently, the gas volume sampled was integrated equally
50
-------
over the entire 31 minute active portion of the test. This
resulted in equal weighting of the cold and hot start tests, but
decreased the number of samples handled by a factor of three.
This single sample integrating technique was necessary, however,
to provide sufficient sample for further analysis. All gas samples
were properly sequenced, however, and conform to the Federal
Register procedure, except that an additional 5 second of sampling
time is provided for on each bag to allow for sample residence
time in the tunnel.
With these methods additional studies of sulfate formation
was begun.
RESULTS AND DISCUSSION
Fairly extensive discussion of chemical reactions which
produce sulfuric acid (for it is this species which accounts for
the sulfate) in the exhaust of catalyst-equipped cars and the
thermodynamics of those processes have been recently presented (6,7)
Those discussions have shown that, if thermodynaitdc equilibrium
is achieved, sulfate formation will vary linearly with exhaust SO2
51
-------
concentration (hence fuel sulfur) and 'with the square root of
oxygen concentration (7). Increasing catalyst temperature from
480° C (yoo°F) to 580° C (1080°F) decreased equilibrium sulfate
yield fi.om about 903. to 70% of the fuel sulfur. Further increase
to 600° C (1260° F) decreases equilibriuirrsulfate to 40% of the
fuel sulfur converted (7). Actual conversion data is far below
these figures, hov/ever, probably because of storage of sulfate
as aluminum sulfate on the catalyst surfaces (4-10). Some
evidence has been presented to the effect that some of the sulfate
stored at low temperatures on the catalyst is re-equilibrated at
the higher release temperatures (e.g. at high speed cruise) and
is in part released as SO2 (5). Thus, it appears that an
overall catalyst conversion of fuel sulfur to sulfcite is from
about 55% to about 10% for monolithic catalysts, depending on
driving conditions. For pelleted catalysts the extent of sulfate
storage is much greater and the conversion varies from about 2%
(4,5,6) under 1975 FTP conditions to about 40% (7) under high speed
cruise with air injection. Since most pelleted catalyst models
will not use air pumps, the in-use maximum for the upcoming model
year GM non-air injection products will be about 25°« if operated
long enough to achieve equilibrium (4,6). However, pelleted
catalysts are capable of emitting much of the stored sulfate in
52
-------
the first ten minutes or so of• high speed driving. Thus, apparant
fuel conversions of greater than 100% arc possible under very
real conditions (4,6,7). Because of the great difficulty
in sorting out storage and formation phenomena, the monolithic
catalyst-air pump combination was used as a model for further
studies. However, even in this case, our data have been none too
reproducible.
Table 1 presents a series of 1975 FTP runs with the base fuel
of 0.0124 wt.% sulfur and that same fuel doped to sulfur levels
of 0.025, 0.05, 0.075 and 0.1 wt.% with thiophene. Conditioning
runs on fuel change consisted of a 1975 FTP, 2 hours of 15mph cruise,
a second FTP, followed by the dataaFTP. Data obtained at 0.025% sulfur
was fairly consistent except for an unexplained shift upwards of
about 20% in the sulfate emissions level for two runs and a shift
downward of 15% in one run. In short, our data was nowhere near
as consistent as that of Esso (6)with this catalyst. Table 1
also shows the CO and hydrocarbon emissions levels and indicates
that these were not materially influenced by fuel sulfur level.
Thus, the extent of conversion decreases with increasing fuel
sulfur and this effect does not appear to be especially tied to
53
-------
catalytic activity for hydrocarbon or CO oxidation. Since the
conversion rate is below that predicted by thermodynamic
equilibrium, it it possible that diffusion to active catalyst
sites may control the process.
Table 2 compares the present results with those of Esso
and General Motors on this system. Our data is significantly
lower than that obtained by either GM or Esso. It is not clear
whether the automobile, catalyst, or experimental techniques
account for the differences.
Table 3 presents the results of steady state tests at
idle to 60 mph. Similar Esso and GM results are shown for
comparison. Clearly the lower speed tests yield higher conversions.
A similar result has been obtained by EPA-Ann Arbor (9). Ford-
Battelle experiments indicate conversions of 40% or better at
steady state. This results is contrasted with the results from
a pelleted catalyst-equipped car, shown in Table 4. Again GM
and Esso data are shown for comparison. Clearly the fact of
decreasing catalyst storage with increasing temperature accounts
for these results.
-------
Table 5 presents a summary of data obtained with non-catalyst
cars under FTP and steady state conditions. A total of sevel
vehicles were investigated, ranging from '72, "73, and '74 model
year conventional vehicles. A '74 rotary engine vehicle and light
duty dicsel powered car have also redently been tested. None
of these emitted detectable water soluble sulfate. X-ray analysis
of the diesel particulate samples indicated substantial amounts
of sulfur present, however, about 4 wt.% of the particulate. The
form of this material is currently under investigation. Both
organically bound sulfur and S02 absorbed strongly on soot may
account for the sulfur found. General Motors has reported very
low sulfate emissions .103 grams/mile for both rotary and diesel
powered cars.
Table 6 presents a comparison of hydrocarbon distributions
found with the two catalyst systems under FTP and Fuel Economy
cycles. The individual hydrocarbons are similar for the two
catalysts for FTP conditions, surprisingly there were no substantial
shift in the hydrocarbon distribution for the highway Fuel
Economy test. Unfortunately, the pelleted catalyst car was
not available for these runs. In summary, the milder, higher
55
-------
speed Highway Fuel Economy test yields a surprisingly high
hydrocarbon output, mainly unreactive hydrocarbons, however.
CONCLUSIONS
J% In those cruise portions of the passenger car
operating envelop most likely to influence atmospheric
sulfate on an isolated roadway, sulfate emissions from various
catalyst cars appear to be nearly the same, i.e., about 0.05 gram/
mile. Apparently, it is the isolated roadway which is likely
to be location of any automotive sulfates problem. Variance
among experimental groups is great, however.
2. Beaded catalysts appear to give substantially lower emissions
rates in urban driving patterns than do monolithic catalysts.
However, sulfate emissions from passenger cars are not likely to
influence the urban sulfates burden.
3. Fuel sulfur level influences catalyst sulfates emissions,
but not in a linear fashion. Lower S0_ exhausts are somewhat more
efficiently converted to sulfate than are exhausts from higher
sulfur fuels.
56
-------
4. . Hydrocarbon emissions patterns are similar for the
various catalysts under a variety of driving patterns, including
both urban and highway driving cycles.
FUTURE WORK
Since shortages of petroleum-based fuels seem inevitable
for the foreseeable future, both the automotive and energy industries
must certainly seriously consider and eventually adopt new
production technologies to remain healthy. It will fall to
research groups to thoroughly investigate the environmental
and energy conservation consequences of new power plants, new
fuels, or of substantial modifications of present fuel, power
plants, and control systems.
For the present, study of the sulfate emissions from
various catalyst systems under both FTP and steady-state
conditions is underway. Parametric studies of sulfate forma-
tion under various catalyst operating conditions of light duty
diesel, stratified charge, and rotary engine emissions, and
on sulfate trap feasibility are cither planned for initiation
within the next few months or have recently begun under EPA
57
-------
sponsorship by both the Office of Research and Development and
the Office of Air and Water programs. Differences in test
results and the wide scatter thus far reported must be
reconciled. More work on methods of test is needed and planned.
Further studies of the detailed emissions patterns of any
significant pollutants emitted from advanced power plants or
fuels are planned for the next few years.
58
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REFERENCES
1. J.6. Gentel and 0. Manary, Final Report on EPA contract
number 68-02-0569 (in preparation).
3. L. Niemeryer, "Estimated Changes in Human Exposure to Sulfates
Attributable to Equipping Light Duty Motor Vehicles with Oxidation
Catalysts", Paper presented at NIEHS Symposium "Health Consequences
of Environmental Controls", Durham, N.C. April 18, 1974.
4. R.L. Bradow, "Overview of Non-Regulated Emissions from
Mobile Sources", NIEHS Sumposium, op.cit.
5. M. Beltzer, R. Campion, and W.L. Petersen, "Measurement of
Vehicle Particulate Emissions", SAE paper 740286, February 25, 1974,
Detroit, MI.
6. General Motors Corporation, "Response to March 8, 1974
Federal Register Regarding Automotive Sulfate Emissions: A
Status Report", May 7, 1974, Detroit, MI.
7. (a) Ford Motor Company, "Ford Response to EPA Request 'for
Data on Automotive Sulfate Emissions", May 7, 1974, Dearborn, MI.
59
-------
7. (b) W.R. Pierson, R.H. Hammerle, and J.T. Kummer, "Sulfuric
Acid Aerosol Emissions from Catalyst-Equipped Engines", SAE
paper no. 740287, February 25, 1974, Detr6*i^;' MI.
8. K.L. Kipp, and D.R. Rhodes, "A Method.-for Determining H2S04
in Automobile Exhaust", NIEHS Symposium, op. cit.
9. D.M. Teague, "804 Emissions from Oxidation and Non-Oxidation
Catalyst-Equipped Vehicles", NIEHS Symposium, op. cit.
10. J. Somers, "Automotive Sulfate Emission Data", NIEHS
Symposium, op. cit.
11. Federal Register, Vol. 35, Nov.1972.
12. J.B. Moran, and 0. Manary, "Effect of Fuel Additives on the
Chemical and Physical Characteristics of Particulate Emissions
in Automotive Exhaust", EPA Report No.-R2-72-066, December, 1972,
Washington, D.C.
13. K. Habibi, Env. Sci. and Technol., 4. 239 (1970).
14. J. Sigsby and R.Jj. Bradow, "Auto Exhaust Particulate Measurement
Method for CVS-diluted Exhaust", NIEHS Symposium, op. cit.
60
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15. S. Tejada, "Determination of Soluble Sulfate from CVS-diluted
Auto Exhaust: An Automated Method , NIEHS Symposium, op. cit.
16. K. Klosterman and R.L. Bradow, "Direct Determination of Sulfur
Dioxide from CVS-diluted Auto Exhaust", NIEHS Symposium, op. cit.
61
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O>
NO
TAELE 1
Sulfate Results - Monolithic Platinum Catalyst
1975 FTP
grams/mile
Fuel S,
ppm
124
250
500
750
1000
No. of
runs
10
11
9
10
10
HC
0.254
0.215
0.187
0.211
0.258
CO
4.34
5.33
5.28
4.90
4.32
NOX
2.55
2.60
2.49
2.63
2.80
Particulates
0.0310
0.0400
0.0574
0.'0563
0.0828
S04
0.00962
0.0139
0.0187
0.0225
0.0290
Fuel S
as SO4
0.0924
0.191
0.378
0.568
0.757
% S
converted
10.4
7.3
4.9
4.0
3.8
-------
TABLE 2
Comparison of Cold Start FTP Sulfate Emissions Data
Monolithic Catalysts
Fuel S, ppm
40
124
250
200
300
320
500
650
670
750
1000
Experimenter
ESSO
EPA/ORD
EPA/ORD
GM
GM
ESSO
EPA/ORD
GM
ESSO
EPA/ORD
EPA/ORD
Particulate
g/mile
0.036
0.031
0.040
—
—
0.183
0.057
—
0.249
0.056
0.083
S04
g/mile
0.014
0.0096
0.014
0.028
0.019
0.061
0.019
0.143
0.134
0.022
0.029
Conversion of
S to SO/i, %
35
10.4
7.3
13.3
7.8
23
4.9
27
23
4.0
3.8
63
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TABLE 3
Steady State Sulfatc Emissions
0.05^5 - Monolithic Catalyst
Run Condition Particulate §0^
Idle 0.050 0.029
15 mph 0.068 0.037
30 mph 0.043 0.025
45 mph 0.048 0.021
60 mph 0.033 0.019
HWFET 0.072 0.031
Esso Data 0.067% S fuel
40 mph 0.210 0.090
GM Data 0.065% s fuel .
30 mph 0.134
40 mph 0.164
60 mph 0.105
-------
TABLE 4
Steady State Sulfate Emissions
0.1% S fuel - pelleted catalyst
Graihs/Mile
Run condition Particulate 804
Idle 0.0022 0.0005
15 mph 0.027 0.013
45 mph 0.111 0.069
60 mph 0.045 0.020
60 mph 0.186 0.121
65
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TABLE 5
Particulate Emissions Non-Catalyst Cars
1975 FTP
0.1% Sulfur Fvcl
Car
Particula-te
g/mile
S04
g/mile
1974 Chevelle
1973 Chevelle
1972 Impala
1971 Ford
(Catalyst Car
Without Catalyst)
0.0323
0.0717
0.0121
0.0232
N.D.
N.D.
0.0008
0.00112
N.D. - None Detected
66
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Table 6
Individual Hydrocarbon Analysis
Pelleted Catalyst-LA-4
no air pump-Bag 1
Hydrocarbons, ppmc
Methane
Ethylene
Acetylene
Butane
Isopentane
N-pentane
Isooctane
Benzene
Toluene
Monolithic Catalyst LA-4
Bag 1
Monolithic Catalyst
Highway Fuel Economy Test
81
31
28
% of total (ppmc/ppmc total)
7.5
8.8
1.7
8.2
5.2
3.7
6.7
5.1
13.4
17.2
9.0
3.5
6.5
6.1
5.0
6.4
3.3
9.1
19.6
8.5
2.1
7.5
8.0
7.0
5.2
6.5
9.1
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Appendix B2.3
Status Report
ROAP 21BCE
Task 02
Characterize Particulate Emissions - Prototype
Catalyst Cars
Concept:
The sulfate and abraded catalyst particle emissions have not been
systematically measured from a variety of catalysts under consistent
conditions. A contract program was instituted to study a w'de variety
of catalyst compositions (15 in all) representative of current and
future production types. Particulate composition and emission rate will
be determined with three different gasolines under FTP, high and
moderate speed steady states, and at idle. Vibration tests will be
carried out in later stages of the program to study relative abrasion
dlasses of catalyst material and potential noble metal emissions. It
is expected that this program will suggest the feasibility of emissions
control by modification of catalyst composition.
Status:
The contract has been let to Exxon Research and Engineering who have
now completed non-catalyst gasoline testing. Catalyst testing with the
first five catalysts is in progress and completed data on the first one
or two is expected by this fall. Completion of the first eight catalyst
determinations including all production catalysts for 75 model year cars
is expected by November 15.
68
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THE CHARACTERIZATION OF FARTICULATE
EMISSIONS FROM PROTOTYPE CATALYST VEHICLES
MONTHLY PROGRESS REPORT NO. 1
FOR PERIOD JUNE 1 TO JUNE 30, 1974
PREPARED BY MORTON BELTZER
'CONTRACT NO. 68-02-1279
Prepared by
Exxon Products Research Division
Exxon Research and Engineering Company
Linden, New Jersey
for
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
July 1974
69
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Section I
Purpose and Scope of Work.
Exxon Research-and Engineering Company, under contract with the
Environmental Protection Agency, is engaged in a research program designed
to measure and characterize the exhaust particulate emissions from a
variety of catalyst systems, both commercial and prototype, that are can-
didates for use in automotive emissions control. Due to such mechanisms
as mechanical and thermal shock, and possible chemical conversion of
catalyst material to a mobile condensed material, particulate emissions
from catalyst equipped vehicles could differ markedly from that of con-
ventional vehicles. Furthermore, catalytic conversion of gaseous exhaust
components to particulate exhaust matter introduces exhaust components
that are not now present in the exhaust from conventional vehicles. A
case in point is the catalytic oxidation of exhaust sulfur dioxide to the
trioxide which is then emitted as sulfate aerosol.
In order to separate vehicle and catalyst effects ^n total
particulate emissions, it will be necessary to measure and characterize
particulate emissions from the vehicles in their conventional configura-
tion before they are equipped with catalysts.
Eight catalyst systems (three monolithic oxidation catalysts,
two beaded oxidation catalysts, and three reduction catalysts will be
tested with three fuels.
The three fuels that will be tested are:
(1) an EPA furnished reference fuel.
(2) the EPA fuel treated with an additive package consisting
of thiophene and t-butyl sulfide to a fuel sulfur level
of 0.1 wt.% sulfur, and TEL as motor mix to a level of
0.05 gms Pb/gal.
(3) A high aromatic content fuel similarly treated.
Both treated fuels shall also contain an additive package com-
prised of Lubrizol 596 (0.27 g/gal) and Paradyne 502 (0.45 g/gal). The
former functions as detergent, corrosion inhibitor, anti-stall, and anti-
icing agent and contains about 2.25 - 2.75 wt.% nitrogen. Paradyne 502
contains 0.75 wt,% nitrogen and functions as a detergent, anti-rust agent,
and deposit modifier.
This fuel selection should allow exhaust particulate character-
ization as follows:
70
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(1) level of composition of exhaust particulate resulting from the
use of an-additive-free fuel in conventional and catalyst
equipped vehicles.
(2) effect of fuel additives on particulate emissions from
conventional and catalyst equipped vehicles.
(3) effect of a high aromatic fuel containing additives on
particulate emissions from conventional and catalyst
equipped vehicles.
Due to its introductory nature and the range of areas covered,
the following sections of this Monthly Technical Progress Narrative are
somewhat detailed. Future monthly reports will be more brief and informal
as desired by EPA.
Section II
A. Work During Period of June 1-30. 1974
The first month of this contract effort was concentrated on
alterations and additions to the particulate sampling system, and an
evaluation of the analytical scheme for metal particulate and organic
exhaust particulate matter. A dry run sequence was also carried out
to establish a working procedure and to determine where problems could
occur. Each of these will be briefly discussed below. In addition four
catalyst systems have been received to date. These systems are being
adapted to the vehicle so that they can be readily interchanged between
the mileage accumulation vehicle and the test vehicle. Both vehicles
have been broken in at this point by a combination of about 2000 miles
of commuter type driving, and 2000 miles on the Mileage Accumulation
Dynamometers (MADS) using the Federal Mileage Accumulation Schedule.
A.I. Revamping and Testing of Sampling System
Probes sampling at a 15 CFM rate instead of the 10 CFM rate
were installed in order to obtain larger samples of particulate for ana-
lysis. In addition, an Anderson Impactor was reactivated to obtain
particle size distributions. It was necessary to check out the internal
agreement between the two probes, and between the Impactor and the two
probes.
A series of runs with a catalyst equipped vehicle was carried out
using these new probes. Agreement between the two sampling probes was
excellent, both for total particulate, and for sulfuric acid emissions.
Several of the test results with an oxidation catalyst equipped vehicle
are shown below.
71
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CORRESPONDENCE BETWEEN 15 CFM
SAMPLING PROBES
Emission Rate, gins/km
Total Participate,
Filter # Filter #
Fuel
Test Sulfur
60 mph, 1 hr 0.046 0.101 0.098 0.041 0.039
" » " 0.098 0.098 0.044 0.042
» " " 0.106 0.104 0.045 0.045
" " " 0.108 0.106 0.042 0.042
11 " " 0.111 0.113 0.046 0.051
A.2. Agreement between Impactor and 15 CFM Filters
Several runs were carried out to check the particulate emission
rate correspondence between the Anderson Impactor and the 15 CFM sampling
probes. The impactor probe samples at 1.5 CFM rate. The impactor as
adapted to our needs contains one mil thick stainless steel shim stock
collection plates, placed on the particulate collection plates normally
used in this impactor.
The shim stock was washed progressively in cyclohexane-toluene
mixture, alcohol, acetone, and then cleaned ultrasonically in a detergent-
containing solution of water. Extensive testing indicated that weight
changes measured on the shim stocks as a result of being used during a
run would be a reliable measure of the weight of material of a given
particle size range.
Initial tests used all seven impactor stages and the absolute
filter. This filter is from the same batch as the 15 CFM filters (Gelman
Type A glass fiber filter). A PTX oxidation catalyst equipped vehicle
was run at 40 mph for one hour and 60 mph for two hours on a 0.046%
sulfur fuel. The results for each run are shown below .
-------
COMPARISON OF IMPACTOR AND 15 CFM SAMPLING PROBES
40 MPH. 1 HR. CRUISE
(A) Total Particulate
gms/km
Anderson 15 CFM Filters
Impact or gins/km #1 #2
Sum of shims (1 to 7) 0.009
Absolute filter 0.071
Shims'+ filter 0.080 0.087 0.087
(B) Sulfuric Acid Emissions
System ems/km
Absolute filter 0.034
#1, 15 CFM filter 0.034
#2, 15 CFM filter 0.033
60 MPH. 1 HR, CRUISE
(A) Total Particulate
gms/km
Anderson 15 CFM Filters
Impactor ems/km #1 #2
Sum of shims (1 to 7) 0.004
Absolute filter 0.124
Shims + filter 0.128 0.130 0.131
(B) Sulfuric Acid Emissions
System ems/km
Absolute filter 0.060
#1, 15 CFM filter 0.055
#2, 15 CFM filter 0.053
73
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The agreement between the impactor and the large filters with
respect to total particulate and sulfuric acid emission rates was within
5%. Over 90% of the particulate and all of the sulfate was less than one
micron in diameter. The participates above one micron were log normally
distributed as shown in Figure I.
It was found that the particulate matter on the shim stocks
was difficult to remove. Accordingly, new shim stocks will be used for
each run.
Preliminary examination of the particulate matter on the shim
stock by X-ray energy non-dispersive analysis in the scanning electron
microscope indicated that this is composed of silicon, sulfur, possibly
aluminum which could be masked by the silicon, and possibly platinum.
These results are to be regarded as strictly tentative at this stage.
A.3. Exhaust Splitter
The exhaust particulate sampler was originally designed to
sample particulate at 32°C for the 1972 or 1975 Federal Test Procedure,
with the minimum dilution rate compatible with that goal. We have found
that at a total flow rate of 450 CFM (exhaust + dilution air), tempera-
ture control is maintained operating with catalyst-equipped and with
conventional vehicles. However, in order to maintain temperature control
for a 70 mph cruise test run with a catalyst equipped vehicle, it is
necessary to dilute the exhaust by venting an accurately known amount of
raw exhaust. To this end, we have designed and tested two types of exhaust
splitters.
The initial approach was to split the raw exhaust so that only
a portion is injected into the flow development funnel. Linear velocity
is maintained in each leg of the splitter. Velocities were to be measured
using Pitot tubes and equalized by adjusting the pressure drop in the vent
leg using a variable speed pump. However, the pressure drops were small
and subject to rapid oscillations, making equalization extremely difficult.
Attempts to damp the oscillations were not successful.
An alternative approach utilized hot wire anemometers with the
same splitting principle and method of flow balance. This method was
shown to work with ambient air but has not been successful to date with
raw exhaust. Several anenometer probes have failed during actual vehicle
runs due to corrosion of the sensing wires. At present, we do not plan
to split the raw exhaust for the 70 mph cruises until we have a workable
splitter. Efforts to develop the splitter will continue. This will be
discussed in Section III of this letter.
B. Analytical Scheme
Chemical analysis in conjunction with measurements of total
particulate emission rates and particle size distributions is required to
characterize exhaust particulate emissions. We have devised a scheme for
-------
10.0
1.0
0.1
FIGURE I
OXIDATION CATALYST
EQUIPPED VEHICLE
0.0467. S FUEL
• • 64.4 km/hr cruise, one hour, cold start
O" 96.5 km/hr cruise, one hour, hot start
I L
t
I I
50 60 70 80
90 95 98 99 99.5 99.9
99.99
CUMULATIVE % MASS < PARTICLE DIAMETER
75
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quantitative analysis for lead, -aluminum, calcium, platinum and other
trace elements, nitrogen, and carbon.
Analytical techniques were developed to measure Ca, Al, Pb, Ni, Fe,
Cu, Cr, Zn, Pt, and C in particulates collected from automotive exhaust.
Emission spectroscopy was used to determine Ca, Al, Ph, Ni, Fe, Cu, Cr, Zn
and Pt collected on an organic filter. X-ray fluorescence was also used
for Pt, and a semi-micro combustion technique for C.
B.2. Emission Spectroscopy (Cat Al, Pb. Ni. Fe. Cu, Cr, Zn. Pt
In this procedure, the above metals are collected on a
44 cm2 Millipore filter. The entire filter is ashed with Mg (N03>2 as
a carrier, the ash blended with graphite containing cobalt and lithium,
and the concentration of each of the metals determined by comparing the
quantometer reading of the sample with that of standards. The concen-
tration range covered is equivalent to 0.1 to 4/^giu/cm^ of sample, cor-
responding to an emission rate range for the 1975 FTP of 2.2 X 10~^ to
0.87 X 10~3 g/km. No interferences .were noted, except for I t by Cr.
The results of metal emissions from a test run with an oxida-
tion catalyst equipped vehicle are given below. The vehicle was operated
at 60 mph for 2 hours. The metals listed below represented 0.2% of the
total particulate emitted during that test run.
EXHAUST PARTICULATE METAL EMISSIONS
Emission Rate
Metal (ems/km)
Ca 0.000039
Pb 0.000071
Cu 0.000017
Al 0.000017
Zn 0.000099
Cr 0.000016
Ni 0.000008
B.2. X-Ray Fluorescence (Pt)
The platinum analysis was performed by exposing circular sections
of the glass fiber particulate filter in the X-ray beam of a Phillips
Number 1220 X-ray spectrometer. The minimum detectable level of platinum
is about O.SS^gms/cm corresponding to about 2.6 X 10"5 gms/km for a
1975 FTP.
A variation of this technique was attempted in order to increase
the sensitivity for platinum. A Millipore filter was used instead of a
glass fiber filter. The entire filter was ashed with Mg (NOo^ the ash
blended with boric acid, pressed into a pellet, and the Pt fluorescence
76
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- 8 -
of the blend measured. Despite 'the fact that the sample was concentrated
prior to analysis, no increase in sensitivity for Ft was obtained.
B.3. Carbon Analysis
Analysis of glass fiber particulate filters from test runs has
shown that the semi micro combustion technique for carbon is not suffi-
ciently sensitive for organics from oxidation catalyst equipped vehicles.
Type A Gelman glass fiber filters were used. The results show that the
organic particulate from a catalyst equipped vehicle is so low that it
cannot be distinguished from a blank filter.
ANALYSIS OF ORGANIC PARTICULATE
ON TYPE A GELMAN GLASS FIBER FILTER
ems/km
No. of Fuel Total As
Tests Catalyst JLJL. Test Particulate Carbon
2 PTX 0.004 75 FTP 0.032 0.004
4 Pelletized 0.004 40 cruise mph 0.004 NIL
3 PTX 0.14 " " 0.263 NIL
B.4. Analytical Techniques for Sulfate
In our previous work we have used a modification of the standard
gravimetric procedure for sulfate, ASTM Procedure D1099. Recently we have
developed a titrimetric method for sulfate. The leach solution is filtered
to remove insoluble material and passed through an ion-exchange column to
remove interfering cations. The resulting solution is buffered with Methene-
amine to a pHj^3 and titrated with 63(0104)2 using Sulfanazo III as an
indicator.o This method which has been found to be sensitive to levels of
2/4gms 504 /cm of filter will be routinely used for sulfate determinations.
C. Preliminary Run
A preliminary run not involving a contract test vehicle, was
carried out to evaluate the particulate measurement and analyses procedure
over the test modes stipulated in the contract.
(1) 1975 FTP
(2) one hour idle
(3) one hour 40 mph cruise
(4) two hour 70 mph cruise
(5) overnight cool-down
(6) 1975 FTP
No major obstacles were encountered in the above run sequence.
The 70 mph, 2 hour cruise will be carried out using the entire auto exhaust
until the exhaust splitter is incorporated in the program. Until that time,
77
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temperatures greater than 32°C will be experienced during the 70 mph
cruise mode.
Section III Current Problems
As discussed in Section A.3. of this'le'tter, the exhaust
splitter has not functioned workably under actual run conditions. Corro-
sion of the stainless steel anenometer sensing wires upon exposure to hot
(>150°C) exhaust containing I^SO^ aerosol has been observed. We should
shortly be receiving anenometer probes with platinum sensing wires.
While more fragile physically (since a thinner Pt wire has to be used
to give the same resistance as stainless steel), the platinum anenometers
should be more chemically resistant to auto exhaust. Anenometer probes
containing tungsten wire will also be tested.
Section IV Work to be Performed July 1-31. 1974
Base case runs on both vehicles on the three test fuels will
be carried out. Gaseous and particulate emissions will be measured, and
chemical analysis of the particulate matter will be performed.
Thermal conditioning of the catalysts will be initiated. When
the additional catalysts are received they will be mounted such that they
can be rapidly interchanged between the mileage accumulation and the test
vehicle.
78
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THE CHARACTERIZATION OF PARTICULATE
EMISSIONS FROM PROTOTYPE CATALYST VEHICLES
MONTHLY PROGRESS REPORT NO. 2
FOR PERIOD JULY 1 TO JULY 31, 1974
PREPARED BY MORTON BELTZER
CONTRACT NO. 68-02-1279
9 AUGUST, 1974
Prepared by
Exxon Products Research Division
Exxon Research and Engineering Company
Linden, New Jersey
for
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
79.
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Section I
Purpose and Scope of Work
Exxon Research and Engineering Company, under contract with the
Environmental Protection Agency, is engaged in a..research program designed
to measure and characterize the exhaust particulate emissions from a
variety of catalyst systems, both commercial and prototype, that are can-
didates for use in automotive emissions control. Due to such mechanisms
as mechanical and thermal shock, and possible chemical conversion of
catalyst material to a mobile condensed material, particulate emissions
from catalyst equipped vehicles could differ markedly from that of con-
ventional vehicles. Furthermore, catalytic conversion of gaseous exhaust
components to particulate exhaust matter introduces exhaust components
that are not now present in the exhaust from conventional vehicles. A
case in point is the catalytic oxidation of exhaust sulfur dioxide to the
trioxide which is then emitted as sulfate aerosol.
t
In order to separate vehicle and catalyst effects on total
particulate emissions, it will be necessary to measure and characterize
particulate emissions from the vehicles in their conventional configura-
tion before they are equipped with catalysts.
Eight catalyst systems (three monolithic oxidation catalysts,
two beaded oxidation catalysts, and three reduction catalysts will be
tested with three fuels.
The three fuels that will be tested are:
(1) an EPA furnished reference fuel.
(2) the EPA fuel treated with an additive package consisting
of thiophene and t-butyl sulfide to a fuel sulfur level
of 0.1 wt.% sulfur, and TEL as motor mix to a level of
0.05 gms Pb/gal.
(3) a high aromatic content fuel similarly treated.
Both treated fuels shall also contain an additive package com-
prised of Lubrizol 596 (0.27 g/gal) and Paradyne 502 (0.45 g/gal). The
former functions as detergent, corrosion inhibitor, anti-stall, and anti-
icing agent and contains about 2.25 - 2.75 wt.% nitrogen. Paradyne 502
contains 0.75 wt.% nitrogen and functions as a detergent, anti-rust agent,
and deposit modifier.
This fuel selection should allow exhaust particulate character-
ization as follows:
80
-------
(1) level of composition of exhaust particulate resulting
from the use of an additive-free fuel in conventional and
and catalyst equipped vehicles.
(2) effect of fuel additives on particulate emissions from
conventional and catalyst equipped vehicles.
(3) effect of a high aromatic fuel containing additives on
particulate emissions from conventional and catalyst
equipped vehicles.
Section II
A. Work During Period of July 1-31, 1974
A.I. Base Case Runs on the Test and Mileage
Accumulation Vehicle
Each vehicle was put through the following conditioning and
test sequence on each of the three test fuels:
(1) 321.8 km (200 mile) conditioning using the Federal
Durability Cycle followed by a 16 hour soak.
(2) 1975 FTP.
(3) one hour idle.
(4) one hour, 64.36 km (40 mile) cruise.
(5) two hour, 112.63 km (70 mile) cruise.
(6) overnight soak.
(7) 1975 FTP.
In all, thirty runs were carried out. Gaseous emissions were
measured and particulate samples were obtained in each run. Except for
trace metals, particulate analysis has not been started. Analysis will
be carried out in August.
The entire exhaust was injected into the dilution tunnel during
the 112.63 km (70mph) cruises so that temperature at the particulate fil-
ter in these runs exceeded 32°C.
A.2. Catalysts
To date, four catalysts have been received. These systems
81
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have been mounted for interchangeability between the mileage accumula-
tion vehicle and the test vehicle. One catalyst has been conditioned
and thermally stressed for 2896.2 km (1800 miles) on the Federal Dura-
bility Cycle on an 8 hour on, 8 hour off basis. Conditioning of the
other catalysts will be initiated.
The acquisition of the remaining catalysts, with the exception
of the Engelhard reduction catalyst, which is unavailable is currently
being negotiated.
82
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THE CHARACTERIZATION OF PARTICULAR
EMISSIONS FROM PROTOTYPE CATALYST VEHICLES
MONTHLY PROGRESS REPORT NO. 3
FOR PERIOD AUGUST 1 TO AUGUST 31, 1974
PREPARED BY MORTON BELTZER
CONTRACT NO. 68-02-1279
10 SEPTEMBER, 1974
Prepared by
Exxon Products Research Division
Exxon Research and Engineering Company
Linden, New Jersey
for
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
83
-------
Section I
Purpose and Scope of Work
Exxon Research and Engineering Company, under contract with the
Environmental Protection Agency, is engaged in a research program designed
to measure and characterize the exhaust particulate emissions from a
variety of catalyst systems, both commercial and prototype, that are can-
didates for use in automotive emissions control. Due to such mechanisms
as mechanical and thermal shock, and possible chemical conversion of
catalyst material to a mobile condensed material, particulate emissions
from catalyst equipped vehicles could differ markedly from that of con-
ventional vehicles. Furthermore, catalytic conversion of gaseous exhaust
components to particulate exhaust matter introduces exhaust components
that are not now present in the exhaust from conventional vehicles. A
case in point is the catalytic oxidation of exhaust sulfur dioxide to the
trioxide which is then emitted as sulfate aerosol.
t In order to separate vehicle and catalyst effects on total
particulate emissions, it will be necessary to measure and characterize
particulate emissions from the vehicles in their conventional configura-
tion before they are equipped with catalysts.
Eight catalyst systems (three monolithic oxidation catalysts,
two beaded oxidation catalysts, and three reduction catalysts will be
tested with three fuels.
The three fuels that will be tested are:
(1) an EPA furnished reference fuel.
(2) the EPA fuel treated with an additive package consisting
of thiophene and t-butyl sulfide to a fuel sulfur level
of 0.1 wt.% sulfur, and TEL as motor mix to a level of
0.05 gms Pb/gal.
(3) a high aromatic content fuel similarly treated.
Both treated fuels shall also contain an additive package com-
prised of Lubrizol 596 (0.27 g/gal) and Paradyne 502 (0.45 g/gal). The
former functions as detergent, corrosion inhibitor, anti-stall, and anti-
icing agent and contains about 2.25 - 2.75 wt.% nitrogen. Paradyne 502
contains 0.75 wt.% nitrogen and functions as a detergent, anti-rust agent,
and deposit modifier.
This fuel selection should allow exhaust particulate character-
ization as follows:
84
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(1) level and composition of exhaust particulate resulting
from the use* of an additive-free fuel in conventional and
catalyst equipped vehicles.
(2) effect of fuel additives on particulate emissions from
conventional and catalyst equipped vehicles.
(3) effect of a high aromatic fuel containing additives on
particulate emissions from conventional and catalyst
equipped vehicles.
Section II
A. Preliminary Results of Base Case Runs, July 1-31, 1974
Thirty runs were carried out in July in which the particulate
and gaseous emissions of the test vehicle and the mileage accumulation
vehicle operating on the three fuels were measured. There were inter-
vehicle differences with respect to -both types of emissions as shown
below in Tables I and II.
Table I
Comparison of Total Particulate Emissions
Base Case Runs, Vehicles 116 and 115
. *
Total Particulate. gms/km
Vehicle Test Fuel 1 Fuel 2 Fuel 3
**
116 FTP 0.043 0.026 0.026
" Idle [0.197] [0.373] [0.209]
" 40 mph 0.006 0.007 0.005
" 70 mph 0.009 0.012 0.008
115 FTP** 0.017 0.022 0.014
" Idle [0.070] 0.094 0.115
" 40 mph 0.002 0.004 0.005
" 70 mph 0.003 0.005 0.004
Idle emissions, bracketed numbers are in (gms/hr).
FTP values are averaged values of initial and final
tests on each fuel.
85
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Unlike the earlier work, the instrument was calibrated differ-
ently by using a S02 in N2 calibration gas. Based on recent work at
Exxon and corroborated by the instrument manufacturer, it was shown that
SC-2 in air (the diluted exhaust samples are predominantly air) gives a
much lower response. The data shown in Appendix II have been corrected
using a factor of 1.4 based on recent calibration tests using S02 in air
and S02 in N2«
In about one-fourth of the base case runs in which S02 was
measured, agreement between the experimental S02 emission rate and the
theoretical based on fuel consumption was within 10%. In general, the
discrepancies between experimental and expected S02 emission rates were
about ± 25%. We are planning to investigate the causes for these dis-
crepancies .
A.3. Sulfate Emission Rates
Sulfuric acid emission rates are shown in Appendix III. The
sulfate levels while low are somewhat higher than what was obtained in
earlier results from tests on conventional vehxcles carried out in our
laboratory. The sulfate emission rate appears to be independent of fuel
sulfur content. For example compare Federal Cycles (numbers 1 and 5 with
6 and 10). The average sulfate emissions for the first pair of 75 FTF's
is 0.0022 gms/km, while it is 0.0024 gms/km for the latter although the
sulfur content of the fuel used in runs 6 and 10 was six times greater
than that used in runs 1 and 5. The percent conversions calculated on
the basis of sulfate measured to fuel sulfur consumed consequently are
higher the lower the fuel sulfur content. These results indicate that
there may be some background level of sulfate which should be backed out
of emission rates obtained in each run although it is not clear at this
stage what the reason is. As will be shown in Section II, the sulfate
emissions of the test vehicle equipped with a catalyst are generally
higher than what was obtained in the absence of a catalyst with the ve-
hicle operating on a higher sulfur fuel, and depends markedly on fuel
sulfur content.
A.4. Metal Emission Rates
Metal emission rates were obtained in each vehicle test for Ca,
Al, Zn, Cr, Fe, Cu, Ni, and Pb. The detailed metals emission data are
shown in Appendix IV. The emitted metals constituted a small fraction
of the total particulate. The lowest total particulate emission rate
obtained was during a 40 mph cruise on vehicle 115 operating on the EPA
reference fuel 0.002 gms/km (Appendix I, Test No. 18). Even in this case,
the metals constituted at most 9% of the total particulate.
x
Table III below shows Ca and Al emission rates for each vehicle
operating on each of the test fuels.
86
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TABLE. Ill)
oo
Ca and Al Emission Rates, (gins/km)
Vehicle Operating on Indicated Fuels
Vehicle
116
it
it
it
115
ii
ii
it
Values
**
Test
75 FTP**
Idle
40
70
75 FTP
Idle
40
70
for the Idle
Fuel 1
Ca
0.00020
[<0. 00008]
0.00003
0.00011
0.00005
0.00004
0.00001
<6 x 10-6
Cruises, brackets
Al
<0. 00005
[<0. 00008]
< 0.00001
6 x 10-6
0.00006
Fuel
Ca
0.00015
[0.0022]
0.00004
0.00001
0.00004
<0. 00004 [<0.0004]
<6 x 10-6
<6 x 10-6
are in [gms/hr]
0.00002
0.00001
•
2
Al
0.00013
[0.0015]
0.00002
<0. 00001
=0.00003*"
[<0.0004]
<6 x 10-6
<0. 00001
Ca
0.00004
[0.0012]
0.00002
0.00001
0.00004
[0.0004]
0.00001
0.00002
Fuel 3
Al
=0.00003*
[<0.0004]
<6 x 10-6
<0. 00001
•\-0.00003
[<0.0004]
<6 x ID"6
0.00002
Averaged values of initial and final 75 FTP runs for vehicle-fuel combination.
= Average of two values, one of which is below the detection limit.
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A.5. Carbon Content of Exhaust Partlculate
It was previously noted (Monthly Progress Report No. 1, Section
B.3) that the semi-microcombustion technique for carbon is not suffi-
ciently sensitive for organics from oxidation catalyst equipped vehicles.
The Type A Gelman glass fiber filters used in this program although osten-
sibly free of organic binder gave high carbon blanks, equivalent to about
an emission rate of about 0.014 gms/km for the 1975 FTP, 0.004 gm/km for
40 mph, 1 hour cruise and 0.001 gm/km for the 70 mph, 2 hour cruise. In
many of the base case runs, the blank carbon correction exceeds the mea-
sured carbon content of the particulate loaded filters. In other cases,
the blank carbon correction exceeds the total particulate emission rate.
In still other cases, the measured carbon content corrected for the blank
exceeds the total particulate.
Carbon analysis was performed on the first thirty base case
runs. In 14 cases, the blank carbon correction exceeded the measured
carbon values. Table IV below shows those runs in which the measured
carbon values exceeded the blank. It can be seen that these cases in-
clude those in which the organic particulate (as carbon) exceeds the
total particulate.
Table IV
Organic Particulate Emissions
Base Case Runs
Emission Rate
gms/km
Total
Run No. Run Type Particulate As Carbon
1 75 FTP 0.050 0.053
2 Idle (1) [0.197] [0.846]
4 70 (2) 0.007 0.017
9 70 (2) 0.012 0.0001
14 70 (2) 0.008 0.0001
In Run No. 1 above, the carbon level is comparable to the total
particulate level. It is possible that the relatively high particulate
loading obtained in this run is due to the high level of organic particulate.
In general, the semi-microcombustion technique for particulate
apparently is only reliable when the organic particulate loadings on the
filters are very high. Since a major portion of the program to be carried
out involves oxidation catalyst systems which further reduce organic par-
ticulate levels, the semi-microcombustion technique appears to be unsuit-
able. Similar considerations probably apply to those tests in which a NOX
reduction catalyst would be used, since the organic emission output of the
program vehicles operating in the conventional mode is quite low.
88
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Section III
A. Work During Period of August 1-31. 1974
A.I. Runs with Catalyst Equipped Test Vehicle
Runs with the test vehicle equipped with catalysts were started.
The first catalyst tested was a PTX-IIB monolithic oxidation system. The
conditioning and test sequence was identical to that previously used in
the first 30 base case runs (Monthly Report No. 2, Section II, A.I).
Unlike the base case runs, problems were encountered during the
112.6 km/hr (70 mph) cruises. In the first high speed cruise, (Run No.
34), misfire and spark plug failure occurred some 20 minutes into the run.
This caused a catalyst temperature increase to about 1040°C for about 10
minutes. The test was terminated, new plugs installed, and the vehicle
checked out.
A 1975 FTP the next day.(Run No. 35) showed that the catalyst
was inactive as a result of the.-temperature excursion the previous day.
The CO, HC, and SOo emissions'were considerably higher than what was
obtained on the initial 19.75 FTP run with the catalyst (compare Run No. 31
with Run No. 35, Appendix* V. The CO, HC, and S02 emissions were similar
to what was obtained when the vehicle without, a..catalyst was tested on
the same fuel (thus, compare Run No. 35, Appendix V, with Runs No. 16 and
20, Appendix II. Tests with the deactivated catalyst were terminated.
The vehicle was re-equipped with a fresh PTX-IIB catalyst which
was subjected to accelerated conditioning prior to testing in order to
make up for lost time and closely adhere to the program schedule.
Some 20 runs were carried out in August, but in no case were
we able to carry out a high speed cruise for the entire two hours. Tire
blowouts were responsible in most cases for the shorter duration high
speed cruises. In all the high speed cruise runs, gaseous and particu-
late samples were obtained and emission rates could be presented on a
normalized basis.
Although sulfuric acid analyses for most of the catalyst car
runs have not been carried out, the large increase in total particulate
emissions with the higher sulfur content fuels is indicative of sulfate
formation. Table V shows the average of the initial and final FTP
total particulate emissions for the PTX-IIB catalyst on the three fuels.
89
-------
Table V
Average Total Particulate Emissions
Vehicle 115. 1975 FTP
(guts/km)
Fuel
% PTX-IIB No
Sulfur Catalyst Catalyst
0.019 0.037 0.017
0.110 0.160 0.022
0.091 0.179 0.014
It will be noticed, comparing Appendix V with Appendix III
that when the low sulfur fuel was used, there are cases wh.a the total
particulate and sulfuric acid emission rates are comparable whether or
not the vehicle was equipped with the PTX-IIB catalyst. This may be in-
dicative of sulfate storage occurring. The relative effects of storage
would be expected to be greater, the lower the fuel sulfur content.
Section IV
Catalysts
Four catalysts have been conditioned and thermally stressed.
We have just received a Matthey-Bishop monolithic oxidation catalyst.
This system will be mounted and conditioned for the program test se-
quence. Delivery of the GEM 68 (Gould NOX Reduction Catalyst) is
expected shortly.
90
-------
APPENDIX I
TOTAL PARTICULATE EMISSIONS. BASE CASE RUNS
*
Emission Rate
Test No. Run Type Fuel (gins/km)
1 75 FTP EPA 0.050
2 Idle (1) " [0.197]
3 40 (1) " 0.006
4 70 (2) " 0.009
5 75 FTP " 0.036
6 75 FTP EPA+ 0.029
7 Idle (1) " [0.373]
8 40 (1) " 0.007
9 70 (2) " 0.012
10 75 FTP " 0.023
11 75 FTP HA+ 0.030
12 Idle (1) " [0.209]
13 40 (1) " 0.005
l4 70 (1) " 0.008
15 75 FTP " 0.022
16 75 FTP EPA 0.015
17 Idle (1) " [0.070]
18 40 (1) " 0.002
19 70 (2) " 0.003
20 75 FTP " 0.019
21 75 FTP EPA+ 0.034
22 Idle (1) " [0.094]
23 40 (1) " 0.004
24 70 (2) " 0.005
25 75 FTP " 0.010
26 75 FTP HA+ 0.014
27 Idle (1) " [0.115]
28 40 (1) " 0.005
29 70 (2) " 0.004
30 75 FTP " 0.014
EPA = EPA furnished reference fuel
EPA+ - EPA reference fuel plus additive package
HA+ = High aromatic fuel plus additive package
75 FTP = 1975 Federal test procedure
Idle (1) ° One hour idle
40 (1) = 40 mph (64.36 km/hr) cruise for one hour
70 (2) = 70 mph (112.63 km/hr) cruise for two hours
Runs 1-15 were with Test Vehicle No. 116
Runs 1-16 were with Test Vehicle No. 115
(Idle total particulate emissions, brackets, are in gms/hr)
91
-------
APPENDIX II
GASEOUS EMISSIONS. BASE CASE RUNS
Test
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
EPA+
HA+
75 FTP
Idle (1)
40 (1)
70 (2)
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FI?
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
= EPA f ui
• EPA re:
= High ai
= 1975 F(
= One hoi
= 40 mph
= 70 mph
Emissions Rate gms/tan
Fuel
EPA
it
ii
ii
it
EPA+
it
it
ii
it
HA+
ii
ii
ii
it
EPA
ti
it
ii
ii
EPA+
ii
ii
ii
it
HA+
ii
ii
CO
8.76
[170.38]
7.54
5.90
8.58
9.09
HC
1.23
[9.24]
0.417
0.05
1.57
1.38
NOX
0.86
[19.12]
0.61
1.76
0.97
1.02
S02
___
___
___
0.239
2.63
8.59
9.49
[169.92]
4.23
2.62
8.24
6.33
[21.69]
3.15
2.32
6.84
6.23
[29.4]
3.09
1.72
6.28
7.13
[35.14]
1.92
0.61
6.61
0.06
1.21
1.62
[24.43]
2.60
0.010
1.80
0.78
[10.85]
0.18
0.04
3.70
0.71
[7.06]
0.17
0.05
0.99
0.75'
[8.56]
0.17
0.05
0.74
EPA reference fuel plus additive package
High aromatic fuel plus additive package
1975 Federal test procedure
One hour idle
40 mph (64.36 kn/hr) cruise for one hour
70 mph (112.63 km/hr) cruise for two hours
Runs 1-15 were with Test Vehicle No. 116
Runs 1-16 were with Test Vehicle No. 115
(Idle gaseous emissions, brackets, are in gras/hr)*
0.73
1.00
1.38
[2.93]
0.34
0.60
1.17
0.97
[3.05]
0.28
0.86
0.78
0.77
[2.20]
0.29
0.86
0.85
0.84
[6.30]
0.43
0.54
0.84
0.181
0.301
0.363
[4.47]
0.154
0.154
0.347
0.048
[1.260]
[0.025]
[0.035]
0.076
0.284
[3.262]
0.202
0.167
0.295
0.318
[5.26]
0.160
0.136
0.301
92
-------
APPENDIX III
SULFURIC ACID EMISSIONS. BASE CASE RUNS
Test No.
Run Type
Fuel
H2&04 Emission Rate
(gms/km)*
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
EPA
EPA+
HA+
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
Idle (1)
40 (1)
70 '(2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 <2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (I)1
40 (1)
70 (2)
75 FTP
EPA
ii
ii
ii
ii
EPA+
ii
it
ii
n
HA+
n
ii
n
n
EPA
ii
n
n
n
EPA+
ii
n
ii
n
HA+
n
n
n
n
= EPA furnished reference fuel
B EPA reference fuel plus additive
= High aromatic fuel plus additive
= 1975 Federal test procedure
= One hour idle
= 40 mph (64.36
= 70 mph (112.63
km/hr) cruise for
km/hr) cruise for
0.0018 (2.3)
[0.0045] ( )
0.0010 (1.8)
0.0020 (3.2)
0.0027 (3.2)
0.0026 (0.55)
[0.0273] (0.48)
0.0005 (0.15)
0.0048 (1.5)
0.0022 (0.45)
0.0018 (0.41)
[0.0282] (0.44)
0.0001 (0.03)
0.0032 (1.17)
0.0006 (0.14)
0.0004 (0.50)
[0.0209] (0.18)
0.0002 (0.36)
0.0011 (2.00)
0.0014 (1.64)
0.0032 (0.60)
[0.0209] (0.03)
0.0005 (0.14)
0.0017 (0.51)
0.0015 (0.31
0.0015 (0.36)
[0.0242] (0.40)
0.0004 (0.13)
0.0017 (0.14)
0.0016 (0.39)
package
package
one hour
two hours
% of
Total
Particulate
3.6
[2.3]
16.6
22.2
7.5
9.0
[7.3]
7.1
40.0
7.3
6.0
[13.5]
1.3
14.5
2.7
2.7
[29.9]
10.0
36.7
7.4
9.4
[22.2]
12.5
34.0
15.0
10.7
[21.0]
8.0
42.5
11.4
Runs 1-15 were with Test Vehicle No. 116
Runs 1-16 were with Test Vehicle No. 115
(Idle total particulate emissions, brackets, are in gras/hr)*
Numbers in parentheses in column 4 are percent conversions fuel sulfur to
sulfate.
93
-------
APPENDIX IV
METAL EMISSIONS. BASE CASE RUNS
EMISSION SATE (gam/ton)*
Test
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
EPA+
HA-*-
Run
Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2j
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
1 l
= EPA furnished
= EPA reference
• High aromatic
Fuel
EPA
II
If
If
II
EPA+
ii
it
ii
ii
HA+
ii
ii
ii
if
EPA
n
it
n
n
EPA+
n
n
11
ii
HA+
ii
n
"
ii
reference
fuel plus
fuel plus
Ca
0.00025
[<0.0008]
0.00003
0.00011
0.00016
0.00014
[0.0022]
0.00004
0.00001
0.00017
0.00014
[0.0012]
0.00002
0.00001
0.00009
0.00007
[0.0004]
0.00001
<6 x 10-6
0.00002
0.00005
[< 0.0004]
0.00002
<6 x 10-°
0.00004
0.00007
[0.0004]
0.00001
<0. 00001
0.00002
fuel
Al
<0. 00005
[<0.0008]
<0. 00001
6 x 10-6
0.00006
0.00020
[0.0015]
0.00002
0.00001
0.00006
0.00006
[<0.0004]
<6 x 10~6
<0. 00001
0.00004
0.00007
[<0.0004]
<6 x 1(T6
<6 x 10-6
<0. 00002
0.00004
[<0.0004]
<6 x 10-6
<6 x 10~6
<0 * 00002
0.00004
[<0.0004],
<6 x 10" 6
<6 x IB"6
<0. 00002
75
Zn
0.00035
[0.0008]
0.00010
0.00009
0.00064
0.00027
[0.0035]
0.00005
0.00003
0.00080
0.00027
[0-0006]
0.00002
0.00003
0.00040
0.00016
[0.0006]
0.00001
0.00001
<0. 00002
0.00007
[0.0004]
0.00001
<0. 00001
0.00006
0.00010
[<0.0004]
<6 x 10-6
<0. 00001
0.00007
Cr
0.00005
[<0.0008]
0.00003
<0. 00001
0.00005
0.00007
[0.0009]
0.00002
<0. 00001
0.00009
0.00020
[0.0006]
<6 x 10-6
<6 x 10-6
0.00005
0.00007
[< 0.0004]
< 0.00001
<6 x 10-6
<0. 00002
0.00012
[<0.0004]
<6 x 10~6
<6 x 10-6
<0. 00002
0.00004
[<0.0004]
<6 x 10-6
<6 x ID'6
-------
APPENDIX V
EMISSIONS FROM PTX-IIB EQUIPPED VEHICLE(a) ON EPA REFERENCE FUEL
Emission Rates, gms/km
Test
No.
31
32
33
34
35
36
37
38
39
40
Catalyst
FTXIIB
PTXIIB
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
rartlculate Emissions
Total
Particulate
0.032
[0.104]
0.018
0.114
00.39
0.031
[0.294]
0.018
___
0.043
Gaseous Emissions
H2S04
0
[0
0
0
0
0
[0
0
0
.013
.068]
.009
.045
.007
.002
.103]
.012
.004
(15
(5
(13
(32
(5
(1
(4
(12
(2
.0)
.7)
.7)
.1)
.0)
.5}
.7)
.8)
.7)
__co
0
[6
0
0
4
3
[7
0
0
1
.77
.11]
.22
.15
.84
.26*+
.70]
.05
.06
.18
HC
0
[2
0
0
0
0
[4
0
0
0
.70
.08]
.050
.010
.92
.29
.45]
.04
.23
.63
NOx
1
[6
0
0
1
0
[8
0
5
0
.66
.98]
.38
.18
.11
.91
.66]
.148
.54
.74
SO;
0.035
[1.54]
0.045
0.003
0.057
to.o
[0]
0.0
0.0
0.0
(a) Vehii
EPA
EPA+
HA+
75 FTP
Idle (1)
40 (1) •
70 X2) •
:le No. 115
EPA furnished reference fuel
EPA reference fuel plus additive package
High aromatic fuel plus additive package
1975 Federal Test Procedure
One hour idle
3 40 mph (64.36 km/hr) cruise for one hour
> 70 mph (112 . 63 km/hr) cruise for. two hours
Numbers In parentheses, Column 5, are Z conversions, fuel sulfur to
**
*
• Temperature excursion due to misfire
- New catalyst system
*> Below limit of detection of S(>2 instrument
0 Defective vacuum breaker
-------
THE CHARACTERIZATION OF PARTICIPATE
EMISSIONS FROM PROTOTYPE CATALYST VEHICLES
MONTHLY PROGRESS REPORT NO. 4
FOR PERIOD SEPTEMBER 1 TO SEPTEMBER 30, 1974
PREPARED BY MORTON BELTZER
CONTRACT NO. 68-02-1279
10 OCTOBER, 1974
Prepared by
Exxon Products Research Division
Exxon Research and Engineering Company
Linden, New Jersey
for
Environmental Protection Aqency
Research Triangle Park, North Carolina 27711
96
-------
Section I
Purpose and Scope of Work
Exxon Research and Engineering Company, under contract with the
Environmental Protection Agency, is engaged in a research program designed
to measure and characterize the exhaust particulate emissions from a
variety of catalyst systems/ both commercial and prototype, that are can-
didates for use in automotive emissions control. Due to such mechanisms
as mechanical and thermal shock, and possible chemical conversion of
catalyst material to a mobile condensed material, particulate emissions
from catalyst equipped vehicles could differ markedly from that of con-
ventional vehicles. Furthermore, catalytic conversion of gaseous exhaust
components to particulate exhaust matter introduces exhaust components
that are not now present in the exhaust from conventional vehicles. A,
case in point is the catalytic oxidation of exhaust sulfur dioxide to the
trloxide which is then emitted as sulfate aerosol.
In order to separate vehicle and catalyst effects on total
particulate emissions, it will be necessary to.measure and characterize
particulate emissions from the vehicles in their conventional configura-
tion before they are equipped with catalysts.
Eight catalyst systems (three monolithic oxidation catalysts,
two beaded oxidation catalysts, and three reduction catalysts will be
tested with three fuels.
The three fuels that will be tested are:
(1) an EPA furnished reference fuel.
(2) the EPA fuel treated with an additive package consisting
of thiophene and t-butyl sulfide to a fuel sulfur level
of 0.1 wt.% sulfur, and TEL as motor mix to a level of
0.05 gms Pb/gal.
(3) a high aromatic content fuel similarly treated.
Both treated fuels shall also contain an additive package com-
prised of Lubrizol 596 (0.27 g/gal) and Paradyne 502 (0.45 g/gal). The
former functions as detergent, corrosion inhibitor, anti-stall, and anti- •
icing agent and contains about 2.25 - 2.75 wt.% nitrogen. Paradyne 502
contains 0.75 wt.% nitrogen and functions as a detergent, anti-rust agent,
and deposit modifier.
This fuel selection should allow exhaust particulate character-
ization as follows:
97
-------
(1) level and composition of exhaust particulate resulting
from the use of an additive-free fuel in conventional and
catalyst equipped vehicles.
(2) effect of fuel additives on particulate emissions from
conventional and catalyst quipped vehicles.
(3) effect of a high aromatic fuel containing additives on
particulate emissions from conventional and catalyst
equipped vehicles.
Section II
A. Work During Period of September 1-30, 1974
The test sequences (Monthly Report No. 2, Section II, A..:)
were carried out with three more catalyst systems. These incl'^^d two
monolithic oxidation catalysts and a pelletized oxidati.cn cat, .yst.
Monolithic catalysts tested were a Universal Oil Products (UOP) system
and a Matthey Bishop system, hereinafter referred to as MONO (2) and
MONO (3) respectively. The Engelhard PTX-IIB discussed in the previous
monthly is hereinafter referred to as MONO (1).
The pelletized oxidation catalyst was an Engelhard system,
hereinafter referred to as Pellet (1).
Total particulate, sulfuric acid, gaseous and metal emission
rates were measured. Metal analyses have not been completed for the
MONO (3) runs.
A.I Total Particulate Emission Rates
Table I shows the average of the initial and final FTP total
particulate emissions for each of the catalysts on the three fuels. The
results obtained with the PTX-IIB catalyst, MONO (1) reported in the
previous monthly are also shown in order to compare the four oxidation
catalysts tested thus far in this program.
TABLE I
Average Total Particulate Emission Rate
(1975 FTP. Vehicle 115 Equipped with Indicated Catalyst Systems)
Fuel gins/km
%
Sulfur MONO (1) PELLET (1) MONO. (2) MONO (3)
0.019 0.037 0.049 0.032 0.025
0.110 0.160 0.071 0.097 0.068
0.091 0.179 0.063 0.088 0.055
98
-------
The detailed total particulate emission results are given in
Appendices I to IV.
A.2 Sulfuric Acid Emission Rates
Table II shows the sulfuric acid emission rates corresponding
to the runs presented in Table I. Also shown in Table II are the percent
conversions (numbers in parentheses), based on fuel consumption and
measured sulfate particulate.
Both the sulfuric acid emission rates and percent conversions
are generally lover than what had been obtained in earlier work (1, 2)
using this particulate sampling system.
TABLE II
0.003(2.1)
0.057(10.4)
0.069(15)
0.003(2.6)
0.018(2.1)
0.' Oil (2. 2)
0.002(1.9)
0.025(4.6)
0.020(4.2)
0.003(3.1)
0.024(4.3)
0.020(7.7)
Average Sulfuric Acid Emission Rate
(1975 FTP. Vehicle 115 equipped with oxidation catalyst systems)
gms/km*
Fuel
%
Sulfur MONO (1) Pellet (1) MONO (2) MONO (3)
0.019
0.110
0.091
(* Numbers in parenthesis are averaged % conversions)
Several factors could be responsible for the differences
between the above results and the results of the earlier work. In
the present work, the test sequence is different from any previous
sequence we have used. In addition, the catalysts used in this program
are essentially fresh catalysts in terms of exposure to sulfur-containing
fuels. Similar considerations apply to the exhaust systems used in the
test vehicle systems.
By contrast, the percent conversions obtained on the 64.36 km/hr
(40 mph) cruises are generally somewhat higher than what was previously
obtained, inducating that the test sequence may be the most dominant
parameter affecting sulfate emissions. The cruise results are shown in
Table III below.
(1) M. Beltzer, R. J. Campion, and W. L. Petersen, "Measurement of
Vehicle Particulate Emissions," SAE Paper 740286, February, 1974.
(2) Esso Research and Engineering Company, Submission to EPA, Data on
Automotive Sulfate Emissions, May, 1974.
99
-------
TABLE III
Sulfuric Acid Emission Rates for 40 mph, 1 hour Cruise Conditions
_ (Vehicle 115 'Equipped with Oxidation Catalyst Systems)
gins/km*
Fuel %
Sulfur MONO (1) Pellet (1) MUNO (2) MONO (3)
0.019 0.012(12.8) 0.001(1.5) 0.013(20.3) 0.006(9.4)
0.110 0.101(30.1) 0.104(27.2) 0.183(47.8) 0.055(15.3)
0.091 0.076(25.7) 0.078(22.4) 0.165(52.1) 0.043(13.1)
(* Numbers in parentheses are % conversions)
Appendices I to IV show the detailed sulfui^c irid em.'
results. The data for MONO (1), the PTX-IIB of the third monthly are
also included in liiis report to allow rapid comparison of the emission
characteristics of the four catalyst systems tested to date.
A. 3 Gaseous Emission Rates
Appendices I to IV also show the detailed gaseous emission
results for CO, HC, NOX, and
A. 4 Metal Emission Rates
Emission rates of Ca, Al, Zn, Cr, Fe, Cu, Ni, Pb, and Ft were
obtained in each test run when vehicle 115 was equipped with a catalyst.
The analysis for Ft has not yet been completed, nor has the remaining
metal analysis been completed for the MONO (3) catalyst tests (Runs 81-95).
Appendices V to VII show the detailed metal emission rates when vehicle
115 was equipped with MONO (1) and (2) and Pellet (1) catalyst systems.
No detectable quantities of platinum have been found on the
filters analyzed to date (Runs 31 to 45) . The minimum detectable level
of Ft by our X-ray fluorescence analysis procedure is 0.35 ugms/cm . Con-
sequently, the maximum emission rates for platinum based on negative . '
results, the accumulated test mileage and the minimum detection level is
5.6 x 10-5 gms/km for the 1975 FTP, 1.55 x 10~5 gms/km for the 40 mph
one hour cruise, and 4.43 x 10~6 for the 70 mph two hour cruise. For
the idle cruise, the corresponding maximum emission rate in gms/hr is
1 x 10" 3. The platinum emission results obtained to date are given in
Appendix V. It will be noticed that the platinum emission rates for the
70 mph cruises differ from the 4.43 x 10~6 gms/km cited above. This is
because Runs 34, 39 and 44 were terminated due to misfire or blown tires be-
fore the full 225.26 km (140 miles) could be accumulated. Consequently, the
100
-------
platinum emission rates for these runs are based on the mileage accumu-
lated prior to run termination. Similar considerations apply to the
emission rates of total particulates, l^SO^, the other metals, and to
the gaseous exhaust components as well.
To make an initial assessment of the effect of the catalysts
on metal emissions rates, the emission rates for six metals obtained on
the Federal Cycles for vehicle 115 were plotted, Figures I to VUI. The
abscissa (test number) are cardinal numbers only with respect to the
Federal Test Cycles. These figures consequently are not intended to
depict metal emission rates under consecutive continuous testing since
three other tests or a conditioning procedure occur between successive
Federal Test Procedures. Nevertheless, using this approach, it is
possible to draw some tentative conclusions.
Figure I shows that the aluminum emission rate increases
sharply when the vehicle is equipped with the various oxidation catalysts.
It should be noted that if aluminum is used as a platinum surrogate, even
at the highest aluminum FTP emission rate (about 0.001 gins/km), the
platinum could be as much as 5.6% of the aluminum content and still be
below our detection limits. Since the platinum content of the catalyst
is well below 1 wt % of the substrate, it is not surprising that no
platinum has been detected in the samples analyzed to date.
Iron emission rates for the 75 Federal Test Procedures are
shown in Figure II. While there is an increase in iron emissions when
the vehicle is equipped with a catalyst, the relative increase is con-
siderably lower than that for aluminum emissions. A possible reason
for the increased iron levels above that obtained when the vehicle was
operated in the conventional mode may be due to reaction of parts of
the exhaust train with catalytically produced I^SC^ aerosol. This
could result in increased iron emissions above that due to normal attri-
tion.
A test of this hypothesis will come when the vehicle is equipped
with a NOX reduction catalyst. It would be expected that iron emissions
would decrease to the base case levels in this case.
Figure III depicts the lead emission rates. There is a small
increase in the lead emission rate when the vehicle is equipped with
catalysts. This, however, may be due to the vehicle becoming conditioned
to fuels containing lead at about the 0.05 gms/gal level. The vehicle
is operated on lead sterile fuel until a 200 mile conditioning procedure
prior to the first test sequence. It is probable therefore that if this
is taken into consideration, the lead emission rates are independent of
whether or not the vehicle is equipped with a catalyst.
101
-------
Figure IV shows the zinc emission rates increase when the
vehicle is equipped with the oxidation catalysts. It is not certain
what the source of the zinc is. We plan to analyze a standard 1974 GM
muffler to determine if there •**» any 'Jnc on its internal surfaces.
The increased zinc emissions in the case of a catalyst equipped vehicle
could be ascribed to corrosion as a result of contact with
Figures V and VI show the nickel and calcium emission rates
respectively. The emission rates of both these metals is considerably
lower than the rates for lead, zinc, and iron. Here too, the emission
rates with a catalyst equipped vehicle are greater than when the vehicle
is in the conventional mode. Nickel may be due to corrosion by the
H2SO^ of stainless steel (sampling system) or cold rolled steel (exhaust
system). The calcium may be a low level impurity in the catalyst sub-
strate that is attriting.
Figures VII and VIII show the FTP emission rates for chromium
and copper respectively, the pattern also being an approximate sawtooth.
The sawtooth emission pattern shown in tne figures may In part
be due to deposits being built up on the mileage accumulation and emitted
on the first run of the test sequence, that is the first FTP. The higher
metal emission rates on many of the first FTP's of the run sequence would
tend to substantiate the above hypothesis. However, there are cases
where the metal emissions on successive FTP's are comparable and do not
show the sawtooth pattern. This could be due to re-entrainment of de-
posited material from the inner surfaces of the exhaust system. Since
re-entrainment of deposited material into the exhaust stream occurs on
a seemingly erratic basis, this phenomenon could account for the gaps
in the approximate periodicity of the sawtooth emission pattern.
In addition the periodicity does not match for all the metals.
This can be seen by comparing the iron and copper emission rates. What
is a crest in the emission rate of one metal corresponds to a trough in
the emission rate of the other, on the same FTP. This indicates that
different mechanisms for metal emissions may be operative. For example
accumulation of one metal may be occurring while another is being depleted
through emission.
Section III
Catalysts
The Grace NOX reduction catalyst has been mounted, and con-
ditioned for the test program. The GEM 68 (Gould NOX reduction catalyst)
has been received. This catalyst has been mounted and is undergoing
conditioning.
The last two catalyst systems (both oxidation catalysts) are
expected shortly. These in turn will be mounted, conditioned, and tested
as the previous systems.
102
-------
FIGURE I
ALUMINUM EMISSION RATES
ON FEDERAL TEST CYCLES
CATALYST SYSTEM
<-
NONE
( MONO (1)
£—PELLET (1) —}
100
90
80
70
60
50
40
30
20
10
10 15 20
NUMBER OF 1975 FEDERAL TEST PROCEDURES
30
-------
FIGURE II
220
200
180
160
x
A
1
§
M
CO
120
100
80
60
40
20
£ NONE
IRON EMISSION RATES
ON FEDERAL TEST CYCLES
CATALYST SYSTEM
10 ' 15
NUMBER OF FEDERAL CYCLES
20
25
-------
l/l
FIGURE III
LEAD EMISSION RATES ON
FEDERAL TEST CYCLES
10 15 20
NUMBER OF 1975 FEDERAL CYCLES
-------
( NONE
100
90
80
70
60
50
30
20
10
FIGURE IV
ZINC EMISSION RATES
ON FEDERAL TEST CYCLES
CATALYST SYSTEM
MONO (1)
)
^""PELLET (1) "V \~M01
10. 15
NUMBER OF FEDERAL CYCLES
20
-------
FIGURE V
NICKEL EMISSION RATES ON FEDERAL TEST CYCLES
10 15
NUMBER OF FEDERAL TEST CYCLES
-------
CALCIUM EMISSION RATES ON FEDERAL TEST CYCLjES.
25
20
J
w 15
H
CO
CO
10
10 15
NUMBER OF FEDERAL TEST CYCLES
-------
50
FIGURE VII
CHROMIUM EMISSION RATES
ON FEDERAL TEST CYCLES
CATALYST SYSTEM
10 15
NUMBER OF FEDERAL CYCLES
-------
FIGURE VIII
COPPER EMISSION RATES ON
FEDERAL TEST CYCLES
CATALYST SYSTEMS
100
S~ NONE
80
I
Id
1
60
40
eu
04
O
20
10 15
NUMBER OF FEDERAL TEST CYCLES
20
25
-------
APPENDIX I
MONO (1) EQUIPPED CHEVROLET 115
% Fuel Catalyst
lest No. Sulfur Type Run Type
36 0.019 PTX-II3 75 FTP
37 " " Idle (1)
38 " " 40 (1)
39 " " 70 (2)
40 " " 75 FTP
41 0.110 " 75 FTP
42 " " Idle (1)
43 " " 40 (1)
44 " " 70 (2)
45 " " 75 FTP
46 0.091 " 75 FTP
47 " " Idle (1)
48 " " 40 (1)
49 " " 70 (2)
50 " " 75 FTP
Emission Rates, gms/kro
Particulate Emissions
Total
Particulate
0.031
[0.294]
0.018
0.039
0.043
0.169
[0.106]
0.262
0.150
0.150
0.226
[0.100]
0.192
0.146
0.131
H2S04*
0.002 (1.5)
[0.103] (4.7)
0.012 (12.8)
0.010 (13.2)
0.004 (2.7)
0.060 (11.1)
[0.048] (7.0)
0.101 . (30.1)
0.055 (12.2)
0.053 (9.7)
0.087 (19.2)
CO
3.26
[7.70]
0.05
1.18
1.45
[5.32]
0.20
0.024
2.03
1.40
[0.028] (0.5) -yf^[7.26]
0.076 (25.7)"^ 0.28
0.057 (15.7)
0.050 (10.7)
2.01
Gaseous Emissions
HC
0.29
[4.45]
0.04
0.63
0.80
[5.62]
0.08
0.003
0.42
0.28
[6.10]
0.08
0.28
NOX
0.91
[8.66]
0.15
0.74
1.20
[3.91]
0.52
0.19
0.88
1.33
[3.91]
1.04
1.31
S02
•vO
0
0
0
0
0.134
[2.55]
0.057
0.009
0.139
0.080
[2.14]
0.050
0.098
Numbers in Parentheses are % Conversions Based on Emitted Sulfate
Bracketed Numbers are Emission Rates in gms/hr
0.019% S = EPA Reference Fuel
0.110% S = EPAf
0.091% S = HA+
-------
APPENDIX II
PELLET (1) EQUIPPED CHEVROLET 115
Emission Rates, gins/km
Participate Emissions
Test No.
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
% Fuel
Sulfur
0.019
it
it
ii
ti
0.110
II
II
It
II
0.091
n
ii
n
ii
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
Total"
Particulate
0.
[0.
0.
0.
0.
0.
[0.
0.
0.
0.
0.
[o.
0.
0.
0.
061
130]
009
115
036
059
099]
246
287
083
062
062]
201
117
064
H2S04**
0.003
[0.022]
0.001
0.027
0.002
0.008
[0.052]
0.104
0.103
0.029
0.016
[0.0 ]
0.078
0.046
0.006
( 3.19)
( 1.76)
(-1.52)
(36.00)
( 2.08)
( 1-42)
( i.oi)
(27.15)
(25.31)
( 5.02)
( 3.16)
( 0.0 )
(22.41)
( 5.71)
( 1.17)
Gaseous Emissions
CO
2.528
[0.81 ]
0.019
2.501
1.528
[7.506]
0.154
0.086
1.327
2.162
U.f76]
0 218
0.044
2.808
HC
0.217
[1.458]
0.016
0.224
0.349
[3.964]
0.075
0.029
0.176
0.324
[2.333]
0.089
0.008
0.219
NOX
1.
[0.
0.
-
1.
1.
[8.
0.
1.
i.
1.
[8.
0.
3.
1.
370
54 ]
008
—
318
229
73 ]
601
581
013
194
932]
740
111
171
S02
0.015
[o.o ]
0.0
0.093
0.043
[0.544]
0.0
0.0
0.058
0.061
0.0
0.022
0.129
0.066
**
Bracketed numbers are emission rates in gms/hour for the idle cruises.
Numbers in parentheses, Column 4, are % conversions, SO2
sulfate measured.
based on fuel consumption and particulate
-------
APPENDIX III
MONO (2) EQUIPPED CHEVROLET 115
Emission Rates, gins/km
Particulate Emissions
Test No.
66
67
68
69
70
=: 71
OJ
72
73
74
75
76
77
78
79
80
% Fuel
Sulfur
0.019
ii
it
ii
ii
0.110
II
It
tl
II
0.091
ii
ii
ii
ii
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
Total*
Particulate
0
[0
0
0
0
0
[0
0
0
0
0
[0
0
0
0
.029
.064]
.037
.031
.035
.104
.073]
.490
.168
.090
.134
.142]
.462
.138
.042
H2S04**
0.003
[0.021]
0.013
0.011
0.001
0.022
[0.011]
0.183
0.065
0.027
0.033
[0.034]
0.165
0.061
0.008
( 2.88)
( 1-71)-
(20.31)
( 7.43)
( 0.99)
( 3.93)
( 0.16)
(47.78)
( 8.05)
( 5.29)
( 6.78)
( 0.56)
(52.05)
( 7.79)
( 1.57)
Gaseous Emissions
CO
2.652
[22.766]
0.129
0.174
1.770
1.742
[ 4.946]
0.119
0.121
2.124
1.800
[ 4.136]
0.132
0.147
1.863
HC
0
[11
0
0
0
0
[ 4
0
0
0
0
[ 4
0
0
0
.274
.416]
.042
.018
.191
.250
.277]
.048
.014
.264
.191
.158]
.033
.013
.150
NOX
1.091
[6.728]
0.694
1.955
0.927
1.079
[5.098]
0.505
0.118
0.622
1.277
[6.836]
0.706
3.570
1.305
S02
0.061
[0.0 ]
0.0
0.031
0.029
0.190
[0.0 ]
0.031
0.117
0.186
0.074
[0.0 ]
0.043
0.107
0.004
**
Bracketed cumbers are emission rates in gms/hour for the idle cruises.
Numbers in parentheses, Column 4, are % conversions, SC>2
sulfate measured.
H2S04, based on fuel consumption and particulate
-------
APPENDIX IV
MONO (3) EQUIPPED CHEVROLET 115
Test No.
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
% Fuel
Sulfur
0.019
ii
11
"
ii
0.110
II
II
II
II
0.091
n
11
ii
ii
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)**
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 pxP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
Emission Rates, gms/kmt
Particulate Emissions
Total*
Particulate
0.028
[0.185]
0.014
0.025
0.021
0.086
[0.068]
0.118
0.141
0.050
0.069
[0.101]
0.087
0.097
0.040
Gaseous Emissions
H2S04
0.003 (3.15)
CO. OH (0.0)
0.006 (9.38)
0.010 (7.19)
0.003 (3.09)
0.032 (5.66)
CO.OD (0.0)
0.055 .(15.32)
0.068 (16.71)
0.016 (2.9)
0.024 (5.07)
CO.OJ (0.0)
0.043 (13.1)
^0
0.058 (15.8) ,&
0.015 (10.3)
CO
1.373
[ 8.834]
0.200
0.427
0.959
1.035
[ 8.067]
0.267
0.555
2.663
1.040
[5.430]
J(* ".^88
0.549
2.087
EZ
0.232
[ 5.584]
0.047
0.033
0.146
0.241
[ 6.361]
0.058
0.033
0.323
0.244
[4.061]
0.049
0.030
0.253
NOX
1.083
[11.524]
0.598
2.208
0.578
1.116
[ 7.020]
0.648
2.430
1.136
1.313
[8.381]
30.890
2.938
2.112
SO 2"
0.031
[ 0.961]
0.037
0.022
0.023
0.245
I 3.694]
0.197
0.213
0.275
0.233
[2.960]
0.160
0.194
0.388
t Idle emission rate, bracketed numbers are in gms/hour
* S02 .calibrated from S02 in.air calibration curve (no correction factor was used)
** 60 mph (96.54 km/hr) supplants the former 70 mph cruise test runs
K
-------
APPENDIX V
METAL EMISSIONS. CHEVROLET 115 EQUIPPED WITH MONO (1) CATALYST
Emission Rate (gins/km)*
Test
No.
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
43
49
50
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (J)
40 (1)
70 (2)
75 FTP
% Fuel
Sulfur
0.019
II
II
It
II
0.019
II
II
II
II
0.110
II
II
II
II
0.091
II
M
II
II
Ca
0.00010
[<0. 00180]
0.00004
0.00021
O.OOOlb
0.00010
[ 0.00180]
<0. 00003
0.00009
0.00013
0.00016
[ 0.00160]
0.00003
<0. 00002
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Al
>0. 00010
[ 0.00180]
<0. 00003
0.00079
0.00051
0.00029
[ 0.00400]
0.00005
0.00016
<0. 00010
0.00021
[<0. 00180]
0.00004
O.OOOOJ
<0.00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Zn
>0. 00033
[ 0.00180]
<0. 00003
0.00204
0.00202
>0. 00100
[ 0.01440]
0.00011
0.00027
0.00039
0.00100
[<0. 00180]
0.00016
0.00015
0.00048
0.00043
[ 0.00220]
0.00003
>0. 00024
0.00079
Cr
0.00013
[ 0.00180]
<0.00003
0.00031
0.00025
0.00016
[<0. 00180]
<0.00003
<0.00058
<0. 00010
O.C0037
[<0. 00180]
0.00003
0.00004
<0. 00010
0.00019
[<0. 00180]
<0. 00003
0.00001
0.00011
Fe
0.00202
[ 0.03600]
0.00010
0.00440
0.00202
>0. 00200
[>0.0018 ]
0.00021
>0. 00058
>0. 00100
>0. 00202
[ 0.00320]
>0. 00028
>0. 00020
>0. 00100
>0. 00100
[ 0.00240]
0.00006
>0. 00012
>0. 00100
Cu
0.00051
[ 0.00920]
<0. 00003
0.00115
0.00092
0.00038
[<0. 00180]
<0. 00003
0.00008
<0 .00010
0.00075
[<0. 00180]
0.00005
0.00006
0.00045
0.00065
[<0. 00180]
<0.00003
0.00003
0.00072
Ml
0.00010
[ 0.00180]
<0. 00003
0.00021
0.000.12
<0. 00010
[<0.0018 ]
0. 00100
[ 0.006GO]
0.00015
0.00046
0.00056
0.00101
[ 0.003iO]
0.00024
>0. 00020
>0.00100
0.00100
[ 0.00400]
O.OOuOA
>0. 00012
O.OOOiiS
Pt
<0. 00006
[<0. 00100]
<0. 00001
<0. 00002
<0. 00006
<0. 00006
[<0. 00100]
<0. 00001
<0. 00003
<0. 00006
<0. 00006
1^0. 00100 ]
<0. 00001
<0. 00001
<0. 00006
—
—
—
—
___
* Bracketed nuiibcrs arc idle emission races of metals in gms/hour.
** Replacement PTX-I1B (Runs 36-50) after first PTX-1IB deactivated (Run 34) due to excessive temperature rise resulting from misfire.
-------
APPENDIX VI
METAL EMISSIONS. CHEVROLET 115 OjUIPPt.D WITH PELLET (1) CATALYST
Emission Rate (gins/km)*
Test
No.
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle U)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
% Fuel
Sulfur
0.019 0
[<0
0
0
0. 00028
>0. 00100
0.00046
[<0. 00180]
<0. 00003
0.00006
0.00016
0.00020
[ 0.00200]
< 0.00003
0.00001
0.00022
Zn
0.00076
[ 0.00260]
0.00004
>0. 00057
>0. 00200
0.00037
[<0. 00180]
0.00005
0.00012
0.00019
0.00027
[<0. 00180]
<0. 00003
0.00002
0.00075
Cr
0.00021
[<0. 01800]
<0. 00003
>0. 00026
0.00024
0.00028
[<0. 00160]
<0. 00003
0.00005
<0. 00010
0.00018
[<0. 00180]
<0. 00003
<0. 00001
0.00012
>0
[>0
0
>0
>0
>0
[ o
0
0
>0
>0
[ o
0
>0
>0
Fe
.00202
.01800]
.00028
.00057
.00200
.00202
.00760]
.00018
.00073
.00100
.00101
.C '20]
.00^23
10010
.00202
Cu
0.00025
[<0. 01800]
0.00004
>0. 00028
0.00059
0.00048
[<0. 00180]
<0. 00003
0.00010
0.00043
0.00037
[<0. 00180]
<0. 00003
0.00001
0.00078
Ni
0.00019
[<0.001SO]
0.00003
0.00026
0.00019
0.00026
[<0. 00180]
<0. 00003
0.00006
<0. 00010
0.00021
[<0. 00180]
<0. 00003
<0. 00001
0.00015
Pb
X). 00100
[0.00860]
0.00016
>0.00057
>0. 00100
>0.00202
[0.00480]
0.00015
>0. 00036
0.00050
0.00076
0.00200
0.00007
0.00003
0.00057
Bracketed numbers are Idle emission rates in gms/hour.
-------
APPENDIX VII
liETAL EMISSIOKS. CHEVROLET 115 EQUIPPED WITH MONO (2) CATALYST
Emission Kale (gms/km)*
Test
No.
66
G7
68
69
70
71
72
73
74
75
76
77
78
79
80
Run Type
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
70 (2)
75 FTP
Z Fuel
Sulfur
0.019
II
II
II
II
0.110
II
II
II
II
0.091
II
II
"
II
Ca
0.00025
[0.00240]
0.00005
0.00002
0.00015
0.00018
[0.00440]
0.00005
<0. 00010
0.00020
0.00019
[0.00380]
0.00006
0.00007
0.00022
Al
0.00030
[ 0.00180]
<0. 00003
0.00002
0.00031
0.00032
[ 0.00640]
O.OOOOJ
0.00001
0.00018
0.00016
[<0.00180]
<0. 00003
0.00007
0.00021
Zn
0.00035
[<0. 00180]
<0. 00003
0.00008
0.00100
0.00048
[ 0.00280]
0.00004
0.00001
0.00022
0.00025
[<0. 00180]
<0. 00003
0.00016
0.00018
Cr
0.00015
[<0. 00180]
<0. 00003
0.00002
<0. 00010
0.00026
[ 0.00240]
<0. 00003
<0. 00001
<0. 00010
0.00012
[<0. 00160]
<0. 00003
0.00008
<0. 00010
Fe
>0. 00101
[ 0.00740]
0.00010
0.00016
'0.00202
>0. 00202
[>0. 01800]
0.00021
>0. 00008
0.00087
0.00202
[ 0.00280]
0.00016
0.00016
0.00085
Cu
0.00030
[<0. 00180]
<0. 00003
0.00003
0.00060
0.00028
[ 0.00260]
<0. 00003
<0. 00001
0.00034
0.00030
[ 0.00180]
<0. 00003
0.00008
0.00038
Ml
0.00017
[<0. 00180]
<0. 00003
<0. 00001
<0.00010
0.00027
[ 0.00260]
<0. 00003
<0. 00001
<0. 00010
0.00010
[<0. 00180]
<0. 00003
0.00008
<0 .00010
Pb
0.00059
[<0. 00180]
O.OG004
0.00008
0.00053
O.OOOB7
[ 0.007&0]
0.00007
0.00002
0.00029
0.00037
[ 0.00200]
0.00014
>0. 00008
0.00039
* Bracketed numbers are idle emission rates in gas/hour.
-------
THE CHARACTERIZATION OF PARTICULATE
EMISSIONS FROM PROTOTYPE CATALYST VEHICLES
MONTHLY PROGRESS REPORT NO. 5
FOR PERIOD OCTOBER 1 TO OCTOBER 31, 1974
PREPARED BY MORTON BELTZER
CONTRACT NO. 68-02-1279
10 NOVEMBER, 1974
Prepared by
Exxon Products Research Division
Exxon Research and Engineering Company
Linden, New Jersey
for
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
118
-------
Section I
Purpose and Scope of Work
Exxon Research and Engineering Company, under contract with the
Environmental Protection Agency, is engaged in a research program designed
to measure and characterize the exhaust particulate emissions from a
variety of catalyst systems, both commercial and prototype, that are can-
didates for use in automotive emissions control. Due to such mechanisms
as mechanical and thermal shock, and possible chemical conversion of
catalyst material to a mobile condensed material, particulate emissions
from catalyst equipped vehicles could differ markedly from that of con-
ventional vehicles. Furthermore, catalytic conversion of gaseous exhaust
components to particulate exhaust matter introduces exhaust components
that are not now present in the exhaust from conventional vehicles. A
case in point is the catalytic oxidation of exhaust sulfur dioxide to the
trloxide which is then emitted as sulfate aerosol.
In order to separate vehicle and catalyst effects on total
particulate emissions, it will be necessary to measure and characterize
particulate emissions from the vehicles in their conventional configura-
tion before they are equipped with catalysts.
Eight catalyst systems (three monolithic oxidation catalysts,
two beaded oxidation catalysts, and three reduction catalysts will be
tested with three fuels.
The three fuels that will be tested are:
(1) an EPA furnished reference fuel.
(2) the EPA fuel treated with an additive package consisting
of thiophene and t-butyl sulfide to a fuel sulfur level
of 0.1 wt.% sulfur, and TEL as motor mix to a level of
0.05 gins Pb/gal.
(3) a high aromatic content fuel similarly treated.
Both treated fuels shall also contain an additive package com-
prised of Lubrlzol 596 (0.27 g/gal) and Paradyne 502 (0.45 g/gal). The
former functions as detergent, corrosion inhibitor, anti-stall, and anti-
icing agent and contains about 2.25 - 2.75 wt.% nitrogen. Paradyne 502
contains 0.75 wt.% nitrogen and functions as a detergent, anti-rust agent,
and deposit modifier.
This fuel selection should allow exhaust particulate character-
ization as follows:
119
-------
(1) level of composition of exhaust particulate resulting
from the use of an additive-free fuel in conventional and
and catalyst equipped vehicles.
(2) effect of fuel additives on particulate emissions from
conventional and catalyst equipped vehicles.
(3) effect of a high aromatic fuel containing additives on
particulate emissions from conventional and catalyst
equipped vehicles.
Section II
A. Work During Period of October 1-31. 1974
The test sequences (Monthly Report No. 2, Section II, .A.I) were
carried out with two NOX reduction catalysts. These catalytic systems
supplied by W. R. Grace and Gould Incorporated are herelnaftei referred
to as REDN (1) and REDN (2) respectively. In order to assess the NO
reduction capabilities of these systems, the exhaust gas recycle EGR was
disconnected. The air pumps from the mileage accumulation vehicle and
the test vehicle were disconnected to minimize the occurrence of lean
operating conditions over the catalysts during mileage accumulation or
testing. Carburetion was not modified for either vehicle. Analysis of
the raw exhaust upstream to the catalysts at about 16, 32, 48, 64, and
96 km/hour showed that the catalysts are exposed to a net rich exhaust
in these cases except for slightly lean operation at 64 km/hour. The
REDN (2) catalyst package contains an oxygen control system called a
"Getter" upstream to the reduction catalyst which functions by scav-
enging the residual oxygen in raw exhaust.
Total particulate, sulfuric acid, gaseous and metal emission
rates were measured. Metal analyses have been completed for the REDN (1)
runs; partial analyses are available for the REDN (2) runs.
A.I. Total Particulate Emission Rates
Table I shows the average of the initial and final FTP total
particulate emission rates for both NOX reduction catalysts on the three
test fuels.
Table I
Average Total Particulate Emission Rate
(1975 FTP, Vehicle 115 Equipped with Indicated Catalyst Systems)
gms/kin
Fuel %
Sulfur REDN (1) REDN (2)
0.019 0.012 0.027
0.110 0.017 0.020
0.091 0.030 0.025
120
-------
The fuel sulfur content does not appear to have a marked influence
on the total particulate emission rate as in the cases where the vehicle
was equipped with oxidation catalysts. This is readily evident if one
compares the above Table with the results in Table I, Fourth Monthly
Report. In fact the lack of dependence of particulate emission rates
on fuel sulfur content is similar to what was exhibited in the base case
runs, Table I, Third Monthly Report. The detailed total particulate
emission rates for these catalyst systems are given in Appendices 1 and
II.
A.2 Sulfuric Acid Emission Rates
Table II shows the sulfuric acid emission rates corresponding
to the runs in Table I. Also shown in Table II are the percent con-
versions (numbers in parentheses) based on fuel consumption and measured
sulfate particulate.
Table II
Average Sulfuric Acid Emission Rate
(1975 FTP, Vehicle 115 Equipped with Reduction Catalysts)
fims/km
Fuel %
Sulfur REDN (1) REDN (2)
0.019 0.001 (1.7 ) 'vfl.OOl (1.7 )
0.110 0.004 (0.87) 0.002 (0.33)
0.091 =0.001 (0.22) <0.001 (0.11)
The low levels of sulfuric acid emissions, independent of fuel
sulfur content, arc consistent with the results shown in Table I, which
indicate the lack of dependence of total particulate emissions on fuel
sulfur content.
Although sulfuric acid emissions were low under cyclic test con-
ditions and negligible on the idle cruises, readily detectable quantities
of sulfate were detected on the steady state cruises. The levels were
generally well below the sulfate levels obtained when the vehicle was
equipped with oxidation catalysts. Table III shows the sulfate emissions
for the two reduction catalyst systems at 40 and 60 mph cruises.
121
-------
Table III
Sulfuric Acid Emission Rates
at 40 and 60 raph Cruises with
Reduction Catalyst Equipped Vehicle
% Fuel Run gins/km, H2SO^ with Indicated Catalyst
Sulfur Type REDN (1) REDN (2)
0.019 40 (1) 0.002 ( 3.45) 0.002 ( 3.70)
11 60 (2) 0.001 ( 1.52) 0.006 ( 9.68)
0.110 40 (1) 0.065 (18.1 ) 0.044 (13.10)
11 60 (2) 0.027 ( 6.91) 0.039 ( 9.97)
0.091 40 (1) 0.043 (14.01) 0.034 (11.85)
" 60 (2) 0.024 ( 7.19) 0.040 05.04)
A.3 Gaseous Emission Rates
Emission rates for CO, HC, NOX, and SC<2 are also shown in
Appendices I and II.
The NOX emissions from both catalyst systems was comparable
to what was obtained with the vehicle equipped solely with EGR. Steady
state cruise A/F ratio measurements prior to actual vehicle tests in-
dicated net rich operating conditions. However, A/F ratio measurements
during the transient portions of the test cycle Indicate that the re-
duction catalysts have been exposed to a net lean environment during a
major portion of both the test procedures and the conditioning sequence
prior to testing. Thus, both reduction catalysts were not operated at
conditions recommended by the catalyst manufacturer. Consequently the
results obtained with these catalysts under our test conditions are not
to be considered as representative of the true NOX reducing capabilities
of these catalysts.
A.4 Metal Emission Rates
Metal analyses for the MONO (3) catalyst test runs (Runs 81-95)
have been completed. The MONO (3) metal emission rates are shown in
Appendix III. Platinum analyses have not yet been completed for the
MONO (3) runs.
Metal emission rates REDN (1) and REDN (2) are shown in Ap-
pendices IV and V.
In the Fourth Monthly Report, the metal emission rates measured
on the 1975 Federal Test Cycles were plotted to make an Initial assess-
ment of the effect of catalysts. In this report, these plots are carried
out for nickel and Iron only, Figures I and II respectively. It can be
seen from Figure I that the nickel emission rate increases sharply when
122
-------
the vehicle is equipped with the REDN (2) reduction catalyst. Presently,
it is not known if the increased nickel emission rates observed with the
REDN (2) catalyst are also the result of generally lean or near stoich-
iometric operating conditions. Nickel emissions on the idle cruise tests
were readily detectable when the vehicle was equipped with REDN (2)
system, despite the net rich operating mode of the vehicle. However,
the nickel emissions from the REDN (2) catalyst system may be due to its
lean pre-history. Consequently, at this stage of testing, the nickel
emission rates should not be considered as being typical of this catalyst
system.
Figure II shows the iron emission rates during the 75 FTP's.
Not all samples were available for plotting. FTP Nos. 28 and 29 cor-
responding to Runs 85 and 86 were sent to EPA for Ft analysis and have
not yet been returned for our metals analysis, and the results of the
42nd and 43rd FTP are not yet available. However, based on the limited
data available, there does seem to be a decrease in the iron emission
rate when the reduction catalysts are on the vehicle. With the exception
of one high value (FTP Number 34), the iron emission rates resemble those
of the unequipped vehicle (FTP Runs Nos. 1 to 6). This lends support to
the theory that the increased iron emission rates obtained when the
vehicle is equipped with an oxidation catalyst may be due to reaction
of the exhaust system with the sulfuric acid aerosol.
In many cases, the iron emission rates have exceeded our
original upper calibration limits. We have extended this limit and
will rework those samples which exceeded the original calibration limits.
The upper calibration limits for lead and zinc will also be extended.
The results obtained on the reworked samples will be presented
in the final report.
Section III
Catalysts
Another UOP catalyst has been received from Chrysler Corporation.
This system has been mounted, conditioned and is currently being tested.
An additional pelleted oxidation catalyst purchased from AC
Division of General Motors has been received. This system, a production
unit, is manufactured by Air Products for General Motors. This catalyst
has been mounted and is undergoing conditioning.
123
-------
Section IV
Organic Analysis of Exhaust Partlculate
The analytical program to characterize the nitrogenous and
non-sulfate sulfur components of exhaust particulate has been initiated.
The results of this work will be presented in the next monthly progress
report.
Error Note
The NOX emission rate for Run Number 93 in the fourth monthly
was erroneously reported as 30.890 gins/km. The correct rate is 0.772
gms/km.
The percent conversion Run Number 95 (Appendix IV of fourth
monthly report) was listed as 10.3. The correct value is 3.4%. The
average percent conversion on the FTP for this system (Runs 91 and 95
is therefore 4.2, not 7.7%).
124
-------
250
1!00
150
'•' 100
r-3
A
50
-NONf
•MONO (1)
FIGURE I
HICKEL EMISSION RATES ON FEDERAL TEST CYCLES
CATALYST SYSTEM
-PELLET (I)-
•MONO (2)-
•—MONO (3)
Samples Sent
To EPA
15 20 25
NUMBER OF FEDERAL TEST CYCLES
30
35
-------
FIGURE II
IRON EMISSION RATES ON FEDERAL TEST CYCLES
CATALYST SYSTEM
200 -
160 -
I
- 120 -
10
15 20 25
Number of Federal Cycles
-------
APPENDIX I
REDN (1) EQUIPPED
CHEVROLET
115*
Emission Rates ,
/i **
gms/km
Particulate Emissions
Test No.
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
Exhaust
**
Numbers
***
Z Fuel
Sulfur
0.019
ii
"
ii
it
0.110
II
II
II
II
0.091
it
"
ii
it
Gas Recycle
in Brackets
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
and Air Pump
are Emission
Total
***
Particulate H2S04
0.007
[0.001]
0.005
0.005
0.017
0.016
[ — ]t
0.133
0.076
0.019
0.020
[0.175]
0.118
0.066
0.041
0.002
0.000
0.002
0.001
0.001
0.004
[ 0.000]
0.065
0.027
0.005
0.001
[ 0.000]
0.043
0.024
<0.001
( 2.15)
( 0.00)
( 3.45)
( 1.52)
( 1.14)
( 0.76)
( 0.00)
(18.1 )
( 6.91)
( 0.97)
( 0.22)
( 0.00)
(14.01)
( 7.19)
(<0.22)
Gaseous Emissions
no
10.177
[42.206]
0.350
1.913
7.298
10.657
[98.550]
0.603
0.208
10.439
10.828
[41.926]
0.474
0.350
14.262
HC
0.375
[ 4.19 ]
0.055
0.057
0.498
0.446
[11.804]
0.099
0.024
0.455
0.454
[13.640]
0.077
0.057
0.531
NO,,
2.006
[ 8.906]
1.469
3.175
1.907
2.138
[10.530]
1.976
1.682
1.860
2.529
[ 7.873]
1.842
4.783
2.705
SO?
0.142
[0.972]
0.027
0.040
0.031
0.339
[4.892]
0.137
0.084
0.333
0.321
[7.495]
0.131
0.202
0.346
Disconnected
Rates in gas /hour
Numbers in Parentheses are % Conversions Based on Emitted Sulfate
Filters Too Fragmented to Obtain Accurate Weighings
-------
APPENDIX II
% Fuel
Test No. Sulfur Run Type
111 0.019 75 FTP
112 " Idle (1)
113 " 40 (1)
114 " 60 (2)
115 " 75 FTP
116 0.110 75 FTP
£ 117 " Idle (1)
118 " 40 (1)
119 " 60 (2)
120 " 75 FTP
121 0.091 75 FTP
122 " Idle (1)
123 " 40 (1)
124 " 60 (2)
125 " 75 FTP
REDN (2)' EQUIPPED CHEVROLET
115
Emission Rates, RUB /km
Particulate Emissions
Total
Particulate
0.041
[0.092]
0.005
0.017
0.013
0.025
[0.169]
0.116
0.110
0.016
0.031
[0.081]
0.089
0.114
0.019
H2S04
0.002 ( 2.33)
0.000 ( 0.00)
0.002 ( 3.70)
0.006 ( 9.68)
<0.001 (<1.10)
<0.001 (<0.18)
0.000 ( 0.00)
0.044 (13.10)
0.039 ( 9.97)
0.003 ( 0.57)
0.001 ( 0.22)
[ 0.000] ( 0.00)
0.034 (11.85)
0.040 (15.04)
0.000 ( 0.00)
CO
12.560
[75.589]
0.131
0.006
8.102
11.558
[ 5.195]
0.180
0.014
6.458
6.173
[ 9.050]
0.140
0.066
6.466
Gaseous Emissions
HC
0.582
[7.247]
0.055
0.003
0.285
0.430
[3.424]
0.046
0.005
0.297
0.452
[4.428]
0.038
0.023
0.327
MOV
1.515
[1.205]
1.721
0.319
1.890
2.032
[6.134]
2.083
0.503
2.967
1.966
[6.588]
2.249
3.865
2.620
S02
0.119
[0.035]
0.024
0.004
0.053
0.290
[1.62 ]
0.139
0.020
0.271
0.243
[1.577]
0.107
0.125
0.242
* Exhaust Gas Recycle and Air Pump Disconnected
** Numbers in Brackets are Emission Rates in gms/hour
*** Numbers in Parentheses are % Conversions Based on Emitted Sulfate
-------
APPENDIX III
Test
^°-
81
62
!.:
84
a'j*
66*
37
08
89
SO
91
92
93
94
Run Type
71 H i-
Idle (1)
40 (1)
00 (2)
75 111'
75 FTP
Idle (1)
40 )1)
60 I?)
75 FT!'
75 FTP
Idle (1)
40 (1)
00 (2)
75 FTP
l>ucl
U.019
0.110
0.091
METAL EMISSIONS, CHEVROLET 115 EQUIPPED WITH MONO (3) CATALYST
Ca
<0. 00010
[<0. 00180]
0. 00010
[<0. 00180]
0.00003
0.00008
0.00018
0.00013
[<0. 00180]
0.00007
>0. 00010
0.00020
<0. 00010
[<0. 00180]
<0. 00003
0.00001
[<0. 00180]
<0. 00003
0.00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
0. 00101
[ 0.01820]
0.00017
>0.00020
[ 0.00360]
>0. 00030
>0. 00018
0.00095
>0. 00020
[ 0.00600]
0.00025
>0. 00020
>0. 00101
Cu
<0. 00010
[<0.001cJO]
<0.00003
O.OOOC4
[<0. 00180]
<0. 00003
0.00002
0.00030
0.00039
[<0. 00180]
<0.00003
0.00003
0.00037
HI
<0. 00010
[<0.001bO]
<0. 00003
<0. 00001
[<0. 00180]
<0. 00003
0. 00010
I 0.00280]
0.00013
0.00009
0.00034 *
0.00048
[ 0.00240]
0.00004
>0. 00010
0.00029
Samples 85. 36 Submitted to EPA for Platinum Analysis
-------
APPENDIX IV
METAL EMISSIONS. CHEVROLET 115 EQUIPPED WITH REDN (1) CATALYST
Emission Rate (gins/km)*
Test
No.
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
Run Type
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP
Idle (1)
40 (1)
60 (2)
75 FTP
75 PTP
Idle (1)
40 (1)
60 (2)
75 FTP
Z Fuel
Sulfur
0.019
M
II
II
II
0.110
II
11
II
II
0.091
H
ii
it
n
Ca
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
^0.00006
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0.00003
<0. 00001
<0. 00010
Al
<0. 00010
[<0. 00100]
<0. 00003
<0. 00001
<0. 00010
0.00010
[<0. 00180]
<0. 00006
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0.00003
<0. 00001
<0. 00010
Zn
0.00025
[<0. 00180]
<0. 00003
0.00008
0.00045
0.00021
[<0. 00180]
<0. 00006
>0. 00010
0.00016
<0. 00010
[<0. 00180]
<0.00003
0.00005
0.00027
Cr
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00006
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Fe
0.00064
[ 0.00580]
0.00014
>0. 00009
>0. 00200
>0. 00100
[<0. 00180 1
>0. 00056
>0. 00009
0.00028
0.00020
[ 0.00220]
0.00011
0.00005
0.00062
Cu
0.0001G
[<0. 00180]
<0. 00003
<0. 00001
0.00025
0.00017
[<0. 00180]
0 00019
0.0)023
I0.003GO]
ii.OOOO?
o.iiuoo:-
0.00036
* Numbers In Brackets are Errission Rates In gms/hour.
-------
APPENDIX V
m.TAL HUSSIONS. CHEVROLET 115 EQUIPPED WITH REDN (2) CATALYST
Emission Rate (gins/km) *
Test
No.
Ill
112
113
114
115
116
117
118
119
120
121
122
123
124
125
2 Fuel
Run Type Sulfur
75 K1J> 0.019
Idle (1)
40 (1)
60 (2)
75 FTP
75 FTP 0.110
Idle (1) "
40 (1)
60 (2)
75 FTP "
75 FTP 0.091
Idle (])
40 (1)
60 (2)
75 FTP
Ca
<0. 00010
[<0.001&0]
<0.00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
^0.00003
<0. 00001
<0. 00010
0.00010
[< 0.00180]
<0. 00003
<0. 00001
<0. 00010
Al
0.00016
[<0. 00180]
<0.00003
<0. 00001
<0. 00010
<0. 00010
[<0. 00180]
<0.00003
0.00002
<0. 00010
< 0.00010
[<0. 00180]
<0. 00003
<0. 00001
<0. 00010
Zn
0.00012
[<0. 00180]
<0. 00003
<0. 00001
<0.00010
0.00016
[<0. 00180]
<0.00003
0.00006
0.00010
0.00022
[<0. 00180]
<0. 00003
0.00002
0.00020
Cr
<0. 00010
[<0. 00180]
0. 00100
[ 0.00400]
0.00006
0.00004
<0. 00010
0.00058
[<0. 00180]
0.00008
>0. 00020
0.00038
0.00165
[ 0.00820]
0.00008
0.00040
0.00047
Cu
0.00030
[<0. 00160]
0. 00202
[ n. 01040]
0.00016
0.00008
>0. 00100
0.00047
[ 0.00260]
0. 00005
0.00010
0.00103
>0. 00202
[ 0.00680]
0.00008
>O.OOP09
>0. 00101
Fb
0.00036
t ').0u2&0]
0.00003
O.COOOb
0.00017
0.00026
[<0. 00180]
o.uocn:
>O.OQ010
O.C002J
0 ,004 3
LvO. 00180]
-------
Appendix B2.4
Status Report
ROAP 21BCE
Task 044
Characterize Particulate Emissions from
Production Catalyst Gars..
Concept:
Aside from the Influence of the catalyst itself, the overall
engineering system for emissions control involved integrated, EGR,
engine modifications, fuel-air ratio modulation and the like. In order
to accurately assess the impact of sulfate emissions, it is necessary
to survey a significant number of production cars which will ^e
available for the first time in October and November 1974. It is
projected that as many as 20 such cars (mainly rental vehicles) will
be surveyed during the current fiscal year.
Status:
Purchase plans for several automobiles to be retained for two years
as part of the test fleet are being arranged. Surveys of auto manufac-
turers are being conducted to select cars for testing. New facilities
and improvements to the present chassis dynamometer test cell are being
constructed to increase that efficiency.
132
-------
Appendix B2.5
Status Report
ROAP 21BCE
Task 001
Survey Gaseous and Participate Emissions - California
1975 Model Year Vehicles
This contract program is intended to ascertain the emissions of
regulated pollutants (CO, HC, NOX) and selected non-regulated pollutants
(particulates and sulfates) from consumer-owned, operated, and maintained
1975 model year catalyst-equipped light-duty motor vehicles certified to
meet the 1975 California Interim Federal Emissions Standards. Vehicles
will be repeat-tested during mileage accumulation. The major intent
of this effort is to determine two important factors:
1. The ability of catalyst-equipped vehicles when owned,
operated, and maintained by the general public to
achieve the regulated emissions standards in-use.
2. The "real-world" emission rate of total particulates
and sulfates from catalyst-equipped vehicles.
All tests will be run with the vehicles in the "as received" condition
utilizing tank fuel which will be analyzed.
The procurement package for this contractual program is being processed
at this time. Award is expected in early 1975.
133
-------
Appendix 82.6
Status Report
ROAP 21BCE
Task 082
Characterization and Measurement of Regulated.
SuIfate .and Partlculate Emissions from In-Use
Catalyst Vehicles - 1975 National Standard
This grant program is a companion to ROAP 21BCE, Task 001, "Survey
Gaseous and Particulate Emissions - California 1975 Model Year Vehicles."
In-use catalyst-equipped vehicles will be tested during mileage accumu-
lation to ascertain the emissions rate of both regulated pollutants
(HC, CO, NOX) and selected non-regulated pollutants (participates id
sulfates). This particular grant will focus on 1975 vehicles equipped
with catalysts, certified to meet the 1975 49-state Interim Federal
Emissions Standards, while the above mentioned contract will examine
vehicles certified to meet the 1975 Interim Federal Emission Standards
for California.
Award of this grant is anticipated in December 1974.
134
-------
Appendix B2.7
United States Department of the Interior
BUREAU OF MINES
BARTLESV1LLE ENERGY RESEARCH CENTER
P. O. BOX 1398
BARTLESVILLE. OKLAHOMA 74003
September 12, 1974 Attachment A to memo dated Sept. 12, 1974
Monthly Progress Report
Work Accomplished Through
August 1974
Project No. 4844
Gaseous Emissions Associated with
Gasoline Additives--Reciprocating Engines
Tests were completed using Texaco TFA 318 fuel additive in the Volks-
wagen (table 1). Tests with the Ford and Chevrolet using the TFA 318
were completed and reported last month. The TFA 318 is a polyiso-
propylene carrier oil and is primarily an induction system cleaning
agent, especially Intake valves. The recommended dosage of 220 Ibs
per 1,000 barrels was used in all vehicles.
Tests were also completed on the Ford, Chevrolet, and Volkswagen
using a combination of Lubrizol 8101 and Texaco TFA 318 fuel additive.
The Lubrizol 8101 is a succamld and is multifunctional dispersant-
type additive for gasoline. The dosage used was 140 Ibs of Lubrizol
8101 per 1,000 barrels of fuel plus 220 Ibs of Texaco TFA 318 per
1,000 barrels of fuel resulting in a total of 360 Ibs of combined
additive per 1,000 barrels of gasoline. Emission data for the three
vehicles are presented in tables 2-4. Routine exhaust emissions (CO,
HC, NOX, aldehydes) were not satistically affected by change in fuels
or additives; however, further examination of the data is necessary
before definitive statements may be made pertaining to the additive
related materials.
Experimental work on the three vehicles and 6 fuel additives is now
complete. Compilation of all experimental data and drafting of the
final report is in progress and a rough draft is expected to be avail-
able within 30 to 60 days.
135
-------
TABLE 1. - Exhaust emissions from 1974 Volkswagen
with TFA 318 fuel additive
Fuel
Clear + TFA 318..
Clear + TFA 318..
Clear + TFA 318..
Clear + TFA 318..
High Aromatic
+ TFA 318
Elapsed
miles
0
10
20
480
1,400
1.420
CO
30.7
27.9
29.4
26.5
32.5
28.5
1975
HC
2.65
2.50
2.60
2.36
2.42
2.46
FTP K/mil
NO.
4.45
4.23
4.42
4.27
3.79
3.96
e
Aldehydes
0.088
.082
.082
.085
.075
.065
TABLE 2. - Exhaust emissions from 1974 Volkswagen with
Lubrizol 8101 + TFA 318 fuel additive
Viiol
ruei
Clear
Clear + 8101 + 318...
Clear + 8101 + 318...
Clear + 8101 + 318...
Clear + 8101 + 318...
High Aromatic
+ 8101 + 318
Elapsed
miles
0
20
30
540
1,580
1.600
CO
30.5
29.0
30.4
28.2
31.4
30.3
1975 FT
HC .
2.61
2.45
2.58
2.65
2.65
2.76
T a/mile
NO
3.9?
3.97
4.22
4.62
4.60
4.71
Aldehydes
0.067
.065
.064
.085
.074
.048
136
-------
TABLE 3. - Exhaust emissions from 1974 Chevrolet with
Lubrizol 8101 and TFA 318 fuel additves
«!__ — 1
ruei
Clear
Clear + 8101 + 318..
Clear + 8101 + 318..
Clear + 8101 + 318..
Clear + 8101 + 318..
High Aromatic
+ 8101 + 318
Elapsed
miles
n
20
40
500
1,500
1 540
CO
38 1
37.4
38.3
51.1
41.1
43.7
1975 Fl
HC
1 09
1.49
1.26
1.17
.96
1.24
•P K/mile
NOx
1 94
1.66
1.75
1.77
2.57
2.01
Aldehydes
0 119
.215
.087
.106
.102
.112
TABLE 4. - Exhaust emissions from 1974 Ford with
Lubrizol 8101 and TFA 318 fuel additves
Vital
ruci
Clear
Clear + 8101 + 318..
Clear + 8101 + 318..
Clear + 8101 + 318..
Clear + 8101 + 318..
High Aromatic
+ 8101 + 318
Elapsed
miles
0
20
40
500
1,500
1,520
CO
35.4
29.4
33.6
33.5
32.8
32.4
1975 F
HC
2.64
2.16
2.46
2.41
2.37
2.30
TP K/mile
NOx
3.84
3.61
3.97
4.03
4.38
4.18
Aldehydes
0 .117
.100
.107
.113
.139
• .118
137
-------
United States Department of the Interior
BUREAU OF MINES
BARTLESVILLE ENERGY RESEARCH CENTER
P. O. BOX 1998
BARTLESVILLE, OKLAHOMA 74003
August 19, 1974 Attachment A to nemo dated August 19, 1974
Monthly Progress Report
Work Accomplished Through
July 1974
Project No. 4844
Gaseous Emissions Associated with
Gasoline Additives--Reciprocating Engines
Tests were completed using Du Pont DMA-51 fuel additive in the Ford,
Chevrolet, and Volkswagen. The DMA-51, a carboxylate, is a multi-
functional cleaning additive and was used at a dosage of 15 Ibs per
1,000 barrels. Routine emission data are presented in tables 1-3.
In addition, tests were completed on the Ford and Chevrolet using
Texaco TFA 318 fuel additive, emission data is presented in tables 4
and 5. The TFA 318 is a polylsopropylene carrier oil and is primarily
an induction system cleaning agent, especially for intake valve stems
and intake ports. The TFA 318 was used at the recommended dosage of
220 Ibs per 1,000 barrels.
The Chevrolet vehicle was involved in a minor accident at about 200 miles
into the test using TFA 318. The accident resulted in damage to the
front bumper and front fender. Exhaust emissions were not measurably
affected, therefore, the test was continued.
138
-------
TABLE 1. • Exhaust emissions from 1974 Volkswagen
with DMA-51 fuel additive
Fuel
Clear
Clear + DMA-51 .
Clear + DMA-51 .
Clear + DMA-51 .
Clear + DMA-51 .
High aromatic
+ DMA-51. . . .
Elapsed
miles
0
10.
20
500
1500
1520
CO
30.6
26.9
34.6
29.9
30.8
27.8
1975 FT
HC
2.51
2.54
2.82
2.66
2.48
2.49
P R/mile
NOv
4.19
4.64
4.98
5.16
4.98
4.47
Aldehydes
0.093
.105
.121
.096
.095
.099
TABLE 2. - Exhaust emission from 1974 Ford
with DMA-51 fuel additive
Fuel
Clear
Clear + DMA-51 .
Clear + DMA-51 .
Clear + DMA-51 .
Clear + OMA-51 .
High Aromatic
+ DMA-51. . . .
Elapsed
miles
0
20
40
500
1500
1520
CO
37.0
27.3
24.8
24.7
26.2
30.3
1975 FT
HC
2.69
2.54
2.12
2.41
2.68
2.63
P g/mile
NOx
3.76
3.10
4.24
4.24
3.88
3.75
Aldehydes
0.115
.147
.156
.160
.146
.150
TABLE 3. - Exhaust emissions from 1974 Chevrolet
with DMA-51 fuel additive
Fuel
Clear. .....
Clear + DMA-51 .
Clear + DMA-51 .
Clear + DMA-51 .
Clear + DMA-51 .
High Aromatic
+ DMA-51. . . .
Elapsed
miles
0
40
60
500
1520
1530
CO
47.7
31.3
35.2
41.5 .
37.8
40.5
1975 FT
HC
1.27
.98
1.10
1.23
1.21
1.49
P g/mile
NOV
1.80
2.02
2.21
2.07
1.81
1.92
Aldehydes
0.128
.112
.128
.118
.158
.114
139
-------
TABLE 4. - Exhaust emissions from 1974 Chevrolet using
Texaco TFA 318 fuel additive
Fuel
Clear + TFA 318. .
Clear + TFA 318. .
Clear + TFA 318. .
Clear + TFA 318. .
High Aromatic
+ TFA 318 ....
Elapsed
miles
0
20
30
550
1490
1510
CO
47.5
38.5
35.4
37.7
29.4
35.6
1975 FTI
HC
2.08
1.56
1.25
1.59
1.02
1.02
» g/mlle
NO
1.&
2.06
2.04
1.42
2.01
2.14
Aldehydes
0.125
.133
.114
.117
.119
.105
TABLE 5. - Exhaust emissions from 1974 Ford using
Texaco TFA 318 fuel additive
Fuel
Clear + TFA 318. .
Clear + TFA 318. .
Clear + TFA 318. .
Clear + TFA 318. .
High Aromatic
+ TFA 318 ....
Elapsed
miles
o
20
30
550
1560
1580
.
CO
30.2
26.6
79.9
24.7
26.4
34.6
1975 FTI
HC
2.51
2.58
2.74
2.27
2.15
2.41
> R/mlle
NOV
3.22
3.25
3.73
3.48
3.83
4.00
Aldehydes
0.151
.159
.154
.145
.120
.113
140
-------
United States Department of the Interior
BUREAU OF MINES
BARTLESVILLE ENERGY RESEARCH CENTER
P. O. BOX 1S98
BARTLESVILLE. OKLAHOMA 74003
June 18, 1974 Attachment A to memo dated June 18, 1974
Monthly Progess Report
Work Accomplished Through
May 1974
Project No. 4844
Gaseous Emissions Associated with
Gasoline Additives—Reciprocating Engines
Tests have been completed on all vehicles using amine neutralized
alkyl phosphate fuel additive (DMA4) at a concentration of 15 Ibs per
1,000 barrels. The emission data are presented in tables 1-3. Tests
are in progress on all vehicles using the succinamide fuel additive
(Lubrizol 8101) at a concentration of 140 Ibs per 1,000 barrels with
about 500 miles accumulated to date.
A problem with the Volkswagen was encountered at about 500 miles into
the test with the Lubrizol fuel additive when a cylinder misfire was
noted. The misfire was caused by a tappet adjusting nut coming loose
-and resulting in a valve that was not seating and a bent push rod.
The push rod was replaced and the valve readjusted. The test was con-
tinued rather than repeated from the beginning after an emission check
showed the emissions to be normal.
Analytical Procedures
Analytical methods for quantifying hydrogen cyanid and cyanogen are
inadequate and are requiring still more analytical development. Tests
for nitromethane and nitroethane in vehicular exhaust are continuing
with 1 to 5 ppm nitromethane and up to 1 ppm nitroethane present in
the raw exhaust, with the rotary engines emitting considerably more
than the reciprocating engines. Comparisons are being made to deter-
mine if the nitromethane and nitroethane content in the exhaust is also
related to additive dosage or engine duty cycle.
141
-------
TABLE 1. - Exhaust emissions from 1974 Volkswagen
with DMA4 fuel additive
Fuel
Clear
Clear + DMA4
Clear + DMA4
Clear + DMA4
High aromatic + DMA4..
Elapsed
mile
0
10
20
470
1,430
1,450
1975 FTP, B/mile
CO
24.5
22.1
23.9
28.5
21.3
26.4
HC
2.35
2.34
2.47
2.68
2.53
2.78
NO*
3,88
3.32
3.25
3.89
4.35
4.18
Aldehydes
0.070
.078
.064
.077
.096
.076
TABLE 2. - Exhaust emissions from 1974 Ford with
DMA4 fuel additive
Fuel
Clear + DMA4
High aromatic + DMA4. ,
Elapsed
mile
0
10
20
490
1,600
1,610
1975 FTP, E/m-'.le
CO
24.3
26.0
27.5
29.9
35.0
37.6
HC
2.19
2.41
2.38
2.61
2.85
2.97
NOv
2.60
3.40
3.35
4.20
3.58
3.94
Aldehydes
0.123
.150
.115
.155
.139
.093
TABLE 3. - Exhaust emissions from 1974 Chevrolet
with DMA4 fuel additive
Fuel
Clear + DMA4
High aromatic + DMA4
Elapsed
mile
0
15
40
490
1,490
1.500
1975 FTP. E/mile
CO
59.7
41.3
30.4
39.7
48.6
50.9
HC
1.30
1.42
.86
1.04
1.62
1.51
NOV
2.24
2.02
2.07
1.81
1.90
1.71
Aldehydes
0.086
.100
.112
.133
.123
.095
142
-------
United States Department of the Interior
BUREAU OF MINES
RARTLFWILLE ENERGY RESEARCH CFNTER
P. O. BOX 1308
BARTI.F.SV1LLE. OKLAHOMA 74001
July 22, 1974 Attachment A to memo dated July 22, 1974
Monthly Progress Report
Work Accomplished Through
June 1974
Project No. 4844
Gaseous Emissions Associated with
Gasoline Additives—Reciprocating Engines
Tests have been completed on all vehicles using succinamide fuel addi-
tive (Lubrizol 8101) at a concentration of 140 Ib per 1,000 barrels.
The emission data are presented in tables 1-3. Tests are in progress
using a Du Pont carboxylate (DMA 51) fuel additive at a concentration
of 15 Ibs per 1,000 barrels. Approximately 800 miles have been completed
to date on each vehicle using the DMA 51.
Analytical Procedures
Preliminary analysis of nitrogen compounds produced in automotive exhaust
using clear fuel and F-310 additive shows that the rotary engine vehicles
produce more nitromethane and nitroethane than the reciprocating engines.
The data scatter does not allow distinguishing any fuel additive effect
per se. The data presented in table 4 represent averages of the
Volkswagen, Ford, and Chevelle while operating on both clear fuel and
F-310 fuel additive. Table 5 represents averages of the rotary engine
vehicle and stationary engine using the same fuels in the same time span.
143
-------
TABLE 1. - Exhaust emissions from 1974 Volkswagen
with Lubrizol 8101 fuel additive
Fuel
Clear + 8101...
Clear + 8101...
Clear + 8101...
Clear + 8101...
High aromatic
+ 8101
Elapsed
miles
0
10
20
560
1,470
1,480
1975 FTP, B/mile
CO
25.9
28.2
24.0
22.8
33.0
32.7
HC
9 73
2.71
2.59
2.43
2.79
2.76
NOV
3.88
'3.99
4.11
4.03
4.24
3.86
Aldehydes
0 084
.086
.074
.086
.097
.082
TABLE 2. - Exhaust emissions from 1974 Ford with
Lubrizol 8101 fuel additive
Fuel
Clear
Clear + 8101...
Clear + 8101...
Clear + 8101...
Clear + 8101...
High aromatic
•f 8101
Elapsed
miles
0
20
30
460
1,500
1,520
1975 FTP. B/mile
CO
38.4
32.5
36.8
41.0
37.0
32.6
HC
2.95
2.90
3.33
2.63
2.60
2.14
NO*
4.56
3.50
3.63
3.57
4.09
2.83
Aldehydes
0.125
.118
.124
.124
.113
TABLE 3. - Exhaust emissions from 1974 Chevrolet
with Lubrizol 8101 fuel additive
Fuel
Clear
Clear + 8101...
Clear + 8101...
Clear + 8101...
Clear + 8101
High aromatic
+ 8101
Elapsed
miles
0
20
40
480
1,460
1,480
1975 FTP, B/mile
CO
50.3
45.9
55.6
38.0
44.6
56.4
HC
1.49
1.35
1.55
1.11
1.19
1.50
NOV
2.00
1.99
1.78
1.48
2.15
1.86
Aldehydes
0.116
.119
.114
.125
.128
.087
144
-------
TABLE 4. - Comparison of F-310 fuel additive and clear fuel
on nitrogen compounds emitted
using reciprocating engines
Grains /test
Bag 1
1 Bag 2 1
Bag 3
Composite,
grams /mile
CLEAR FUEL
Hydrogen cyanide...
0.039
.022
.005
0.022
.022
T
0.045
.022
.004
0.009
.006
.001
F-310 FUEL ADDITIVE
Hydrogen cyanide...
0.054
.016
.005
0.039
.023
.004
0.052
.019
.005
0.012
.006
.001
TABLE 5. - Comparison of F-310 fuel additive and clear fuel
on nitrogen compounds emitted
using rotary engines
Grama /test
Bag 1
Bag 2
Bag 3
Composite,
grams /mile
CLEAR FUEL
Hydrogen cyanide. . .
0.044
.061
.013
0.025
.020
T
0.017
.093
.018
0.007
.013
.002
F-310 FUEL ADDITIVE
Hydrogen cyanide...
Nitrotnethane
0.018
.059
.012
0.011
.035
.015
0.032
.072
.016
0.005
.014
.004
145
-------
EFFECT OF GASOLINE ADDITIVES
ON GASEOUS EMISSIONS
FINAL REPORT
Prepared for
Office of Research and Monitoring
Environmental Protection Agency
by
FUELS COMBUSTION RESEARCH GROUP
BARTLESVILLE ENERGY RESEARCH CENTLR
BUREAU OF MINES
under Interagency
agreement number EPA-IAG-097(D)
Review copy--Aujtn»t
146
-------
FOREWORD
This report presents a summary of work performed by the Fuels
Combustion Research Group, Bartlesville Energy Research Center, Bureau
of Mines, for the Environmental Protection Agency, (EPA), Office of Research
and Monitoring under Interagency agreement number EPA-IAG-097(D).
Mr. John E. Sigsby, Jr., was the Project Officer for EPA. The
program at Bartlesville was directed by R. W. Burn, Research Supervisor;
J. R. Allsup, Mechanical Engineer, was the Project Leader; Frank Cox,
Research Chemist, was responsible for the analytical development work
and was assisted by D. E. Seizinger, Research Chemist, and Dr. James
Vogh, Research Chemist. Others who contributed to the experimental work
were L. Wilson, D. Thompson, S. Bishop, and L. Nichols, Engineering
Technicians. J. M. Clingenpeel, Chemical Engineer, and R. E. Stevens,
Mechanical Engineering Technician, assisted in the aldehyde and other
routine chemical measurements.
-------
OBJECTIVE
The need to assess the effects of fuel additives upon auto emissions
has become increasingly pressing as the number and variety of additive
materials have been expanded to meet a growing desire for increased
engine life and performance. To be complete, such an assessment must
include not only information pertinent to the direct-contribution of the
additives themselves to the appearance or composition of objectionable
pollutants, but also the indirect contribution resulting from the use of
these materials.
The primary objective of this study is to provide information which
will serve as a basis to establish the methodology essential to standardi-
zation of additive effect testing. The experimental objective is to
provide data indicating the eftect, if any, of each of two fuel additives
upon the character and/or composition of pollutants emitted by two test
engines and three test vehicles.
The experimental methods described in this study for the production,
collection, and analysis of gaseous auto exhaust samples are expected to
contribute to the specification of fuel additive related test procedures.
EXPERIMENTAL APPARATUS
A. Engines and Vehicles
Gaseous emissions from three 1972 Chevrolet Impalas and two
Chevrolet stationary engines were measured. The vehicles were
1972 models with 350 cubic-inch-displacement (CID) engines,
two-barrel carburetors, and automatic transmissions. Mileage
on the vehicles at the time of acquisition ranged from 1,500 to
148
-------
3,000 miles; therefore, no break-in mileage was accumulated.
The stationary engines were new, but otherwise equivalent to
the vehicle engines. Stationary engine break-in was according
(table 1)
to the Environmental Protection Agency (EPA) 28-hour schedule /
For mileage accumulation, the vehicles were put into "typical"
user service by assignment of the vehicles to BERC employees
whose normal routes consisted of about equal amounts of city
and highway driving. Vehicle inspection and refueling were
conducted by technicians assigned to the project. The sta-
tionary engines were operated repetitively over the LA-4 test
schedule.
B. Fuel
Due to delays in receipt of the EPA fuel, the program was
begun using Indolene clear as the basic fuel. Approximately
5,200 miles were accumulated on the three vehicles using
Indolene fuel. One test cycle with stationary engine B using
clear fuel for 5,000 miles and F-310 for 5,000 miles was com-
pleted before the change to EPA fuel was made. Inspection data
for the Indolene and EPA fuels are given in tables 2 and 3,
respectively.
C. Instrumentation
Analyses of exhaust components which were included in the
program and are considered to be routine are:
149
-------
TABLE 1. - New engine break-in procedure (28 hours)
1. Warm up engine to 180° F coolant outlet temperature at 1,000 rpm,
no load. Set spark advance and best idle according to manufacturer's
specifications.
2. Run 1 hour at 1,500 rpm, no load, automatic spark advance and fuel
flow. Shut down, retorque cylinder heads, and drain and change
lubricating oil.
3. Run cycle 1:
4. Run cycle 2:
RPM
1,500
2,000
2,400
2,600
2,000
RPM
1,500
2,000
2,500
3,000
2,000
Manifold vacuum,
inches Hg
15.0
14.0
14.0
14.0
11.0
Manifold vacuum,
inches Hg
7.0
7.0
7.0
7.0
7.0
Time,
hours
5.0
Time,
hours
0.2
.6
1.0
1.0
.2
3.0
5. Repeat cycle 2.
6. Run cycle 3:
Manifold vacuum,
RPM
2,000
2,500
3,000
3,500
2,800
inches Hg
WOT*
WOT
WOT
WOT
WOT
Time,
hours
1.0
1.0
1.0
.5
.5
4.0 x 4
cycles = 16 hours
* Wide open throttle.
150
-------
TABLE 2. - Inspection data for Indolene Motor Fuel HO III
API gravity
Distillation, %F:
Initial boiling point
107. Evap.
50% Evap.
907. Evap.
Maximum
10% Slope
Reid Vapor Pressure
Oxidation stability, min.
Gum, mg/100 ml (after
Heptane wash)
TMEL, grm. lead/gal
Sulfur weight, 7.
Olefin, %
Aromatic, %
Saturates, %
Octane Research (Clear)
Octane Research (3 cc TEL/gal)
Phosphorus, gms/gal
Sensitivity (Clear)
Sensitivity (3 cc TEL/gal)
ASTM
method
D287
D86
D86
D86
D86
D86
D86
D323
D525
D381
D526
D1266
D1319
D1319
D1319
D2699
D2699
ACM 21.00
Specification
control limit
58.0-61.0
75-95
120-135
200-230
300-325
NMT 415
NMT 3.2
8.7-9.2
NLT 600
NMT 4.0
Nil
NMT 0.10
NMT 10
NMT 35
Remainder
96.0-98.5
NLT 103.0
NMT 0.01
7.0-10.5
NMT 9.0
Sample No.
D-18032
59.1
94
133
224
323
412
2.7
8.7
1440+
1.6
0.02
0.017
5.6
32.6
61.8
97.1
104.1
0.0
10.3
8.3
151
-------
TABLE 3. - Inspection data for unleaded gasoline blend
Research Octane Number
Motor Octane Number
Ron-Mon
Reid Vapor Pressure, psia
Distillation, ASTM D-86, °F:
10%
50%
95%
100%
API gravity at 60° F
FIA Analysis, %:
Aromatics
Olefins
Paraffins
ASTM gum, mg/100 ml
Stability, hrs
Sulfur, ppm
Phosphorous , ppm
Lead, g/gal
Diene Number, meq/liter
2/
Fuel Composition, LV % - :
Benzene
Toluene
n-Butane
Isopentane
n-pentane
Results
93.2
84.7
8.5
10.2
123
199
325
383
61.6
24.0
8.3
67.7
0.57
24+
127^'
1
0.00004
0.0
0.1
8.1
8.0
8.3
5.4
Specification
Minimum
91.5
82
8
9.8
-
-
320
-
-
24
7
62
ionobservable
24+
-
-
-
-
-
-
-
-
~
Maximum
93.5
85
10
10.2
140
250
350
380
-
28
10
69
-
100
30
0.01
1
4
15
12
12
8
NOTE.-Fuel was inhibited with 5 lbs/1000 bbls of Du Pont 22
oxidation inhibitor.
I/ Fails specification, waiver obtained from customer.
2_/ Benzene and toluene were determined by infrared analysis
by direct calibration techniques.
152
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1. Total hydrocarbon (HC) by flame lonization detection
(FID)--Sectarian 400.
2. Nitrogen dioxide (N09) and oxides of nitrogen (NO )
£ X
by chemiluminescence—Thermo Electron 10A.
3. Carbon monoxide (CO) and carbon dioxide (CX^) by non-
dispersive infrared (NDIR)--Beckman 315.
4. Detailed hydrocarbon by gas-liquid chromatography
(GLC) and FID—modified Perkin-Elmer 900 (1-2)
5. Total aldehydes by 3-methyl-2-benzothiazolone hydrozone
(MBTH) colorimetry—Spectronic 20 (3_)
The samples for total aldehyde analysis were metered directly
from the constant volume sampling (CVS) system into the MBTH
reagent solution. With this exception,samples for all routine
analyses were collected from the CVS system in light-proof
Tedlar bags.
Instrumentation prepared for additive specific exhaust compo-
nents include:
1. F&M 810 chromatograph fitted with FID, alkali flame,
and electron capture as optional detectors.
2. F&M 810 chromatograph fitted with FID and alkali
flame parallel detectors and two-pen recorder.
3. Perkin-Elmer 900 fitted with a Coulson electrolytic
conductivity detector (figure 1).
4. F&M 810 chromatograph oven system fitted with modified
Beckman DU spectrophotometer (figure 2).
153
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EXPERIMENTAL PROCEDURES
The methods for analysis of HC, NO,, NO , CO, and CO? are well established
£• X "
and will not be discussed in detail.
A. Organic Manganese Analysis—Methodology
Sample collection was accomplished by drawing diluted exhaust
from the CVS system with a Metal Bellows pump. The sample was
pumped through a 4 in X 3/8 in O.D. stainless steel column
packed with Crhomosorb 102 at ice temperature. Sample flow
was measured with a rotometer placed downstream from the col-
lection column.
The sample was recovered and analyzed according to the following
procedure:
1. To prevent loss of light sensitive manganese compounds,
workup should be carried out in semi-darkness.
2. Backflush the Chromosorb 102 collection column
with acetone to a total volume of about 5 ml.
3. To the acetone solution, add 0.2 ml of a sec-butyl-
benzene solution of a known weight of cyclopentadienylmanganese-
tricarbonyl (CMT-internal standard).
4. Extract the acetone solution three times with 2 ml
volumes of pentane.
5. Bubble dry nitrogen through the pentane solution until
it is evaporated to about 0.3 ml of organic (upper) phase
(water generally separates from the organic material upon
evaporation).
154
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6. Nate the exact volume of the organic layer.
7. Inject 20 |j,l Into a chromatograph equipped with a flame
photometric detector (modified Beckraan DU).
8. Quantitate by peak height relative to that of the
CUT internal standard.
Fuel, lube oil, and intake valve deposits were also analyzed for
organic manganese content. The fuel was diluted to a specific
volume with a benzene solution of CMT and injected into the
chromatograph. Methylcyclopentadienylmanganesetricarbonyl
(MCMT) content was calculated from relative peak heights. The
lube oil was also analyzed in this manner. Weighed samples of
deposits from the manifold side of the intake valves were
digested in a known volume of benzene containing CMT and chromat-
ographed.
Conditions for the chromatographic determination were:
1. Column: 11-1/2 feet X 1/8 in O.D. stainless steel
tubing packed with 4 pet Apiezon L on 90/100 mesh Anachrom ABS.
2. Carrier: helium flowing at 55 c/min
3. Temperature program: 8° C/min from 100° C to 180° C
4. Emission line measured: 403.3 mp,
B. Inorganic Manganese Analysis—Methodology
A Gelman, Type A, glass fiber filter was placed in the sample
line as near as possible to the CVS system. As sample was
drawn by the sample pump for delivery to the Chrpmosorb 102
155
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column, exhaust participates were collected on the filter.
Since MCMT has an appreciable vapor pressure, it was assumed
that all organic manganese was swept through and only inorganic
manganese retained by the filter. The filter was analyzed for
inorganic manganese in the following manner.
1. Place the entire glass fiber filter in a Teflon beaker
and digest with 3N HC1 near 80° C for 15 minutes.
2. Quantitatively transfer beaker contents to a plastic
filtering apparatus containing an acre1 washed cei'ulose membrane.
3. Thoroughly wash the filtering apparatus and retained
solids with 3N HC1.
4. Transfer the filtrate first to a Teflon beaker for
heat evaporation to a few milliliters, then to a 25 ml
volumetric flask.
5. Dilute to volume with 1.5N HC1 and analyze by atomic
absorption (flame) spectroscopy.
6. Use 1.5N HC1 as an instrument blank and correct data
according to the value obtained from parallel analysis of an
unused glass fiber filter.
Deposits from the manifold side of the intake valves and combus-
tion chamber deposits were semi-quantitatively analyzed for
total manganese content by neutron activation analysis.
156
-------
G. Analyses for Nitrogen Compounds --Methodology
Sample collection for nitrogen compound analysis is exceptionally
difficult due to their wide variety of chemical and physical
properties. Several collection methods were attempted but proved
to be inadequate. As a result, vapor samples were taken directly
from the CVS system (or bag) and injected into the PE-900
chromatograph via a 25cc gas sample loop.
Differences in the properties of the nitrogen compounds made
it necessary to analyze with three separate chromatographic
columns. Chromatographic conditions for the analysis of ammonia,
light aliphatic amines, and pyridine were:
1. Column: 10 feet X 1/8 in O.D. stainless steel tubing
packed with 15 pet Carbowax 600 plus 10 pet KOH on 80/100 mesh
Gas-Chrom R
2. Carrier: Helium flowing at 48 cc/min
3. Temperature program: Hold at 25° C for 2 minutes,
then program at 5° C/min to 120° C
Substances such as acetonitrile, pyrrolidine, and cyclohexylamine
can also be analyzed on this column.
Chromatographic conditions for the analysis of all of the pre-
ceding nitrogen compounds (but with less resolution), N-nitros-
amines, nitroso aromatics, nitro aroma tics, aromatic nitriles,
and aromatic amines were:
157
-------
f. Column: 3 feet X 1/8 In O.D. stainless steel tubing
packed with 15 pet Carbowax 1540 plus 10 pet KOH on 80/100
mesh GC-22
2. Carrier: helium flowing "at 52 cc/min
3. Temperature program: Hold at 35° C for 2 minutes,
then program at 6.5° C/min to 180° C
Molecular size for this column is limited to about Cg.
Chromatogrnphic conditions for th<- ^-a lysis of cyanogen, hydrogen
cyanide, nitromethane, and acetonitrile were:
1. Column: 2-1/2 feet X 1/8 n. O.D. stainiess steel
tubing packed with Carbopack B treated with 3-4 drops of H-jPO,
2. Carrier: helium flowing at 42-1/2 cc/min
3. Temperature program: -70° C for 6 minutes then 13°
C/min to 180° C
Detection capability for the nitrogen analyses was provided by
a Coulson electrolytic conductivity cell. Nickel wire was
used as the reduction catalyst, the furnace temperature was
700° C, and the hydrogen flow through the quartz catalyst tube
was 17 cc/min. To prevent moisture condensation, the conductivity
cell was warmed by heating tape from the furnace exit to the gas-
water mixing chamber.
158
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D. Emission Measurement--Methodology
Emissions from three vehicles and two stationary engines were
for 10 minutes at 50 tnph
measured. Prior to testing, each vehicle was driven/to purge
the charcoal canister (evaporative loss trap), then immediately
placed in a soak area at about 75° F and allowed to stand over-
night. Stationary engine test preparation consisted of a shut-
down period lasting at least five hours. Exhaust was tested as
the vehicles and engines were being operated according to the
LA-4 test schedule on chassis and stationary engine dynamometers.
A single CVS bag sample was collected at a constant rate for the
duration of the test. The Roots blower in the CVS pumped a
nominal 330 cfm. This sample was analyzed for total HC, NC^,
NOX, CO, C02, and individual hydrocarbon compounds. CO, HC,
and NOV were calculated in accordance with the Federal Register,
X
Vol. 36, No. 128, Friday, July 2, 1971, section 1201.87.
A test cycle for the engine or vehicle, includes a period of
mileage accumulation with additive-free fuel (4,000-5,000 miles)
to establish baseline emissions and a period of mileage accumu-
lation with the fuel plus additive to establish the effect,
if any, of the additive upon emission levels or trends. Four
test cycles were completed with the two stationary engines; each
engine being tested with AK33X additive at 0.125gMn per gallon
fuel and F-310 additive at 14.2 ml additive plus carrier per
gallon fuel. Mileage accumulation with additive-containing
fuel was 4,000-5,000 miles.
159
-------
One test cycle was completed with each of three vehicles. After
baseline emissions were established (approximately 5,000 miles)
one vehicle was switched to fuel containing AK33X, F310 was
added to the fuel for the second vehicle, and the third vehicle
remained on additive-free fuel. Slightly more than 9,000 miles
were accumulated with additive-containing fuel.
As each test cycle was completed, each engine (both stationary
and vehicle) was disassembled and photographed. Samples of
engine deposits were taken and, when AK37X had i ^en the additive
used, the deposits were analyzed for organic manganese. The
oil from the engines and vehicle using AK33X was also analyzed
for organic manganese.
RESULTS AND DISCUSSION
A. Manganese Determination-Methodology Background
The primary objective of the study is to provide methodology
which can be applied to the determination of the effect of gaso-
line additives upon emissions and the fate of the additive
itself. While the method for organic manganese analysis was
developed specifically for this program, the method (or modi-
fications of the method) should be applicable to the analysis
of other organo-metallic compounds. As for inorganic manganese
analyses, atomic absorption methods are well established for
this and other metallic ions.
160
-------
Chromosorb 102.was very effective as a sample collection medium.
Retention capability was high and recovery from the column was
simple and efficient. A collection efficiency check was made
by applying 0.943 p.g of GMT to the upstream end of the 4 in X
3/8 in O.D. Chromosorb 102 column. After.exposure to 275 liters
of CVS exhaust flowing at 12 liters/min, nearly 99 pet (0.932
pg) of the sample was recovered by direct analysis of the
acetone wash. A large variety of porous polymers is commercially
available. Stability and diverse physical and chemical properties
(pore size, surface area, acid-base properties, polarity, etc)
make them likely candidates for application to collection of
other volatile organo-metallics.
In the early stages of method development, n-tridecane was added
to the recovered sample to minimize loss of the MCMT during
evaporation. No problems occured with small chromatographic
injections, but when the sample size was increased to 20 yJL,
the n-Cjj caused MCMT peak spreading. Chromatographic response,
in terms of peak height, was then dependent upon sample size
as well as concentration. This problem was circumvented by
replacing n-Cji with sec-butylbenzene. MCMT evaporative loss
with sec-butylbenzene was about 5 pet, but addition of the
internal standard (GMT) before the extraction process negates
work-up losses. One possible improvement to the method might
»
be to remove most of the moisture from the porous polymer column
with a dry nitrogen purge prior to recovery, wash the column with
acetone (or pentane), add the internal standard, evaporate to
a small volume, and inject a portion into the chromatograph.
161
-------
The detection system (figure 2) for organic manganese analysis
consisted of a Beckman DU Spectrophotometer equipped with standard
photomultipHer and flame attachments and the Spectral Energy
Recording Adapter (SERA) to allow transfer of the photomultiplier
signal to a strip chart recorder. The only modification to the
system was interchange of the burner oxygen and fuel supply
lines. Oxygen and fuel supplied to the burner in this manner
produce an exceptionally small flame which, in turn, allows
more precise optical focus by limiting the volume in which the
sample is oxidized. Chromatographic effluent was ' J to the
flame through a heated line connected to the sample capillary
of the burner.
Nickel, iron, and chromium trifluoroacetylacetonates have been
chromatographed and detected in this laboratory with the manga-
nese Instrumentation. The less stable corresponding manganese
chelate decomposed within the chromatographic system. One con-
sideration to be given with respect to chromatographic flame
emission analysis is that, although the method may (in many
instances) be made specific for the desired element, the triple
resonance line of manganese is relatively intense. When coupled
with the chromatograph as little as 10 moles of manganese
can be detected with each injection. The sensitivity for other
elements may limit the usefulness of the method. Trace quanti-
ties of some elements, such as phosphorous and lead, are not
suited to detection by flame emission.
162
-------
B. Manganese Determination—Test Results
Figure 3 shows the results of a typical analysis. It is apparent
from this chromatogram that; (1) only extremely high concen-
trations of hydrocarbons are capable of producing interference
(and then only if they are eluted from the column with the
internal standard or desired compound), (2) peak quality is
good, and (3) complete separation of the desired components is
achieved. The peaks in the figure represent 1.07 X 10 moles
GMT (known quantity) and 3.79 X 10"11 moles MCMT (calculated
value). The sample was prepared according to the procedure
given previously and calculation back to the CVS exhaust concen-
tration gives a value of 5.10 X 10~* ppb. Thus, the gaseous
sample stream concentration that is detectable by the method is
less than 2 X 10"2 ppb.
The procedure for manganese determination was developed early
in the prgoram; therefore, the data for AK33X additive related
materials are complete. Figures 4 A, 5A, and 6A show the
manganese present in the exhaust when AK33X is a fuel component.
The organic manganese (MCMT) maximum exhaust levels varied consid-
erably for the two stationary engines and the vehicle ranging
from 1 ug/mile to 5 pg/mile. Expressed in other terms, these
o
values represent CVS exhaust concentrations of 1.40 X 10 ppb
«2
and 7.45 X 10 ppb .respectively. Up to 0.042 percent of the
163
-------
MCMT consumed was emitted unaltered and no organic fragments
of the molecule were detectable in the exhaust. Under similar
conditions, Ethyl Corporation has previously reported (4)
considerably higher values. Engine characteristics, propor-
tional sampling,trapping methods, or the inability of the Ethyl
Corporation method to detect the organic molecule itself may
have been factors in the differences in the reported values;
but the most likely contributor was the exceptionally high con-
centration of manganese (1.25gfa/gal) in the fuel used for the
Ethyl Corporation tests.
It is interesting to note, though not unlikely, that comparison
of figures 4 with 4A, 5 with 5A, and 6 with 6A show that changes in hydro-
carbon emission levels are generally accompanied by corresponding
changes in MCMT emission levels. Both hydrocarbon and MCMT
emissions were increasing at 4,000-5,000 miles with additive.
The stationary engine cycles were terminated at about this point.
Continued mileage accumulation with the vehicle shows hydro-
carbons and MCMT decreasing somewhat to an apparent stabilization.
The hydrocarbon emission trend using AK33X additive is more
easily recognizable by direct comparison of the total hydro-
carbon emissions to those using clear fuel or F310 additive
(figure 11). The values for figure 11 were taken from the
detailed hydrocarbon analysis tables contained in Appendix A.
164
-------
Inorganic manganese emissions from the stationary engines,
figures 5A and 6A, tend to increase along with the MCMT
emissions. Figure 4A, however, fails to indicate a trend for
inorganic manganese emissions from the vehicle. One possible
explanation for this is the relatively mild duty cycle of the
stationary engines (repetitive Federal test cycles) in comparison
to the vehicle (user service). This assumption was given credence
by visual comparison of combustion chamber deposits (to be dis-
cussed later in this report).
Manganese mass balance was low with an exhaust emission range
of 4-30 percent of ingested material. Since the combustion
efficiency of MCMT was 99.4 pet or better, this is due largely
to engine and exhaust system retention of inorganic manganese.
Intake manifold deposits ranged from 4.2 pet to 5.7 pet manganese
(only 0.03 pet or less of this was MCMT). From 7.3 pet to 13.1
pet of the combustion chamber deposits was manganese. Non-
homogeneity of particulates within the CVS stream and losses
within the CVS system could contribute to erroneous values for
the inorganic manganese actually emitted, but program emphasis
was not placed upon particulate sampling.
Engine lube oil used in conjunction with AK33X additive testing
was analyzed for MCMT content and found to range from 0.95 (ig/tnl
to 2.68 pg/ml depending upon mileage accumulation and lube oil
165
-------
added during the test cycle. Lack of test procedure infor-
mation prevents quantitation of MCMT bypass, but estimates made
from the levels found in the oil indicate approximately 2 pg/mile.
This is comparable to the MCMT levels released to the atmosphere
through the exhaust system. Insofar as a potential health
hazard is concerned, organic manganese in the lube oil should
be given special consideration for two reasons: (1) it is
retained by solution in a definite volume of liquid as opposed
to eventual dilution by diffusion in the atmosphere and (2) lube
oil is an efficient U.V. light filter which pr*. ents photo-
chemical decomposition (there was no detectable difference
between fresh samples and those exposed to fluorescent lighting
for up to five months).
Periodic checks of the fuel confirmed that the manganese concen-
tration was within 15 pet of the desired level.
C. Nitrogen Compound Determlnation--Methodology Background1
Isolation of the proposed nitrogen bearing compounds from
exhaust would be an awesome project within itself. Nonspecific
detection systems produce complex exhaust chromatograms in which
not all components appear individually, especially those present
at low concentrations. The development of the chromatographic
techniques for analysis of these compounds was undertaken with this
in mind.
systems
Four types of detection/with some degree of specificity
were available; electron capture, alkali flame ionization,
166
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microcoulometry, and electrolytic conductivity. Electron capture was
considered primarily for confirmation of the presence of aromatic
nitro compounds and N-nitrosoamines, the latter to be accomplished
by conversion to nitramines with hydrogen peroxide and trifluoro-
acetic anhydride or trifluoroacetic acid. With careful atten-
tion to parameter adjustments, alkali flame ionization can be
made to differentiate between most organic nitrogen compounds
and hydrocarbons with essentially complete specificity. The
response of nitrogen compounds to alkali flame, however, is not
solely dependent upon the number of nitrogen atoms, but also the
molecular structure, ftitro compound and hydrogen cyanide responses
were comparatively small and ammonia failed to respond detectably.
The failure of ammonia to respond led to experiments in which
ammonia was mixed with the carrier gas to reduce amine tailing.
A column packed with Ucon LB550X-KOH on Chromosorb W was being
considered at that time for amine separation and the effectiveness
of ammonia in the carrier was demonstrated, but detector specificity
nitrogen compounds as compared to
for/ hydrocarbons was decreased from complete to about 10:1.
Another characteristic of the alkali flame detector which was
considered in judging its applicability was its extreme sensi-
tivity to temperature and gas flow fluctuations.
The remaining two detectors are comparable in terms of nitrogen
sensitivity and selectivity. The selectivity is good for both,
and both respond to any nitrogen compound which is reduced to ammonia
when exposed to nickel catalyst in a hydrogen atmosphere at
elevated temperatures. The Coulson electrolytic
167
-------
conductivity detector was chosen over the Dohrmann microcoulom-
eter because of its relative simplicity of operation and mainte-
nance. The electrolytic conductivity cell requires no periodic
cleaning, electrode maintenance, or electrolyte preparation;
up to the point of bubble formation within the electrode capillary,
hydrogen and carrier flows can be varied over a considerable range
without significant damage to 'peak quality or detector response;
light coke deposits can easily be removed from the nickel wire
catalyst by in situ treatment with oxygen; and the detector
functions satisfactorily with background signals up to about 4 mV.
The cell water and/or water conditior'.iig resins mst be changed
periodically when the background signal becomes excessive, but under
normal conditions, this occurs only after several weeks of con-
tinuous operation.
The variety of nitrogen compounds of interest was considered
when selecting materials for chromatographic columns. Liquid
phases containing nitrogen compounds were rejected a priori to
minimize the probability of excessive background signal and
reduced peak signal due to column bleed. The acid-base properties
of the compounds to be separated were considered as the principal
factor in determining chromatographic behavior. Several column
materials and variations were tested before those which performed
acceptably for the entire spectrum of compounds to be analyzed.
Chromosorb 103 and several variations of Carbowax-KOH combinations
were tested for amine analysis. Porapak Q, S, and QS, Carbosieve B,
and Carbopack A were tested for hydrogen cyanide analysis. The
168
-------
neutral compounds were found to give good quality chromatograms
when separated by the columns prepared for analysis of the basic
or acidic components.
The nitrogen compound classes proposed for study were
amines, pyridines, N-nitrosoamines, and nitro compounds. Indi-
vidual compounds included were hydrogen cyanide and cyanogen.
On first analysis, it appears that the basic compounds (amines
and pyridines) can be isolated from the remaining compounds via
salt formation with hydrochloric acid and extraction of the
neutral and acidic compounds. Further examination, however,
reveals that the neutral and acidic compounds become sensitized,
to various degrees, to hydrolysis upon addition of mineral acid.
Furthermore, hydrolysis of compounds containing the -C:N group
produces ammonium ion and N-nitrosoamines produce secondary
amines; thus interfering with the analysis of the basic compounds.
At best, this method of collection and/or isolation is applicable
to the basic compounds, and only then if consideration is given
to the fact that some of the analyzed components may be hydrolysis
products of non-basic nitrogenous compounds.
Not only the wide range of physical properties (vapor pressure,
solubility, acid base character, etc.) but also the complex
chemistry of these nitrogen compounds is responsible for the
difficulty in their collection, recovery, and analysis. Common
exhaust products with which these compounds may react under
favorable conditions include water, nitrogen oxides (plus water),
aldehydes, ketones, phenols, and unsaturates. In addition,
169
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reactions may take place among the nitrogen bearing species.
Hydrogen cyanide may polymerize, nitroso compounds may
dimerize or react with aromatic amines, and ammonia or amines
add to nitriles under favorable conditions. The presence of
some nitrogen compounds enhances the reactivity of other nitrogen
compounds. For instance, ammonia enters into the addition of
hydrogen cyanide to aldehydes or ketones, and alkylamines
or pyridines act as condensing agents for nitroparaffins and
aldehydes or ketones.
In light of the foregoing discussion, it is evident that
(1) reactions may proceed during sample collectir and processing
and (2) maintenance of sample integrity during this period is
likely to be difficult.
Initial efforts concerning sample collection were based on the
idea of class separation during sampling. A sample collection
train was constructed consisting of a wet cation exchange column,
a wet anion exchange column, and a cold trap at dry ice temperature.
A methanol scrubber at ice temperature was subsequently installed
upstream from the cold trap to prevent plugging by water freeze-
out. The ion exchange resins were wetted by water condensed
from the sample stream. Hopefully, amines and pyridines would
be retained by the cation exchange column, hydrogen cyanide (and
possibly nitroparaffins) retained by the anion exchange column,
and neutral compounds trapped by the cold solvent. The system
was tested by spiking an exhaust stream with the various compounds.
170
-------
When practical, known quantities were injected; but the purities of
hydrogen cyanide, cyanogen, and N-nitrosoamines were not known
and only manufacturer estimates were available for the aqueous
solutions "of light aliphatic amines. Recovery calculations
were based on the detector response to pyridine (known purity)
and the number of nitrogen atoms per molecule as well as detector
response.to equivalent amounts of the individual compounds in-
jected directly into the chromatograph. The system was partially
successful. Amine and pyridine recoveries from the cation ex-
change column were in the 50 to 75 percent range with comparable
nitrile and N-nitrosoamine recoveries from the cold solvent
scrubber. Minimum detection levels were estimated for those
compounds recoverable from this system. These levels for undiluted
exhaust were:
1. Pyridine - 0.02 ppm
2. Aromatic amines - 0.02 ppm
3. C^-C^ aliphatic amines - 0.10 ppm
4. Nitriles - 0.30 ppm
5. ^2-C^ N-nitrosoamines - 0.15 ppm.
These figures are only estimates since the efficiency of the
system and test repeatability were not considered to be adequate.
Hydrogen cyanide, cyanogen, and nitroparaffins were, for practical
purposes, lost; however, the chromatographic technique for
these compounds had not yet been fully developed.
Methanol alone cannot be used as a solvent for scrubbing
the sample stream. Chromatograms of a methanol solution of the
various nitrogen compounds gave peaks which did not correspond
to any of the individual compounds. Some of these unidentified
171
-------
peaks diminished or grew upon standing, giving evidence of
slow, continuing reactions within the solution. Water solu-
tions of formic and acetic acid were also checked for poten-
tial as scrubber solutions, but experimentation indicated
that the basic nitrogen compounds could not be concentrated by
evaporation and recovered in the original form.
All of the previously discussed sample collection tech-
niques failed to establish the presence of nitrogen bearing
compounds (other than NO ) in auto exhaust even with F310
A
additive present in the fuel. This is not surprising since
testing with synthetic- samples gave evi-' mce that jne of the
techniques were sufficiently quantitative or repeatable.
At this point, a different approach was taken in an effort
to demonstrate the presence or absence of the nitrogen compounds
in exhaust at some detectable limit that could be established
with a reasonable degree of confidence. Direct chromatographic
injection of the exhaust (discussed in the Experimental Procedures
section of this report) provides a means to obtain an exhaust
component profile that is least likely to be altered from the
true composition. No intermediate sampling or recovery steps
are involved with this technique, and the chromatographic
response can be related directly back to the exhaust concentration.
Even with this simple introduction system, some precautions are
essential. Separate, preconditioned syringes and sample loops are
necessary for acidic or basic component analysis. For instance,
total loss of small amounts of ammonia results from subsequent
172
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injection into the sample loop used for hydrogen cyanide
analysis. The Coulson electrolytic conductivity detector was
calibrated with known quantities of pyridine and the response
found to be very nearly 5X10" moles nitrogen atom per milli-
volt. Operating at 4 mV full scale the noise level is slightly
less than one division (0.04 mV). Considering the detection
limit to be twice the noise level, 4X10~ moles nitrogen atom
becomes the limit. With a 25cc sample loop, this converts to
0.04 ppm nitrogen atom in the diluted CVS) exhaust. This is
up to twenty times less sensitive than the estimated detection
limits for the sampling train collection technique, but the
reliability of direct, gaseous sampling tends to compensate for
this loss. Results of CVS exhaust analyses by direct injection
were:
1. HCN - 1.0-1.5 ppm found and confirmed.
2. CH,NO_ - 0.2-0.3 ppm found and confirmed.
3. NCCN - trace possible but presence not confirmed.
4. CHoCN - trace possible but low levels are rapidly destroyed
by exhaust.
5. NH, - possible exhaust component but interference peak
prevented definite identification.
Nitrogen compounds either not present or present at levels below
0.04 ppm include:
1. Aliphatic and aromatic amines.
2. Pyridine.
3. C. and larger aliphatic and aromatic nitriles.
4. C^ and larger aliphatic and aromatic nitro compounds.
5 C
' 2-C4 N-nitrosoamines.
173
-------
Hydrogen cyanide and nitromethane consistently appear in exhaust
chromatograms regardless of the presence of F310 additive in the
fuel. Though stable in exhaust, the appearance of cyanogen was
intermittent and could be due to sample syringe hold-over from
previous analysis of synthetics. This is also true of aceto-
nitrile, but experimental evidence shows this compound to be
unstable in exhaust as well. Vapor samples give a chromatographic
peak near the retention time of ammonia even in the absence of
the compound, thus small quantities could be present and remain
hidden. No chromatographic peaks appeared corresp tiding to any
of the remaining nitrogen compounds, so, if present, their exhaust
concentrations were below the detection limit.
Chromatography of the basic nitrogen compounds is illustrated
in figures 12 and 13 . Amines and pyridine were separated to
show peak quality. Approximate locations are indicated for
other amines and compounds representative of the neutral classes
which are eluted from these columns. Vapor samples injected
downstream from the column have shown that the major portion of the
tailing effect takes place within the detector rather than the
column. Figures 14 and 15 are chromatograms of synthetic and
exhaust components, respectively, which are eluted from the
carbopack B-H,PO^ column. For figure ISA, 25cc of gaseous
sample was drawn from the sample line and immediately injected into
the chromatograph. Samples for figures 15B, 15C, and 15D were
taken from a single CVS cold-start bag after aging 1 hour, 1.5 hours,
and 2 hours in the absence of light. Comparison of the exhaust
174
-------
chromatograms can leave little doubt that there is continuous
sample deterioration. With age, hydrogen cyanide decreases and
nitromethane decreases and/or is swamped by a growing peak. Peak
A diminishes with time and peaks B, C, D, E, and F appear and
grow at various times and rates. Little effort was directed
toward identification of the lettered peaks, but oxides of
nitrogen are eluted in areas A-B and E-F giving responses
similar to those of the aged exhaust sample.
Nitrogen Compound Determination—Test Results
The methodology for nitrogen compound analysis was not
adequately developed in time to obtain meaningful data pertinent
to the effect of F310 additive on nitrogenous emissions.
ENGINE DEPOSITS
Induction System
Carburetor
Carburetor throats and bases were examined for deposit
buildup. The deposits were found to be almost equally independent
of fuel additive or duty cycle. Deposits on the carburetor bases
arenas well as the following items,shown pictorally in appendix B
Intake Manifold Passages
The deposits were generally equal in amount from both addi-
tives in the stationary engines. The F310 additive resulted in
softer tar-like deposits in the intake passages of the stationary engines
compared to more crusty deposits resulting from all other engine and vehicle
conditions. The clear fueled vehicle contained more deposits in the intake
passages than did the other vehicles or engines. The F310 additive
vehicle produced unusually clean intake passages as compared to Chose of
the other two vehicles or the stationary engines even after F310 use.
This suggests that the cleaning ability of the additive is dependent upon
duty cycle. It is reasonable
175
-------
Engine Head
Deposits on the engine heads were similar in amounts and
composition to deposits on the piston heads just described; the
major exception being extremely white deposits on the exhaust
valve face of the stationary engines which used F310. This
effect was present but much less pronounced with the vehicles
than with the engines suggesting a duty effect.
Spark Plugs
Spark plug deposits from the AK33X fuel again showed the
characteristic reddish color and, in addition, on one stationary
engine the deposits were so great that che spark gr was being
bridged. The deposits were still very soft and fine. The vehicle
using AK33X did not have nearly so great a quantity of plug
deposits as the engine, also the second engine test with the
AK33X additive resulted in less plug deposits than the first test.
Undoubtedly the duty cycle has a great effect on plug deposits
using the AK33X additive. The plug deposits from tests other than
those using AK33X were similar in color and composition.
Exhaust Valve Stems
Deposits on all the exhaust valve stems were similar in
amounts and composition. The reddish color continued on the exhaust
valves using the AK33X, while the valves of the engine using F310
exhibited a pronounced white color. The white color, however, was
not present on the valve stems of the vehicle using F310.
176
-------
1. Dimitriades, B., and D. E. Seizinger. A Procedure for Routine Use
in Chromatographic Analysis of Automotive Hydrocarbon Emissions.
Environmental Science and Technology, v. 5, No. 3, March 1971,
pp. 223-229.
2. Dimitriades, B., C. J. Raible, and C. A. Wilson.. Interpretation of
Gas Chromatographic Spectra in Routine Analysis of Exhaust Hydro-
carbons. Bureau of Mines Report of Investigations No. 7700, 1972,
19 PP.
3. Coordinating Research Council, Inc. Oxygenates in Automotive Exhaust
Gas: Part I. Techniques for Determining Aldehydes by the MBTH
Method. Report No. 415, June 1968, 21 pp.
4. Brandt, M., et al. Information for the National Research Council
Concerning Methylcyclopentadienyl Manganese Tricarbonyl. Ethyl
Corporation communication, September 8, 1972.
177
-------
Helium
Hydrogen
D.C. Bridge Conductivety cell / Furonce
Scrubber
Coulson electrolytic conductivety detector
FIGURE I .-Chromatogrophic system for analysis of nitrogen compounds.
-------
Helium-
Chromatograph
Oxygen
Hydrogen —*
Burner
Beckman Model DV
Spectrophotometer
Spectral
energy
recording
adapter
Recorder
FIGURE 2.-The detection system for organic manganese analysis.
-------
80
70
60
50
40
o
£.
o
CO
30
20
10
I
I
10
6 4
TIME , mi nutes
FIGURE 3.-Exhaust analysis for MCMT
180
-------
. 4
M
Z
o
« 3
i
Ul
Clear fuel
AK 33X additive
' .125g Mn/gol
2,000
4,000
6,000 8,000
MILES
10,000 12,000
14,000
FIGURE 4.-Effect of mileage accumulation on exhaust emissions
AK33X vehicle.
KEY
Inorganic Mn x 1
Organic Mn > 10
6 3
>»
m
E
at
I 2
in
in
\ \
2,000 4,000
^
AK33X
1 1
*-" vv
additive •
1 ' 1
6,000 8,000 10,000 12,000 14,0
MILES
FIGURE 4A -Effect of mileage accumulation on manganese
emissions AK 33X vehicle .
181
-------
JB
i 4
(A
Z
o
UJ
Clear fuel
-»•«-
AK33X odd- ive
.I25g Mn/gal
I
2 POO
4,000 6,000
MILES
8,000
10,000
FIGURE 5.-Effect of mileage accumulation on exhaust emissions
stationary engine A with AK33X .
E
a
-------
E
o
-------
i4
E
o
CO
z
o
CO
CO
i 2
UJ
HC
Clear fuel
F3IO fliJitive
14.2 ml/gal
2,000
4,000 6,000
MILES
8,000
10,000
FIGURE 7.-Effect of mileage accumulation on exhaust emissions
stationary engine A with F3IO.
«>
- 4
. 3
CO
O
CO
CO
2
HC
Clear fuel
F 310 additive
' 14.2 ml/gal *"
2,000
4,000 6,000
MILES
8,000
10,000
FIGURE 8.-Effect of mileage accumulation on exhaust emissions
stationary engine Q with F3IO.
-------
E
o
w
" 4
(/>
z
o
COx 10
Cleor fuel
2,000 4,000 6,000 8,000 10,000
MILES
12,000 14,000
FIGURE 9.-Effect of mileage accumulation on exhaust emissions
control vehicle.
COx 10
E
o
en
z
O
i
2z C leor f ue I
I
F 310 additive
14.2 ml/gal
2,000 4,000 6,000 8,000 10,000
MILES
12,000 14,000
FIGURE 10.-Effect of mileage accumulation on exhaust emissions
F 310 vehicle .
185
-------
280
260 —
240 —
ZZO —
u
u
E
200
180
160 —
140
2,000
4,000 6,000
MILES WITH ADDITIVE
8,000
10,000
175
ISO
125
100
75
Stationary engine A
50_
I
F3IO
I
1,000 2,000 3,000
175
ISO
125
100
75
50
Stationary engine B
AK33X
F3IO
I
4,000 5,000 0 1,000
MILES WITH ADDITIVE
I
I
I
2,000 3,000 ' 4,000 5,000
FIGURE II -Total CVS exhaust hydrocarbons by GLC.
186
-------
80
60
40
20
J Inl corbo.o.-KOH
Corntr: He, 52 cc/minute
Initial temperature: -35'C tor 6 mmgtet
Final temperature. 180'C
Temperature program :£5*C/minule
• Indicated retention time
*>X y
K-)
r
z
\
CH3NM2
I
I
N
z
= : 1
> V, »
i * 5 i yv
*
i
•z.
OJ
I
0
i
z
CM
X
CM
0
e
X
u>
u
Al t\j
z o
Z Z
z z
X
If!
<-> a Z
1/li
r
K_
10 IS 20
TIME , minulei
FIGURE 12.-Chromatogram of synthetic amines and pyridine, .08 mV/division
80
60
40
80
60
20
10 feet carbooai - KOH
Carrier: He . 48 cc / minute
Initial t«mperature:-2S*C for 6 minute*
Final temperature: I20*C
Temperature program: S*C/minute
• Indicated retention time
o
i.s:: i I .
N i i i "S z
£ «2« %| * %
* i ?, 5 *» •=
H ° o ~ ~ 55
Jv i f\^ yv i t _^ i
z
m
r
tf>
0
y\_
S 10 19 20
25
TIME, mlnutet
FIGURE 13-Chromologrom of synthetic amines and pyridine , .08 mV / division .
25 feet carbopack 8-H3PQ4
Carrier: He, 42 cc/ minute
Initial temperature -70*C for 6 minutei
Final temperature: ISO'C
Temperature program: ll'C/minute
A_
10
20
25
TIME , minutei
FIGURE 14.-Chromatogram of synthetic acidic and neutral nitrogen compounds , .04 mV / divis ion .
187
-------
10 IS
TIME , minulei
FIGURE l5.-Chromatog.ram for acidic and neutral nitrogen compounds. CVS
exhaust, .04 mV/division .
188
-------
TAHLF A-1. - Detailed Hydrocarbon Analyali
Accumulated mileage..
Fuel
Peak
No. Compound
16 n -Pen tone. 2-mechyl-l-butene.
18 Cyclapentane, 3-nethyl-l-
20 2-Methylpentnne,
3,3-dlmetl.yl-l-butena
22 1-Hcxene. 2-ethyl-l-butene...
24 Metbylcyclopcntane,
3-mcthvltran>-2-pentene....
27 Cjclohexene,
2,3-dlnethylpentano,
32 2,ft-Dlneihylhexane,
IS fnlucne, 2 ,3-dinethylhexane. .
41 2 . S-QlnethylheptBtie .
- y
to l-Methyl-3-ethylbenzene
4} 1 -Methyl -2-ethylbenzene
SO «cc-Butylbfnzene. n-decane...
TOCJ! hydrocarbona by CC. ...
4,7iO
Indolenc v F-310
CVS
exhaust
17.39
19.95
2.54
23.45
12.46
.81
€.64
4.61
.98
1.20
.28
3.46
.16
1.59
.58
.24
1.16
.13
1.23
1.33
.72
.13
.69
.70
1.44
9.84
2.94
.99
7.59
.84
.44
2.32
3.09
3.48
29.71
2. 28
1.21
1.58
.12
.18
.13
2.46
5.92
3.56
.31
1.89
.84
.75
3.82
.42
205.70
CVS
eichauat
with
aerubh*f
17.39
2.54
.11
.21
2.24
3.46
1.08
.08
1.23
1.22
.74
.67
.53
1.40
.19
2.10
.81
7.44
.67
.34
2.38
3.05
3.48
1.07
.62
.52
1.24
.27
.14
.12
.06
.13
.18
.02
.15
.07
.17
.14
f-310 Vehicle. poirC
6,070
Indnlcno* F-310
rvs
exhaust
16.56
15.77
1.94
19.96
8.63
.29
' 4.94
2.67
.61
.75
.12
1.77
.09
.89
.34
.14
.73
.07
.62
.69
.38
.06
.35
.39
.77
7.78
1.40
.47
3.71
.37
.19
1.27
1.45
1.63
21.25
.68
.85
.16
.07
.04
1.65
4.29
2.56
.22
1.40
.63
.54
3.63
144.90
CVS
exhautt
with
Mrrubb'r
16.56
1.94
.14
.10
1.01
1.77
.53
.04
.62
.63
.40
.36
.27
.68
.15
1.06
.41
3.72
.32
.17
1.22
1.46
1.63
.51
.31
.26
.63
.13
.07
.08
.04
.08
.12
.01
.03
.10
.11
.09
7,420
EPA + F-310
CVS
cxhauat
12.81
18.88
1.67
18.24
9.61
4.85
3.49
.79
.96
.38
2.99
.25
2.39
.34
.19
.52
4.26
.44
.69
.38
.40
.26
.37
.40
6.37
2.62
.57
4.57
.82
.44
.96
.50
.39
18.81
2.16
1.44
.36
.90
.12
.31
1.67
4.83
2.72
.24
1.33
.54
.53
2.45
.68
CW
exhauat
vlth
•eruhher
12.81
1.67
.15
.07
1.81
2.99
2.25
5.08
.44
.43
.22
.15
.15
.17
.02
2.07
.38
4.57
.53
.25
.80
.61
.39
.33
.92
.95
.24
.68
.02
.16
.06
.32
.04
.07
.09
8,550
EPA .| F-310
CVS
exhauat
12.95
18.12
1.53
18.11
9.20
.97
4.63
4.26
.77
.93
.34
3.92
.25
3.12
.36
.20
.52
5.25
.51
.78
.40
.40
.26
.39
.32
5.52
3.15
.60
5.63
.89
.48
.97
.48
.25
19 32
2.40
1.55
.20
.85
.06
.20
1.46
4.72
2.35
.16
1.11
.47
.43
1.69
.49
CVS
exhauBt
vlth
He rubber
12.95
1.53
.07
.10
2 50
3.92
3.01
5.66
.51
.53
.31
.21
.17
.14
.04
2.71
.49
5.63
.67
.34
.92
.47
.25
.30
.97
1.01
.07
.69
.02
.19
.10
.35
.04
.06
.01
w.l
M'A • 1
ns
egliauM
i: '•
II HI
l.M
16.70
7.41
. >:
4.11
3 el
.»
.41
.01
3.U
.10
1.90
.11
.09
.36
S.7t
.40
.47
.20
.15
.16
.26
.1)
S.38
1.6)
.67
6.8S
1.31
.57
1.2)
.6)
.31
21.40
2.f>
1.94
.2)
1.10
.or
.77
1.61
5.20
2.56
.10
1.2*
.10
.57
1.91
.5)
. I-
i >l
*• • •<
»ii
* 1 •'
i <
t
.li
1 1.
J.ri
1. 01
.to
.11
.71
.2)
.18
.11
.04
1.])
.1*
4 %l
.11
.M
i.n
.M
.»!
.«
I.JO
i.r»
.19
.!»
.0*
.to
.1'
.*«
,n§
.04
01
.It
160.65 157.19 1S0.3J
* Includes »xhaust hydrocarbons not reported in detailed analyaie.
189
-------
F-310 Vehicle. ppmC--Continued
Accumulated mileage...
8 n-Butane, 1 ,3-butadiene
14 n-Pentane. 2-methyl-l-butene
18 Cyclopentane. 3-methyl-l-
20 2-Methylpencane,
2 ,3-dimethyl-l-butcne
22 1-Hexene, 2-ethyl-l-butene. .
24 Methylcyrlopentane,
3-methyltranB-2-pentene. . .
27 Cyclohexcne,
2,3-dLmethylpentane.
32 2,4-Dimethylhexanc,
35 Toluene. 2,3-dlncthylhexane.
41 2.3-ntmcthylheptane.
47 l-Hethyl-2-ethylbeniene
49 1 ,2 ,4-TrIaietliylbeniene
50 rec-Putylbenzene, n-decane..
EPA + F-310
CVS
exhsust
12.91
18.40
1.S9
18.27
9.57
4.86
3.93
.75
1.05
.40
3.05
.07
2.71
.23
.09
.36
5.51
.36
.41
.17
.12
.16
.25
.09
6.06
3.71
.70
6.73
.98
.S3
1.16
.59
.29
22.54
2.55
1.69
.19
.98
•.06
.23
1.66
5.47
2.65
.18
1.33
.52
.45
1.76
.47
CVS
exhaust
vlth
scrubber
12.91
1.59
.20
.10
1.88
3.05
2.43
4.53
.36
.37
.21
.16
.14
.12
.04
3.19
.59
6.73
.84
.43
1.16
.59
.29
.36
1.13
1.20
.09
.87
.04
.29
.14
.45
.01
.06
.08
.02
.11
10.550
EP> + F-310
CVS
exhaust
13.65
18.64
1.57
18.90
8.08
4.87
3. 84
.41
.44
.04
3.41
.10
2.93
.21
.08
.35
5.58
.32
.34
.15
.12
.15
.20
.10
6.35
3.15
.57
5.96
.82
.43
.99
.50
.19
21.75
2.19
1.43
.31
.81
.01
.15
1.60
5.36
2.58
.11
1.22
.49
.41
1.86
.39
CVS
exhaust
with
scrubber
13.65
1.57
.42
.40
1.93
3.41
2.89
5.07
.32
.28
.16
.15
.11
.08
.45
2.89
.52
5.96
.69
.36
.95
.50
.19
.28
1.09
1.09
.11
.76
.01
.19
.09
.41
.15
.08
.07
.09
EPA + F-310
CVS
exhaust
11.85
16.81
1.52
16.49
7.96
.67
4.20
4.29
.60
.73
.14
4.10
.13
3.29
.26
.12
.40
6.24
.43
.51
.23
.17
.16
.20
.09
5. 15
3.32
.60
6.37
.87
.47
1.08
.56
.25
20.52
2.54
1.67
.16
.96
.04
.21
1.S4
5.51
2.52
.IS
1.46
.57
.48
1.89
.44
CVS
exhaust
with
scrubber
11.85
1.52
.13
.10
2.61
4.10
3.19
5.57
.43
.42
.22
.14
.14
.11
.04
3.09
.55
6.37
.78
.41
1.03
.57
.25
.30
1.02
1.07
.07
.79
.03
.26
1.27
.44
.19
.11
.11
.11
EPA + F-310
CVS
exhaust
9.84
15.00
1.32
13.67
7.73
4.06
3.37
.39
.75
.07
3.31
.14
2.92
.27
.16
.41
5.61
.37
.40
.26
.20
.24
.29
.19
4.98
3.43
.66
6.72
1.04
.S3
1.19
.63
.33
20.73
2.02
1.58
.15
.96
.07
.29
1.66
5.33
2.S2
.26
1.29
.53
.55
1.65
.26
CVS
exhaust
vlth
scrubber
9.84
1.32
.19
.09
1.93
3.31
2.67
5.24
.37
.39
.18
.16
.17
.15
.OS
3.19
.59
6.72
.86
.44
1.00
.61
.33
.42
1.40
1.37
.10
.87
.04
.28
.13
.44
.17
.10
.11
.10
EPA+F-310
CVS
exhaust
10. IS
17.69
1.59
15.84
9.03
4.76
4.07
.67
.98
.29
3.80
.17
3.27
.28
.16
.47
6.33
.47
.49
.34
.29
.25
.34
.22
5.31
3.76
.68
7.18
1.07
.56
1.21
.61
.30
23.02
2.69
1.78
.19
1.00
.06
.25
1.78
5.68
2.76
.23
1.44
.54
.46
1.91
. .55
CVS
exhaust
with
scrubber
10.15
1.59
.09
.09
2.20
3.80
3.06
5.50
.47
.51
.31
.28
.22
.20
.05
1.51
.66
7.18
.96
.50
1.17
.63
• .30
.36
1.14
1.12
.09
.82
.03
.25
.16
.45
.04
.22
.13
.15
.13
*To»l hydrocarbons b, CC.,.. !«•« »*•" 153.27 144.90 166.86
* Includes exhsust hydrocarbons not reported In detailed analysis
190
-------
TABLE A-2. - Det«lled Hydrocarbon Analyst!
Accumulated mileage..
Peak
No. Compound
1 Methane
2 Ethylene
11 3-Mothyl-l-butene
14 n-Pentane. 2-aeehyl-l-butene
17 2-Mcthyl-2-butene
18 Cyclopentane, 3-methyl-l-
19 2,3-Dimethylbutana
20 2-Nethylpentane,
22 1-Kexene, 2-ethyl-l-butene..
24 Mathylcyclopentane,
3-oethyltrana-2-pentene. . .
27 Cyclohexene,
2,3-dlmethylpentana,
28 3-Hathylhexane
32 2,4-Dlmethylhexane.
35 Toluene, 2,3-dlmethylhexane.
36 2-Methylheptane
18 2,2,9-Trtmethylhezane
40 2,3,5-Trlaethylhexane
41 2,5-Dlmethylheptana,
43 £-Xyleno, m-«ylene
44 i-Xylene
*» l-Methyl-3-ethylbeniene
47 l-Hethyl-2-ethylbenien*
*« fesltylene
-* I.2.t-Trtnethylben»ne
vl •^•Huiylbenrenel n-decane..
•'.•i.l livilrncarhona by CC....
4^740
Indolenc
CVS
exhauat
17.49
19.75
2.50
24.75
12.77
1.21
6. 25
5.26
1.08
1.45
.36
3.98
.22
1.77
.61
.28
1.17
.19
1.31
1.48
.85
.21
.75
.73
1.40
9.61
2.59
1.04
7.09
.76
.38
2.11
2.87
3.22
28.32
2.12
1.15
1.46
.28
.14
.08
2.39
6.06
3.68
.37
2.13
.98
.67
4.40
.JO
212.42
+ AK33X
CVS
exhauat
with
acrubber
17.49
2.50
.14
.29
2.93
3.98
1.22
.09
1.31
1.28
.82
.75
.53
1.32
.19
1.99
.78
7.09
.62
.30
2.20
2.89
3.22
.95
.35
.40
1.04
.21
.13
.11
.06
.13
.20
.09
.24
.12
.28
.22
AK33X Vehicle. penC
5,305
Indolent + AIO3X
CVS
exhauat
17.10
19.02
2.55
23.31
12.39
1.20
6.27
4.40
1.04
1.51
.46
2.91
.14
1.40
.46
.21
1.01
.13
.98
1.12
.63
.14
.57
.55
1.06
8.78
2.00
.68
5.56
.56
.28
1.66
2.24
2.48
25.18
1.63
.84
1.15
.24
.13
.10
2.30
5.43
3.31
.38
2.00
.90
.82
4.18
.57
191.64
CVS
exhaust
with
scrubber
17.10
2.55
.15
.25
2.10
2.91
.95
' .07
.98
1.01
.66
.62
.44
1.11
.17
1.52
.60
5.56
.54
.27
1.74
2.16
2.48
.78
.46
.38
.90
.21
.11
.09
.05
.11
.16
.01
.03
.13
.06
.13
.11
7.170
EPA+AK33X
CVS
exhaust
14.61
23.32
2.27
21.47
12.32
6.40
5.03
.88
1.44
.43
4.15
.31
3.28
.45
.27
.70
5.29
.60
.60
.52
.47
.36
.50
.49
7.46
3.15
.64
5.59
.74
.37
1.06
.67
.48
24.09
2.11
1.33
.36
.76
.06
.19
2.02
5.87
3.20
.17
1.48
.63
.33
2.54
.60
190.29
CVS
exhaua t
with
acrubber
14.61
2.27
.18
.13
2.65
4.15
2.99
5.37
.60
.59
.28
.25
.22
.30
.05
2.43
.50
5.59
.67
.31
1.03
.64
.48
.36
.80
.81
.27
.59
.02
.15
.01
.30
.04
.08
.03
.12
8.030
EPA + AK33X
CVS
exhaust
16.01
24.35
2.40
23.93
11.05
61 36
4.78
.68
.68
.07
4.30
.14
3.69
.36
.15
.58
6.73
.63
.69
.31
.15
.28
.36
.33
8.08
4.17
.84
8.47
1.17
.60
1.60
1.07
.79
29.83
3.21
2.03
.34
1.12
.07
.25
2.40
7.42
3.77
.24
2.16
.80
.76
2.93
.64
210.72
CVS
exhauat
with
scrubber
16.01
2.40
.15
.13
2.32.
4.50
3.43
5.88
.63
.63
.37
.34
.31
.38
.09
3.78
.77
8.47
1.02
.30
1.60
1.06
.79
.52
1.24
1.29
.41
.93
.05
.25
.10
.46
.01
.06
.13
.01
.03
.13
9.434
EPA + AK33X
CVS
exhaust
18.07
28.43
2.76
27.36
14.82
7.74
7.08
1.07
1.67
.50
6.88
.40
5.73
.39
.34
.83
10.65
.85
1.28
.71
.59
.51
.71
.55
8.40
5.92
1.23
11.08
1.70
.90
1.94
.96
.48
35.69
4.09
2.74
.30
1.60
.10
.40
2.93
9.22
4.41
.33
2.31
.94
.84
3.21
.80
CVS
exhauat
with
scrubber
18.07
2.76
.24
.21
4.19
6.88
3.50
10.31
.85
.94
.54
.48
.40
.34
.12
5.40
1.06
11.08
1.48
.74
1.92
.96
.48
.59
1.93
2.06
.16
1.53
.09
.49
.39
.82
.12
.10
.19
.28
.26
271.80
:<••)•• nhauac hydrocarbons not reported In detailed analysis.
191
-------
TABLE A-2. • Detailed Hydrocarbon Analysla
Peak
No. Congound
1 Methane
3 Ethane
11 3-Hethyl-l-butene
14 n-Pen:ane, 2-methyl-l-butene
IB Cyclopentane, 3-methyl-l-
19 2,3-Dlnethylbutane
20 2-Hethylpentane,
2,3-dlaethyl-l-butene
Zl 3-Hechylpentane
22 1-Hexene, 2-ethyl-l-buteue..
23 n-riexane, c_U-3-he«ne
24 Methylcyclopentane,
J-methyltranE-2-pentena...
27 Cyclohexene,
2,3-dlmethylpentane,
28 3-Methylhexane
32 2,4-Dlnethylhexane.
35 Toluene, 2,3-dlmethylhexane.
41 2,5-Dlmelhylheprane,
46 l-Hethyl-3-etlwlbeniene
47 l-M*chyl-?-ethylbenirne
JO i£c_-Butylbeniena, n-decane..
10.353 1
EPA 4
CVS
exhaust
15.90
31.22
3.09
26.87
16.05
1.46
8.40
6.70
1.15
1.66
.30
5.45
.28
4.57
.47
.23
.65
8.24
.59
.78
.37
.27
.29
.35
.17
9.00
4.38
.87
8.18
1.26
.65
1.26
.64
.30
32.29
3.54
2.25
.65
1.27
.08
.31
2.80
8.31
4.25
.31
2.29
.86
.77
3.52
.81
UC13X
CVS
Exhaust
with
scrubber
15.90
3.09
.53
.48
3.54
5.4!>
4.29
7.72
.59
.64
.34
.30
.26
.21
.07
3.96
.78
8.18
1.11
.58
1.23
.64
.30
.39
1.27
1.35
.25
.94
.03
.25
.16
.47
.18
.09
.10
.10
AKJIX Vehicle. ppnC--Continued
EPA *
CVS
exhaust
17.01
26.91
3.02
22.25
14.17
7.38
5.32
.95
1.47
.33
3.90
.15
3.70
.31
.13
.49
6.91
.45
.56
.24
.15
.23
.32
.14
7.92
4.09
.85
7.43
1.13
.59
1.17
.59
.28
29.44
3.12
2.02
.21
1.14
.07
.27
2.56
7.55
3.87
.25
2.09
.76
.65
2.79
.67
AK3JX
CVS
Exhaust
with
scrubber
17.01
3.02
.36
.13
2.13
3.90
3.17
6.22
.45
.51
.26
.24
.21
.14
.08
3.61
.72
7.43
1.00
.51
1.16
.60
.28
.35
1.19
1.28
.10
.97
.06
.34
.11
.53
.01
.19
.11
.11
.12
1 12.140 I
EPA +
CVS
exhaust
15.85
27.62
?.81
22.31
14.10
7.44
5.40
.77
1.87
.21
3.99
.18
3.53
.37
.18
.51
6.30
.35
.41
.21
.16
.23
.27
.14
8.39
3.21
.64
6.20
.93
.48
1.01
.49
.20
28.57
2.44
1.62
.15
.95
.05
.26
2.55
7.44
3.76
.29
2.07
.77
.68
2.64
.64
tK33X
CVS
Exhauit
with
scrubber
15.85
2.81
.21
.12
2.45
3.99
3.15
4.87
.35
.37
.17
.15
.15
.11
.05
2.93
.57
6.20
.86
.43
1.02
.51
.20
.31
1.08
1.13
.08
.89
.04
.31
.20
.50
.20
.11
.11
.11
1 12.740 I
EPA +
CVS
exhaust
14.15
26.73
2.78
22.12
13.98
7.09
5.82
.84
1.05
.09
4.76
.13
4.13
.30
.11
.46
7.75
.47
.48
.20
.14
.21
.29
.13
7.31
4.37
.83
6.08
1.79
.67
1.42
.68
.32
30.16
3.57
2.32
.25
1.25
.06
.27
2.60
7.94
3.89
.22
.22
.78
.71
2.73
.56
AK33X
CVS
Exhaust
with
14.15
2.78
.13
.12
2.89
4.76
3.75
6.23
.47
.47
.21
.17
.18
.1*
.05
3.85
.72
8.08
1.04
.51
1.35
.67
.32
.43
1.58
1.63
.09
1.15
.02
.26
.16
.65
.24
.15
.15
.14
EPA*
CVS
exhaust
12.27
25.94
2.65
18.80
14.16
7.39
5.67
1.22
1.60
.47
4.25
.16
3.62
.30
.13
.50
6.59
.45
.51
.22
.20
.18
.23
.10
6.52
3.64
.69
6.65
.94
.54
1.14
.52
.22
26.23
3.38
2.12
.23
1.06
.05
.21
2.33
6.65
3.39
.20
1.82
.66
.60
2.96
.83
IkJH
CVS
Exhausc
with
12.27
2. AS
.13
.13
2.62
4.25
3.31
5.26
.45
.47
.28
.20
.15
.12
.C3
3.10
.59
6.65
.82
.42
1.12
.52
'.22
.27
1.04
1.09
.07
.78
.03
.21
.07
.37
.12
.07
.06
.07
•Total •lydiOLAiL..!)! by (X V.I. I/ 217.74 211.23 212.18 200.46
• Iniludct r*liau>i hydrocarbons not reported in detailed analysis.
192
-------
TABLE A-3. - Detailed Hydrocarbon Analvala
Peak
No . CtrnDOund
14 n-Pentane. 2-raethy l-1-bucene
18 Cyclopencane, 3-methyl-l-
19 2,3-Dlaethylbutane
20 2-Mcthylpentane,
22 L-Hexene. 2-cthyl-l-butene. .
29 n-Hexane, £la_-3-hexene
24 Methylcyclopentftne,
3-0ethyltrans-2-pencene...
27 Cyclohexcne,
2,3-dluethylpentane,
32 2,4-Dlmethylhexane,
35 Toluene, 2,3-dlaethylhexane.
41 2,5-Dlnrthylheptana,
66 l*Hcthyl-3-ethyloenzeiie
4* Meiltylene
M> »ec-Biicylben:enc, n-decano..
4,550
CVS
exhaust
16.86
17.79
2.22
23.96
11.01
.98
5.82
4.93
.95
1.06
.31
4.46
.24
1.95
.69
.32
1.35
.22
1.63
1.83
1.03
.26
.92
.92
1.91
8.70
3.33
1.17
9.90
1.12
.52
?.91
3.95
4.49
29.56
2.62
1.42
1.92
.39
.24
.19
2.39
5.73
3.35
.42
2.00
1 .92
.88
3.91
.72
CVS
ethaust
with
acrubber
16.86
2.22
.10
.27
2.98
4.46
1.35
.10
1.63
1.62
.98
.91
.67
1.77
.24
2.75
1.04
9.57
.82
.41
2.93
3.99
4.48
1.29
.73
.57
1.45
.31
.18
.15
.08
.16
.22
.07
.26
.12
.31
.14
•Tnial hydrocnrhonc by CC.... 216.16
Control Vehic a. ppmC
5,950
CVS
exhauat
17.40
17.07
2.20
24.65
10.62
.70
5.72
3.77
.83
1.11
.32
3.43
.19
1.59
.56
.28
1.15
.14
1.23
1.24
.75
.16
.68
•
.65
1.35
8.69
2.42
.83
7.08
.73
.38
2.22
3.06
3.46
26.36
1.91
.96
1.50
.32
.18
.13
2.29
5.62
3.26
.49
2.15
.99
.94
4.12
.77
CVS
exhaust
with
acrubber
17.40
2.20
.13
.16
1.92
3.43
1.07
.09
1.23
1.23
.79
.72
.54
1.39
.27
2.01
.76
7.08
.59
.31
2.28
3.05
3.46
1.04
.60
.49
1.25
.26
.16
.15
.08
.16
.23
.05
.21
.10
.24
.15
CVS
exhaust
12.04
17.02
1.48
17.05
8.48
4.41
3.28
.61
.95
.34
2.93
.26
2.36
.35
.23
.54
4.04
.43
.43
.42
.»3
.26
.38
.36
5.99
2.46
.55
4.53
.76
.41
.93
.50
.40
16.77
1.71
1.22
.29
.88
.13
.34
1.62
4.27
2.47
.26
1.04
.50
.46
1.72
.58
CVS
exhaust
with
acrubber
12.04
1.48
.13
.06
1.81
2.93
2.18
4.16
.43
.39
.17
.16
.17
.19
.02
2.06
.39
4.53
.54
.26
.81
.63
.40
.38
.94
.97
.26
.59
.01
.15
.01
.33
.05
.09
.02
.11
8.725
CVS
cxhauit
13.77
18.34
1.52
19.40
9.35
. .99
4.77
4.20
.73
.97
.42
3.90
.08
3.30
.16
.06
.34
6.42
.41
.42
.17
.10
.16
.22
.13
6.04
3.72
.71
7.10
.99
.51
1.20
.64
.36
21.37
2.39
1.58
.22
.95
.06
.25
1.57
5.09
2.38
.13
1.25
.48
.42
1.58
.42
CVS
exhauit
with
13.77
1.52
.10
.09
2.39
3.90
3.01
5.22
.41
.40
.19
.15
.15
.14
.07
3.44
.62
7.10
.83
.41
1.17
.72
.36
.37
1.16
1.20
.12
.80
.02
.20
.09
.39
.05
.09
.08
9.865
CVS
exhauit
13.45
17.92
1.48
18.36
7.4:
.26
4.30
4.13
.50
.51
.07
3.77
.12
3.03
.25
.11
.39
5.78
.39
.47
.22
.16
.16
.26
.17
5. 80
3.56
.66
6.72
.96
.53
1.21
.63
.31
21.26
2.53
1.74
.19
1.15
.09
.32
1.67
5.57
2.60
.14
1.30
.4)
.42
1.S9
.39
CVS
exhaust
with
13.45
1.48
.24
.13
2.56
3.77
2.90
4.76
.39
.41
.26
.23
.18
.20
.09
3.12
.57
6.72
.87
.43
1.21
.65
.31
.40
1.20
1.30
.10
1.01
.07
.34
.18
.51
.06
.10
09
198.66 153.15 163.42 157.81
mhaujt hydrocarbon] not reported In detailed analybla.
193
-------
TABLE *-). - Detailed Hydrocarbon Anslyilt
Control Vehicle. PpmC--Cnntlnug
-------
TABU A-4. . Detailed Hydroc«rbon Analvala
Peak
No . Compound
1 Met hane
2 Ethylene
8 n- Butane, 1,3-butadlene
1 1 3-Methy 1-1-butene
14 n-Pentane. 2-raothyl-l-butena
17 2-MethyI-2-butcne
IB Cyclopentane, 3-tnethyl-l-
19 2,3-Dlmethylbutane
20 2-Mechylpentane,
2,3-dlmethyl-l-butena
22 1-Hexene, 2-ethy 1-1-butene..
24 Mcthylcyclopentane,
3-methyltranB-2-peneene...
27 Cyclohexene,
2 , 3-dimethy Ipentane ,
28 3-Methy Ihexane
31 Nethylcyclohexane
32 2 ,4-Mmethy Ihexane,
33 2,3,4- rrlaeLhy Ipentane
35 Toluene, 2,3-dimethylhexane.
36 2-Methylheptine
38 2,2,5-Trlnethylhexane
40 2,3.5-Trlmethylheaane
41 2,5-Dimethylheptane,
46 1 -Methyl-3-ethylbenzene
47 l-Methyl-2-ethylbencen
48 Men Itylene
49 1,2 ,4-Trlmethy Ibeniene
SO icc-Butylbenrene, n-decane..
Two |
CVS
exhiuat
9.28
10.56
1.10
11.67
6.57
.93
3.20
4.77
.71
.72
.18
4.15
.17
1.64
.54
.24
.96
.17
1.26
1.35
.75
.16
.65
.62
1.21
4.70
2.18
.82
5.92
.62
.30
1.67
2.39
2.70
16.96
1.47
.75
1.05
.19
.11
• .07
1.31
2.97
1.75
.18
.98
.39
.39
2.19
lent
CVS
exhauat
'with
acrubber
9.28
1.10
.34
3.49
4.24
1.22
.08
1.29
1.26
.80
.72
.45
1.14
> .14
1.65
.61
5.70
.47
.23
1.67
2.33
7.68
.74
.41
.28
.87
.15
.08
.05
.02
.06
.07
.07
.13
Stationary Enalna A. DM&C
1 Toso
Indo
CVS
exhauat
7.68
11.07
1.32
11.34
6.47
.43
3.48
•J.57
.51
1.01
.19
1.63
.13
.89
.48
.27
.64
.10
.51
.53
.•37
.16
.30
.26
.52
4.46
.87
.29
2.50
.19
.09
.66
.95
1.07
11.47
.67
.31
.42
.05
.03
.02
.96
2.07
1.48
.12
.70
.27
.30
1.48
.18
lena
CVS
exhauat
with
acrubber
7.68
1.32
.20
1.33
1.63
.50
.05
.51
.53
.37
.29
.20
.53
.09
.68
.24
2.39
.16
.08
.67
.93
1.05
.28
.15
.07
.34
.06
.04
.02
.04
.09
.02
.02
.03
1 T930 1
Indo
CVS
exhauat
6.83
10.20
1.24
10.47
5.49
.31
2.90
1.91
.40
.36
.10
1.10
.06
.56
.30
.09
.46
.08
.39
.46
.25
.09
.21
.23
.47
3.97
.83
.27
2.55
.24
.10
.65
.76
.88
10.46
.42
.58
.07
.03
.02
.86
1.79
1.33
.09
.57
.24
.28
1.80
Lone
CVS
exhauat
with
acrubber
6.83
1.24
.13
.92
1.10
.33
.02
.39
.40
.25
' .20
.14
•38
.05
.55
.21
2.02
.16
.07
.64
.75
.88
.26
.15
.12
.31
.05
fr
.03
.02
.01
.03
.02
.02
.01
.03
.06
1 41950 1
Indc
CVS
exhaua t
7.53
11.07
1.28
10.42
6.48
.76
3.39
2.43
.62
.68
.27
1.53
.13
.74
.32
.14
.64
.13
.53
.67
.40
.23
.31
.34
.64
4.23
1.10
.36
2.66
.37
.20
.95
1.01
1.21
12.05
.57
.65
.14
.11
.12
1.08
2.16
1.56
.18
1.00
.35
.50
2.17
lena
CVS
exhauat
with
7.53
1.28
.07
.13
1.18
1.53
.43
.03
.53
.53
.36
.26
.20
.51
.06
.76
.28
2.67
.21
.11
.95
1.00
1.21
.32
.18
.12
.37
.06
.04
.03
.01
.03
.03
.02
.05
.02
.01
.02
CVS
exhauat
6.58
10.44
1.24
10.42
6.97
.33
3.30
3.21
.47
.63
.14
2.45
.12
l.OB
.41
.20
.75
.12
.77
.76
.49
.12
.40
.43
.80
4.32
1.28
.45
3.64
.39
.20
1.03
1.40
1.61
13.00
.95
.51
.68
.14
.09
.07
1.08
2.26
1.53
.14
1.04
.31
.31
1.70
.34
+ Af3iX
LVS
exhauat
with
6.58
1.24
.02
.17
1.99
2.45
.67
.05
.77
.75
.49
.36
.27
.69
.08
1.06
.39
3.64
.34
.17
1.01
1.42
1.61
.46
.25
.18
.50
.10
.06
.04
.01
.05
.04
.01
.04
.02
.04
.01
«Tocal hydrocarbons by GC.... 131.75 92.13 89.77 95.01 98.78
Includea gxhauic hydrocarbcna nut reported In detailed analvala.
195
-------
TABLC A-4. - Ik-tailed Hydrocarbon AnalyBla
Accumulated nileoga..
Fuel
Peak
No. Compound
1 Methane
8 n-Butane, 1 ,3-butadiene
14 n-Pentane, 2-netnyl-l-butene
17 2-Hethyl-2-butene
IB Cjrcl open tune, 3-methyl-l-
20 2-Methylpentane.
2,3-dlmethyl-l-bulene
22 1-Hexene, 2-ethyl-l-bucCM..
24 Metnylcyclopentana,
3-nethyltrana-2-pentene. . .
27 Cyclohaxene,
2,3-dlnrthylpentane.
32 2,4-DlBmthylhexane.
35 Toluene, 2,3-dlmethylhexane.
41 2,5-Dlmethylheptana,
46 l-Mothyl-3-ethylbenMne
47 l-MethyI-2-ethylb»nzene
49 1 ,2 ,4-Trlmethylbeniene
SO 'ec-Butylbenrene, n-deiane..
9d3
CVS
exhauat
7.23
11.46
.87
10.65
5.00
.64
2.29
2.95
.48
.57
.19
3.02
.14
2.32
.25
.11
.31
4.14
.34
.47
.25
.25
.16
.23
.17
3.05
2.01
.36
3.89
.55
.28
.59
.29
.15
10.11
1.29
.83
.08
.43
.04
.-"
.74
2.27
1.24
.10
.56
.22
.19
1.12
.32
CVS
exhouBt
with
scrubber
7.23
.87
.06
.11
1.96
3.02
2.35
4.16
.34
.33
.17
.11
.10
.08
.01
1.89
.33
3.89
.49
.22
.36
.29
.15
.19
.51
.54
.04
.45
.02
.07
.04
.16
.02
.03
.06
Stnlionnry Irslnc A. ptifflt--
( ttnr inticd
S.OOO
CVS
exhaust
7.85
14.57
1.18
12.07
5.77
.33
3.15
3.64
.43
.51
.09
3.43
.11
2.74
.24
.11
.34
5.10
.35
.44
.20
.17
.15
.24
.12
4.29
2.55
.47
4.61
.66
.36
.79
.40
.22
14.82
1.70
1.14
.13
.70
.05
.21
1.20
3.65
2.00
.18
.95
.41
.39
1.77
.51
•Tor.nl h}i!rocarhonii by CC 92.51 126.82
rvs
exhaust
with
acruhber
7.85
1.18
.26
.16
2.26
3.43
2.62
4.30
.35
.37
.24
.19
.14
.11
.02
2.23
.40
4.61
.59
.29
.77
.39
.22
.26
.76
.81
.07
.67
.07
.26
.40
.32
.05
.07
.09
6,400
CVS
exhauit
7.49
10.99
.87
3.95
4.36
.22
2.49
2.51
.31
.39
.07
2.44
.08
2.00
.16
.07
.25
3.43
.25
.24
.14
.12
.09
.15
.07
3.31
1.87
.39
3.42
.47
.24
.53
.26
.11
11.11
1.21
.76
i .07
.40
.08
.82
2.67
1.34
.07
.67
.26
.22
1.03
.32
89.54
CVS
exhaust
with
acruhher
7.49
.87
.18
.06
1.49
2.44
1.86
3.36
.25
.24
.09
.08
.08
.07
.04
1.80
.29
3.42
.39
.20
.49
.26
.11
.15
.45
.46
.03
.31
.09
.03
.17
.07
.04
.04
.01
,06
«.?M
CVS
eihauac
7.77
11.47
.93
10.97
3.84
2.46
2.18
.22
.36
.03
1.99
.07
1.70
.14
.08
.23
3.08
.20
.20
.11
.08
.10
.11
.05
3.31
1.53
• .28
2.68
.1*0
.20
.39
.21
.08
10.02
1.00
.62
.06
.30
.01
.06
.72
2.26
1.20
.12
.57
.25
.11
,96
.39
82,51
CVS
rxliault
vlth
acrubber
7.77
i92
.04
.04
1.21
1.99
1.51
2.70
.20
.19
.08
.07
.07
.05
.02
1.33
.24
2.68
.34
.17
.33
.18
.08
.11
.32
.33
.02
.25
.01
.09
.03
.11
.04
.02
.02
,03
i* ; .
CVS
xhauit
7. Of
11.84
.90
10.48
5.22
2.64
2.54
.33
.46
.07
2.29
.08
1.88
.16
.07
.26
3.35
.24
.23
.15
.12
.10
.12
.05
3.29
1.71
.34
3.01
.44
.22
.45
.22
.09
10.61
1.09
.68
.06
.35
.01
.06
.78
2.39
1.33
.17
.67
.30
.26
1.09
,42
• !• .1
Mill
1.
-------
TABLE A-4. - Detailed Hydrocarbon Analvali
Accumulated mileage...
Peak
No. Compound
5 n- Butane, 1,3-butadlene
1 1 3-Nechy 1 - 1 -butane
16 n-Pentane, 2-nethyl-l-butene
17 2-Mechyl-2-butena
18 Cyclopentane, 3-oathyl-l-
20 2-Methylpentane,
2,3-dlnethyl-l-butene
22 1-Hexane, 2-ethyl-l-butenfl..
23 n-Hex
-------
TABLE A-5. - Pet*tied Hydrocarbon MialvtU
Stationary Ending B. ppmC
Paak
.Ho, Compound
2 Ethylena
7 Butene-1, liobutylene
8 n-Butana, 1,3-butadlcne
11 3-Methyl-l-butene
14 n-Pentana, 2-methyl-l-butcne
17 2-Hathyl-2-butana
19 Cyclopencana, 3-mathyl-l-
19 2,3-DtaethylbutaM
20 2-Methylpentana,
2,3-dtaathyl-l.biitena
22 1-Hexena, 2-ethyl-l-butena..
23 n-Hexane. cle.-3-hexene
24 Mathylcyclopantana.
3-nathy ltrana-2-pentena . . .
25 2,4-Dinathylparcane
27 Cyclohaxena,
2 , 3-dlnathylpentane,
28 3-Methylhexana
31 Mechylcyelohexana
32 2.4-Wn.ethylfiexana.
2 . 5-dlnethy lhaxana
33 2.3,4-Trlnothylpeneana......
34 2.3,3-Trlnethylpantana
31 Taluane, 2 ,3-dluethy lhaxana.
3k 2-Methylhaptana
37 3-Hethylhaptana
38 2.2,5-Trlaathylhexana
40 2,3,3-Trlmathylhaxana
41 2,5-Dlmethylheptana.
3,5-dlaathylheptana
42 Ethylbenzrne
44 o-Xylene
46 l-Mcttiyl-3-et'iylbcnione....
47 l-Mcthyl-2-ethylbe.izenG....
48 Keaitylene
49 l,2,4-TTlmi!thylbenzena
50 »c-nutylbGnzene, n-dccano.
Indnl..,,.
CVS
axhanat
7.11
11.28
1.10
10.39
6.70
.40
3.76
3.26
.39
.7J
.22
2.52
.13
1.17
.46
.20
.86
.15
.81
.82
.SI
.11
.43
.44
.88
4.89
.34
4.34
.46
.24
1.40
1.70
1.96
U.JO
1.11
.09
.OS
1.33
l.RS
1.18
LSI
.40
.40
• K-tal hydiociirbona < lubber
7.11
1.18
.07
.18
1.85
2.52
.73
.06
.83
.81
.47
.42
.30
.79
.10
1.21
.43
4.34
.37
.17
1.44
1.67
1.96
.56
.32
.26
.65
.14
.11
.11
.02
.06
.05
.01
.05
.01
.04
.03
4.9JD
Indolene
CVS
exhauat
9.70
13.03
1.46
12.28
9.06
.92
4.71
3.54
.89
1.23
.37
2.71
.25
1.33
.37
.28
1.02
.22
.94
1.17
.66
.25
.51
.54
1.06
5.80
1.68
.58
4.86
.45
.21
1.62
1.98
2.23
19.16
1.32
.64
.93
.16
.08
.06
1.59
3.75
2.30
.29
1.87
.60
.57
2. 83
.50
137. :3
CVS
ex haute
with
9.70
1.46
.10
.17
1.80
2.71
.88
.10
.94
.68
.61
.40
1.04
.24
1.40
.53
4.B6
.50
.25
1.65
1.95
2.23
.65
.37
.30
.76
.21
.10
.07
.03
.08
.07
.02
.12
.05
.13
.10
exhauat
11.24
15.47
1.81
15.42
10.38
1.03
4.97
3.46
.74
.23
2.43
.09
1.15
.44
.16
.89
.12
.86
.91
.51
.09
.45
.46
.91
6.41
1.70
.66
5.09
.47
.22
1.57
2.01
2.24
22.42
.78
1.06
.17
.08
.05
1.75
4.06
2.64
.24
1.47
.59
.56
3.76
104.58
• Include. exh.uac hydrocarbon. ,wt r.,vrt<-d In detailed auly.ls. 198 '
CVS
xhauat
with
-
FsT 1"
CVS
exhauat
8.03
20.34
1.60
11.97
9.03
.66
5.32
5.59
.75
.97
.26
5.23
20
4.24
.42
.22
.63
7.10
.57
.56
.43
.39
.29
.18
.27
4.96
3.88
.73
7.26
1.03
.53
1.22
.62
.31
22.29
2.46
1.65
.16
.93
.05
.23
1.72
J.28
2.68
.16
1.36
.49
.41
1.93
.42
163.93
CVS '
xhauit
with
• .03
1.60
.71
.45
3.43
4.08
6.06
.57
.65
.49
.43
.18
.15
.03
3.31
.63
7.26
.8*
.44
1.16
.60
.31
.36
1.20
1.24
.08
.81
.02
.23
.11
.44
.17
.10
.11
.11
4 31°
CVS
exhauat
10.36
13.08
1.05
15.14
7.18
.65
3.86
4.03
.56
.67
.19
3.90
.18
3.14
.29
.15
.47
5.63
.43
.43
.31
.29
.20
.27
.17
4.49
2.87
.54
4.90
.89.
.46
.89
.43
.23
16.30
2.06
1.34
.16
.75
.06
.19
1.32
4.24
2.18
.22
1.23
.48
.42
1.73
.56
CVS
xhauat
with
10.36
1.01
.07
.10
2.52
3.90
2.92
3.45
.45
.42
.20
.14
.16
.12
.03
2.40
.44
4.90
.63
.32
.75
.41
.23
.31
.94
.91
.07
.69
.03
.19
.18
.40
.26
.15
.11
.18
138.36
'vV.
-------
TABLE A-J. - Detailed Hydrocarbon Analyita
Accumulated mileage..
Peak
No. Compound
11 • 3-Methyl-l-butene
14 n-Pentane, 2-mechyl-l-butene..
17 2-Hethyl-2-butene
18 CycLopentane, 3-methyl-l-
19 2 ,3-DLmethylbutane
20 2-Mothylpentane,
22 1-Hexene, 2-ethyl-l-butene....
21 n-Hexane,. cls-3-hexene
' 24 Me thy Icyclopentane »
% • 3-mcthyUrana-2-pentene
27 Cyclohexene,.
2-3-dlmethylpentane,
28 3-Methylhexane
32 2 ,4-Dlmethy Ihexana ,
34 2,3l3'-Trlmathylpentane
33 Toluene, 2,3-dCmethylhaxane...
36 2-Methylheptane
37 3-Nechylh«ptine
40 2,3,3-Trlmethylhexane
41 2.5-Dlmethylheptane,
44 o-Xyl
-------
TABLE A-6. - Effect of mileage accumulation on exhaust emissions
Stationary Engine A
Miles
Test
temp.,
°F
Barometric
pressure,
nmHg
Fuel
consumed,
Ibs/test
Emissions.
CO
HC
NOx,
uncorrected
NOX,
FTP corrected
K rams Anile
Total
aldehydes
MCMT x 106
Inorganic
Mn x 10"
MCMT
percent
emitted
Kl
1,006
84
CLEAR FUEL
0
1,080
1,400
2,080
2,930
3,900
4,950
100
76
85
91
83
90
86
750.5
755.6
741.5
749.7
745.5
742.5
743.3
4.30
4.23
4.05
4.17
4.21
4.29
4.11
22.0
23.5
23.4
22.5
18.6
17.9
17.5
2.18
1.97
1.39
1.51
1.24
-
1.29
2.34
2.53
2.47
2.35
2.53
2.59
2.45
3.42
2.83
3.12
3.18
3.38
3.66
2.86
5,000
6,090
8,180
9,140
10,040
85
95
83
77
84
744.3
740.0
745.0
747.8
742.7
4.23
4.34
4.80
4.30
4.14
21.6
22.6
18.9
16.1
15.9
1.62
1.85
1.80
2.50
2.72
2.51
2.72
2.70
2.93
2.78
CHANGE TO FUEL CONTAINING AK33X ADDITIVE - 0.125 gMn/GAL
2.73
4.02
3.14
3.07-
3.79
NEW SPARK PLUGS INSTALLED
747.6
4.16
15.0 | 2.11
3.00
NEW TEST CYCLE
3.74
0.146
0
963
1,120
2,930
4,012
4,940
88
84
85
80
76
94
741.1
744.0
743.1
743.2
751.9
746.4
4.61
4.25
4.47
3.85
4.07
3.73
26.3
19.8
17.7
27.2
27.6
23.6
1.64
1.39
1.41
1.86
1.84
1.86
2.05
2.01
2.28
2.09
2.66
2.27
2.48
2.79
2.32
2.76
2.65
2.97
CHANGE TO FUEL CONTAINING F-310 ADDITIVE - 14.2 ML/GAL
5,000
6,400
8.250
9,130
82
60
68
75
748.2
740.0
744.2
757.0
4.02
4.23
4.20
4.07
21.0
29.3
27.4
24.9
1.79
1.50
1.50
1.44
2.52
2.56
3.00
2.76
3.12
2.18
2.61
2.56
0.108
.052
.071
.101
0.00.'
1.02
0.000
0.074
.074
.103
.125
.148
0.00
.00
.37
2.46
2.99
992
1,747
2,127
2,527
1,691
0.000
.000
.003
.021
.027
1,111
0.009
-------
TABLE A-7. - Effect of mileage accumulation on exhaust emissions
Stationary Engine B
Miles
Test
temp.,
°F
Barometric
pressure
nmHg
Fuel
consumed,
Ibs/test
Emissions
CO
HC
NOX,
uncorrected
NOx,
FTP corrected
grams /mile
Total
a Idehydes
MOfT x 106
Inorganic
Mn x 106
MCXT
percent
eoictcd
CLEAR FUEL
0
1,240
2,030
3,990
80
90
93
78
747.1
749.6
749.9
746.4
2.96
4.65
4.04
4.44
18.2
16.1
16.5
20.5
1.37
1.59
1.62
1.79
1.56
2.42
1.97
2.33
1.79
2.75
2.45
2.86
CHANGE TO FUEL CONTAINING AK33X ADDITIVE - 0.125 gMn/GAL
Kl
2 4,000
4,930
5,870
8,515
9,085
85
75
74
80
71
755.0
754.0
747.8
746.0
745.3
4.56
4.07
4.29
4.96
4.79
23.0
35.0
25.5
24.9
36.7
1.82
2.17
1.85
2.52
2.98
2.67
2.50
2.79
2.80
3.29
3.57
2.59
2.77
2.89
3.09
0.109
.164
.130
.130
-
Trace
<0.50
.35
.58
.87
1,031
1,267
1,746
608
2,266
Trace
O.005
.003
.004
.008
NEW TEST CYCLE
0
1,420
2,840
3,650
4,050
76
66
71
74
78
740.0
744.2
740.5
748.7
739.0
4.89
4.88
4.92
5.08
5.04
25.1
38.4
33.8
38.9
34.8
1.68
1.98
2.15
2.09
1.73
2.64
3.72
3.49
4.15
3.64
2.61
3.27
3.59
3.84
4.27
CHANGE TO FUEL CONTAINING F-310 ADDITIVE - 14.2 ML/GAL
4,350
5,540
6,125
7,070
7,930
78
70
76
71
80
739.1
743.3
749.3
741.4
755.7
4.89
4.91
4.98
5.24
5.39
32.8
45.3
38.6
34.1
43.0
1.81
1.77
1.66
1.55
1.66
3.82
3.96
4.45
3.99
4.8Z
4.36
3.87
4.08
4.00
4.10
0.091
.089
.094
.103
.092
-------
TABLE A-8. - Effect of mileage accumulation on exhaust emissions
F-310 Vehicle
Miles
Test
temp . ,
°F
Barometric
pressure
itmHg
Fuel
consumed,
Ibs/test
Emissions, grains /mile
00
HC
NOX,
un corrected
NOX,
FTP corrected
Total
aldehydes
MQfT x 106
Inorganic
Mh x 106
MCMT
percent
emitted
ISJ
O
KJ
CLEAR FUEL
0
1,710
2,743
4,030
4,700
72
67
83
82
93
748.2
745.0
745.9
748.8
741.6
4.60
3.46
4.61
4.92
4.62
59.5
69.6
65.5
65.6
62.1
2.76
2.96
2.62
2.51
2.77
4.78
5.46
4.40
3.86
4.44
55
08
33
06
81
CHANGE TO FUEL CONTAINING F-310 ADDITIVE - 14.2 ML/GAL
4,750
6,070
7,420
8,550
9,150
9,550
10,550
11,880
12,840
13,940
81
86
94
79
80
84
76
66
66
66
745.9
742.5
749.6
743.2
742.2
740.0
744.0
751.1
737.9
744.0
4.77
4.92
4.'98
4.77
4.43
4.62
4.66
4.70
4.70
4.67
64.7
75.8
62.2
58.0
63 >
63.2
66.5
52.7
45.7
49.7
3.11
2.85
2.41
2.39
2.73
2.66
2.66
2.58
2.53
2.53
4.00
4.02
4.40
4.43
3.60
3.59
3.81
5.03
5.63
5.48
4.91
6.51
6.45
5.58
4.57
4.99
4.60
5.63
5.25
5.00
0.086
.093
.065
.089
.072
.077
.090
.105
.054
.086
-------
TABLE A-9. - Effect of mileage accumulation on exhaust emissions
AK33X Vehicle
Miles
Test
temp.,
8F
Barometric
pressure
raraHg
Fuel
consumed,
Ibs/test
Emissions, grams /mile
CO
HC
N°x.
un corrected
NOX.
FTP corrected
Total
aldehydes
MCMT x 106
Inorganic
Hn x 106
MQIT
percent
emitted
N»
O
OJ
CLEAR FUEL
0
1,600 '
1,910
3,190
4,010
4,700
86
80
77
83
80
90
741.1
744.5
739.0
745.9
747.7
748.0
5.07
4.94
4.74
4.58
5.24
4.16
74.4
74.4
79.5
59.3
78.3
63.5
3.09
3.43
3.72
2.89
2.80
2.92
4.34
5.65
4.68
4.89
4.51
3.97
4.85
5.96
4.93
5.93
6.09
5.16
CHANGE TO FUEL CONTAINING AK33X ADDITIVE - 0.125 gMn/GAL
4,740
5,305
7,170
8,030
9,434
10,353
11,390
12,140
12,740
14,050
90
80
87
81
60
70
62
55
76
63
750.0
746.6
744.4
744.1
752.0
744.0
750.4
740.3
742.5
755.5
4.86
4.35
4.89
4.89
5.02
4.96
4.66
4.72
4.56
5.00
61.9
57.4
79.2
57.8
69.7
70.3
56.3
58.8
51.8
56.4
3.02
2.98
2.87
3.69
4.29
3.97
3.52
3.47
3.63
3.52
4.03
4.57
4.54
4.43
5.53
4.70
5.45
5.59
4.84
6.22
5.88
5.48
5.77
5.68
5.04
5.00
5.45
5.59
5.31
5.53
0.088
-
.089
.109
.105
.126
.096
.096
.085
.093
-
1.86
0.80
4.97
4.63
1.29
.82
1.70
2.98
1.44
915
1,857
905
1,440
846
800
1,452
500
1,471
1,095
-
0.016
.006
.037
.042
.010
.007
.013
.024
.011
-------
TABLE A-10.- Effect of mileage accumulation on exhaust emissions
Control Vehicle
Miles
Test
temp.,
°F
Barometric
pressure
mmHg
• Fuel
consumed,
Ibs/test
Emissions, grams/mile
CO
HC
NOX,
uncorrected
NOX,
FTP corrected
Total
aldehydes
MOTT x 106
Inorganic
Mn x 106
MCMT
percent
emitted
CLEAR FUEL
0
1,400
2,250
3,200
4,550
5,950
7,700
8,725
9,865
10,320
11,200
11,725
12,490
13,490
13,840
65
67
83
85
95
85
92
84
80
70
89
74
60
82
65
748.6
745.0
745.9
748.8
748.4
747.8
746.0
744.1
742.5
744.6
740.2
748.0
740.3
737.5
740.0
4.76
4.59
4.68
5.03
4.89
4.73
5.00
4.77
4.34
4.27
5.03
4.41
4.63
4.57
4.50
46.7
48.3
59.2
66.6
63.6
65.7
82.7
67.3
70.2
63.3
80.2
57.8
52.9
59.8
53.0
2.92
2.65
2.81
2.69
2.78
2.99
2.07
2.64
2.65
2.43
2.96
2.30
2.00
2.28
2.47
5.18
5.28
4.27
4.51
3.70
4.52
4.28
3.91
4.23
4.08
4.17
4.78
5.12
4.28
5.32
4.62
4.78
5.18
5.97
5.60
6.80
5.97
5.65
5.01
4.3->
6.W
4.86
5.29
5.0T
4.83
-
-
-
-
-
0.103
.093
.083
.069
.086
.092
.096
-
-
.066
-
''-
-
-
-
-
-
-
-
-
-
-
-
-
-
-------
KJ
o
CJ1
AK33X vehicle
F3IO vehicle
Control vehicle
FIGURE B-l.-Carburetor bases for the AK33X, F3IO,and control vehicles.
-------
KJ
•
AK33X engine A
AK33X engine B
F3IO engine A F3IO engine B
FIGURE B-2.-Carburetor bases for the stationary engines.
-------
NJ
O
AK33X vehicle
F3IO vehicle
Control vehicle
FIGURE B-3.-lntake and exhaust ports for the AK33X, F3IO, and control vehicles.
-------
AK33X engine A
AK33X engine B
NJ
o
00
• i
.'
/
«
F3IO engine A
F3 10 engine B
FIGURE B-4. - Intake and exhaust ports for the stationary engines .
-------
fl
1
•
''I
AK33X vehicle
F3IO vehicle
• . •
« >
i »
Control vehicle
FIGURE B-5.-Intake valve stems for the AK33X, F3IO, and control vehicles.
209
-------
AK33X engine A
AK33X engine B
F3IO engine A F3IO engine B
FIGURE B-6.-Intake valve stems for the stationary engines.
210
-------
AK33X vehicle
F3IO vehicle
Control vehicle
FIGURE B-7.-Piston head for the AK33X, F3IO,and control vehicles.
-------
KJ
-^'
"• ,'.-^ ' •*- • -.* .. *•*
AK33X engine A
AK33X engine B
K
F3IO engine A F3IO engine B
FIGURE B-8.-Piston head for the stationary engines.
-------
AK33X vehicle
F3IO vehicle
t
Control vehicle
FIGURE B-9.-Cylinder heads for the AK33X.F3IO, and control vehicles,
-------
AK33X engine A
F 310 engine A
AK33X engine B
F3IO engine B
FIGURE B-IO.-Cylinder heads for the stationary engines.
-------
n
» •
i
• ••
3 ...
- •
IT
•
•
.
• ,'*"»*lW: .-•«&,
AK33X vehicle
F3IO vehicle
Control vehicle
FIGURE B-ll.- Exhaust valve stems for the AK33X, F3IO, and control vehicles.
215
-------
AK33X engine A
AK33X engine B
F3IO engine A F3IO engine B
FIGURE B-12.-Exhaust valve stems for the stationary engines.
216
-------
'•
AK33X vehicle
ISJ
F3IO vehicle
Control vehicle
FIGURE B-l3.-Spark plugs for the AK33X, F3IO,and control vehicles.
-------
AK33X engine A
AK33X engine B
KJ
00
F3IOengineA FSIOengineB
FIGURE B-l4.-Spark plugs for the stationary engines.
-------
Pibton heod--AK33X engine A
Cylinder head --AK33X engine A
FIGURE B-15.- Piston and engine head for AK33X
engine A .
219
-------
United States Department of the Interior
BUREAU OF MINES
BARTLESV1LLE ENERGY RESEARCH CENTER
P. O. BOX 1398
BARTLESVILLE. OKLAHOMA 74003
AIRMAIL October 9, 1974
Memorandum
To: John E. Sigsby, Jr., Environmental Protection
Agency, Research Triangle Park, NC
From: R. W. Hum, Research Supervisor, BERC
Subject: Monthly progress reports
Accompanying as attachment A and B is a copy of the monthly progress
reports covering work accomplished through September 1974, on the projects
"Gaseous Emissions Associated with Gasoline Additives—Reciprocating
Engines" and "Characterization of Gaseous Emissions from Rotary Engines
Using Additive Fuel."
Attachment A & B
cc v/attach:
Sigsby (4)
Gooding
Cox
Allsup
Seizinger
Fleming
Williams
General files
220
-------
United States Department of the Interior
BUREAU OF MINES
BARTLESVILLE ENERGY RESEARCH CENTER
P. O. BOX 1398
BARTLESVILLE. OKLAHOMA 74003
October 9, 1974 Attachment A to memo dated October 9, 1974
Monthly Progress Report
Work accomplished through
September 1974
Project No. 4844
Gaseous Emissions Associated with
Gasoline Additives—Reciprocating Engines
Experimental work has been completed on all cars and additives for
this study. The final report is in progress and will combine the results
of both the reciprocating and rotary engines work. This report completes
monthly reporting procedures for this project.
221
-------
United States Department of the Interior
BUREAU OF MINES
RARTLESVILLE ENERGY RESEARCH CENTER
P. O. BOX 1398
HARTLESVILLE. OKLAHOMA 74003
October 9, 1974 Attachment B to memo dated October 9, 1974
Monthly Progress Report
Work accomplished through
September 1974
Project No. 4851
Characterization of Gaseous Emissions
from Rotary Engines Using Additive Fuel
Experimental work has been completed on all cars and additives for this
study. The final report is in progress and will combine the results
of both the reciprocating and rotary engines work. This report completes
monthly reporting procedures for this project.
222
-------
United States Department of the Interior
BUREAU OF MINES
BARTLESV1LLE ENERGY RESEARCH CENTER
P. O. BOX 1398
BARTLESVILLE. OKLAHOMA 74003
September 12, 1974 Attachment B to memo dated Sept. 12, 1974
Monthly Progress Report
Work Accomplished Through
August 1974
Project No. 4851
Characterization of Gaseous Emissions
from Rotary Engines Using Additive Fuel
Tests were completed on the Mazda stationary engine using Lubrizol
8101 fuel additive for 15,000 miles. The Lubrizol 8101, a succamid,
is a multifunctional dispersant-type additive for gasoline and was
used at a dosage of 140 Ibs per 1,000 barrels gasoline. No statistical
trend was apparent in the routine emissions during the 5,000 mile
period. Exhaust emission data is presented in table 5.
Tests were completed on the Mazda vehicle using both the Texaco TFA 318
polyisopropylene fuel additive and the combination of Texaco TFA 318
and Lubrizol 8101 fuel additives. Additive dosage was the same as
used in the reciprocating engine tests. Exhaust emission data for
the vehicle is presented in table 6 and 7.
This series of tests completes the experimental work outlined in the
program. Compilation of all experimental data and drafting of the
final report is now in progress.
223
-------
TABLE 5. - Exhaust emissions from 1973 Mazda engine
using Lubrizol 8101 fuel additive
Fuel
Clear + 8101
Clear + 8101
Clear + 8101
PI par 4- ft! 01
Clear + 8101
Clear + 8101
Clear + 8101
Clear
Elapsed
miles
o
n
800
810
2 900
2,910
s Qnn
8,900
8 910
11,700
14,800
14,810
CO
21 8
25 8
27 1
ng
26 5
24 1
00 f.
£.0 ••+
22.9
24 1
22.7
19.3
20.4
1975 Fl
HC
2 60
1 QO
4 13
2 14
3 17
3 05
2 (.a
• DO
2.77
2 70
2.19
2 10
2.25
CP B /mile
NOx
0 59
fid
5R
63
65
77
Ifil
«U1
.73
82
.80
70
.54
Aldehydes
0 901
"\"\L
234
9fifl
362
•>QO
miJi
.164
1P.7
.122
133
.133
TABLE 6. - Exhaust emissions from 1974 Mazda vehicle
using Texaco TFA 318 fuel additive
Filial
Clear + TFA 318..
Clear + TFA 318..
Clear + TFA 318..
Clear + TFA 318..
Clear + TFA 318..
Elapsed
miles
0
10
30
1,000
1,860
2,870
2,900
CO
23.4
24.1
24.0
20.9
22.5
20.2
18.0
1975 I
HC
2.05
2.19
2.05
1.72
2.34
2.08
1.95
?TP g/mile
NOx
1.17
1.20
1.21
1.25
1.23
1.18
1.14
Aldehydes
0 166
.170
.203
.148
.292
.143
.135
TABLE 7. - Exhaust emissions from 1974 Mazda vehicle
using Lubrizol 8101 and Texaco TFA 318 fuel additives
TTiial
rucj.
Clear + 318 + 8101
Clear + 318 -1- 8101
Clear + 318 + 8101
Clear + 318 + 8101
Clear + 318 + 8101
High Aromatic
+ 318+8101....
Elapsed
miles
o
20
30
1,050
2,050
3,050
3,070
CO
20 8
26.7
23.7
22.2
19.8
19.6
17.9
1975
HC
1 77
1.75
2.12
2.37
1.89
1.72
1.61
FTP g/mile
NOX
1 21
1.28
1.33
1.23
1.22
1.32
1.25
Aldehydes
0 130
.137
.146
.154
.125
.151
.124
224
-------
United States Department of the Interior
BUREAU OF MINES
BARTLESVILLE ENERGY RESEARCH CENTER
P. O. BOX 1398
BARTLESVILLE. OKLAHOMA 74003
August 19, 1974 Attachment B to memo dated August 19, 1974
Monthly Progress Report
Work Accomplished Through
July 1974
Project No. 4851
Characterization of Gaseous Emissions
from Rotary Engines Using Additive Fuel
Tests have been completed on the Mazda stationary engine using Du Pont
DMA-4 fuel additive. The DMA-4, an amine neutralized alkyl phosphate,
is a multifunctional cleaning additive and was used at the recommended
dosage of IS Ibs per 1,000 barrels. No significant trends of CO, HC,
or NOX were apparent during the 15,000 mile use with the DMA-4 (table 6)
Tests are now underway using Lubrizol 8101 (a succinamid) at a dosage
of 140 Ibs per 1,000 barrels.
Tests with the Mazda vehicle using DMA-51 (described in reciprocating
engine report) were completed and the emission data is presented in
table 7. Presently Texaco TFA 318 fuel additive is being used in the
Mazda vehicle.
225
-------
TABLE 6. - Exhaust emissions from 1973 Mazda engine
using DMA-4 fuel additive
Fuel
Clear + DMA -4. . .
Clear + DMA -4. . .
Clear
Clear + DMA- 4. . .
Clear + DMA-4. . .
Clear + DMA-4. . .
Clear + DMA-4. . .
Clear + DMA-4. . .
Elapsed
miles
o
10
1020
1030
3030
3040
5500
8580
8590
11500
14800
14840
CO
18.4
19.2
16.4
15.3
13.7
14.1
18.4
17.6
20.8
21.2
26.2
26.0
1975 FT!
HC
2
-------
United States Department of the Interior
BUREAU OF MINES
BARII.hSVII LE F.NFRGY RESF.ARCII CFNTF.R
P. O. BOX 13Q8
IURTI FSVII L.F.. OKLAHOMA 74001
July 22, 1974 Attachment B to memo dated July 22, 1974
Monthly Progress Report
Work Accomplished Through
June 1974
Project No. 4851
Characterization of Gaseous Emissions
from Rotary Engines Using Additive Fuel
Tests with the rotary engine vehicle were completed with the amine neu-
tralized alkyl phosphate fuel additive (Du Pont DMA-4) and the succina-
mide fuel additive (Lubrizol 8101). Emission data are presented in
tables 6-7.
Stationary rotary engine tests were completed with the F-310 fuel addi-
tive and are in progress with the DMA-4 with about 6,000 miles of the
planned 15,000 miles accumulated to date. Emission data for the sta-
tionary engine data are presented in tables 8-9.
227
-------
TABLE 6. - Exhaust emissions from 1974 Mazda vehicle
using DMA4 fuel additive
Fuel
Clear + DMA4..
Clear + DMA4. .
Clear + DMA4..
Clear + DMA4..
Clear + DMA4. .
Clear
Elapsed
miles
0
20
40
990
2,000
3,000
2,010
1975 FTP, g/mile
CO
18.1
16.9
17.0
15.7
23.7
18.3
18.3
HC
1.64
1.71
1.69
1.48
2.45
1.73 -
1.87
NOX
1.30
1.'40
1.34
1.30
1.24
• 1,22
1.24
Aldehydes
0.091
.116
.108
.104
.164
.110
.109
TABLE 7. - Exhaust emissions from 1974 Mazda vehicle
using Lubrizol 8101 fuel additive
Fuel
Clear + 8101..
Clear + 8101..
Clear + 8101..
Clear + 8101..
Clear + 8101..
Elapsed
miles
0
10
20
1,010
1,980
2,990
3,010
CO
20.0
20.5
19.1
17.7
22.1
20.7
34.7
1975 FT
HC
1.89
1.90
1.74
1.63
1.81
1.80
1.59
P, R/mil
NOX
1.27
1.22
1.18
1.33
1.30
1.49
1.35
e
Aldehydes
0.129
.132
.131
.123
.164
.157
.110
228
-------
TABLE 8. - Exhaust emissions from 1973 Mazda stationary
engine using F-310 fuel additive
Fuel
Clear -f F-310..
Clear + F-310..
Clear + F-310..
Clear 4 F-310..
Clear + F-310..
Clear
Clear + F-310..
Clear + F-310..
Clear
Clear + F-310..
Clear
Elapsed
miles
0
10
20
1,000
1,100
3,000
3,020
6,000
9,000
9,010
12,000
12,010
15,000
15.010
1975 FTP, g/mile
CO
25.9
30.4
28.3
21.3
18.3
23.5
18.8
19.9
19.5
16.5
28.7
25.7
22.3
24.7
HC
3.64
3.47
3.18
2.70
2.44
2.98
2.47
2.71
2.63
2.51
3.55
3.35
2.76
3.15
NOx
1.24
1.15
1.14
.94
.96
1.27
1.30
.71
.86
.70
1.10
.87
.74
.76
Aldehydes
0.195
.208
.177
.131
.216
.185
.148
.159
.123
.253
.190
.253
.179
TABLE 9. - Exhaust emissions from 1973 Mazda stationary
engine using DMA4 fuel additive
Fuel
Clear
Clear + DMA4...
Clear + DMA4 . . .
Clear
Clear + DMA 4 . . .
Clear
Clear + DMA4...
Elapsed
miles
0
10
1,020
1,030
3,030
3,040
5,500
1975 FTP, B/mile
CO
18.4
19.2
16.4
15.3
13.7
14.1
18.4
HC
2.54
2.80
2.58
2.17
2.03
1.89
2.15
NOx
0.76
.80
.71
.70
.74
.71
.79
Aldehydes
0.164
.163
.142
.133
.122
.143
229
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United States Department of the Interior
BUREAU OF MINES
BARTLESV1LLE ENERGY RESEARCH CENTER
P. O. BOX 1398
BARTLESVILLE. OKLAHOMA 74003
June 18, 1974 Atta^haent B to memo dated June 18, 1974
Monthly Progress Report
Work Accomplished Through
May 1974
Project No. 4851
Characterization of Gaseous Emissions
from Rotary Engines Using Additive Fuel
Vehicle
Tests wich the rotary engine vehicle were completed using the F-310
fuel additive for a 3,000 mile period. No trend in vehicle emissions
occurred during the use of F-310. After the test period with F-310
the vehicle was driven at highway speeds for 1,000 miles using additive-
free fuel. Apparently the severe driving resulted in a CO and HC
reduction of about 25 pet which has been observed until the present
time at 1,000 miles during the test sequence using DMA4 fuel additive.
Stationary Engine
The stationary rotary engine presently has 9,000 miles accumulated of
the planned 15,000 miles using the F-310 fuel additive. The stationary
engine emission data show a slight decrease in HC emissions during the
0 to 1,000 mile point after which HC emissions have apparently stabi-
lized. The emissions data for both the vehicle and stationary engine
are presented in tables 4-6.
Analytical Procedures
Analytical procedures that serve this project are identical to those
that serve the project "Gaseous Emissions Associated with Gasoline
Additives—Reciprocating Engines." For general discussion of the
status of analytical procedures development see the report covering
that project for the current month.
230
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TABLE 4. - Exhaust emissions from 1974 Mazda
using F-31Q fuel additive
Fuel
Clear + F-310..
Clear + F-310..
Clear + F-310..
Clear + F-310..
Clear + F-310..
Elapsed
miles
0
10
20
1,000
2,000
3,000
3.010
1975 FTP. K/mile
• CO
22.2
20.8
21.2
22.9
22.4
25.3
?6.9
HC
2.04
2.22
2.20
2.59
2.37
2.63
2.->5
NOy
1.12
1.34
1.26
1.26
1.19
1.59
1.97
Aldehydes
0.129
.148
.149
.168
.157
.187
.133
TABLE 5. - Exhaust emissions from 1973 Mazda
stationary engine using DMA4 fuel
additive
Fuel
Clear
Clear + DMA4...
Clear + DMA4...
Clear + DMA4...
Elapsed
miles
0
20
40
990
1975 FTP, g/mile
CO
18.1
16.9
17.0
15.7
HC
1.64
1.71
1.69
1.48
NOV
1.30
1.40
1.34
1.30
Aldehydes
0.091
.116
.108
.104
TABLE 6. - Exhaust emissions from 1973 Mazda
stationary engine using F-310 fuel
additive
Fuel
Clear + F-310..
Clear + F-310..
Clear + F-310..
Clear + F-310..
Clear + F-310..
Clear
Clear + F-310..
Elapsed
miles
0
10
20
1,000
1,100
3,000
3,020
6,000
9,000
9.010
1975 FTP. B/mile
CO
25.9
30.4
28.3
21.3
18.3
23.5
18.8
19.9
19.5
16.5
HC
3.64
3.47
3.18
2.70
2.44
2.98
2.47
2.71
2.63
2.51
NOV
1.24
1.15
1.14
.94
.96
1.27
1.30
.71
.86
.70
A Idehydes
0.195
.208
.177
.131
.216
.185
.148
.159
.123
I 231
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Appendix B2.9
Status Report
ROAP 26AAE
Task 023
Exploratory Investigation of the Toxic and Carcinogenic
Partial Combustion Products from
Oxygen- and Sulfur-Containing Fuel Components
Concept:
A specific chemiluminescence detector with"sensitivity below lOppb
has been developed by the University of Michigan and applied to the
search for new combustion products from gasoline additives. Two
commonly-used additives different from those used in other aspects
of the fuel additive program were studied in simplified combustors.
No new products were found.
Current work in this project involved construction of a new even more
sensitive detector for use in the in-house program and search of engine
exhaust for carcinogens.
232
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Appendix B2.10
Status Report
ROAP 26AAE
Task 023
Exploratory Investigation of the Toxic
and Carcinogenic Partial Combustion Products
from Various Nitrogen-Containing Additives
Concept:
Gas chromatography - mas spectroscopy is being used as the principal
analytical tool in a program which reaches for new products from fuel
additives. A constant volume bomb is used to combustion isooctane -
additive mixtures in a way that potential product yeilds can be maximized,
Thus far, no new products have been found in tests of two commonly used
nitrogenous additives.
233
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Appendix B2.ll
Status Report
ROAP 26AAE
Task 019
Characterize Diesel Gaseous and Particulate Emissions
Concept:
Fuel economy considerations strongly su.gges_t_the desirability of
significant numbers of vehicles fuels with middle distillates in the
U.S. car population. The introduction of diesel or stratified charge
cars is likely to significantly change light-duty vehicle emissions
patterns and an integrated research program to assess these hanges is
necessary.
The attack on this problem will be two-pronged. First, it is
suggested that the complex problem of heavy molecule identification
by guided bv health effects studies. This approach has been discussed
in detail and a copy of the proposed research program is attached
Secondly, a general characterization program in cooperation with OAWM
is proposed to survey the gross emissions potentials of light-duty
engines. Cooperative studies are currently underway and preliminary
test data from that study are attached.
It appears that diesel and stratified charge cars can appreciably
limit urban hydrocarbon and CO vehicular emissions. Particulate carbon
may be a problem, however, For NOX it appears that present humidity
corrections designed for gasoline-powered vehicles and presently applied
to light-duty diesel and stratified charge engines, probably unfairly
increase reported NO values. Better humidity corrections for light duty
A
engines are necessary and it is proposed that these emission factors be
determined in the current program.
234
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LIGHT DUTY DIESEL EXHAUST
EMISSIONS
by
Ronald L. Bradow
Chief, ETCS
235
-------
A light-duty diesel characterization program has been
in progress for some time at Southwest Research Institute
under the auspices of OA'VH. In a cooperative effort with
OA'.YM a series of particulate samples have been obtained and
analyzed in our laboratory in order to assess the impact of
such vehicles on localized emissions problems. Since die-
sel and stratified charge cars appear to be the most reasonable
alternatives to current year catalyst technology, it is im-
portant to assess their relative impact on atmospheric
aerosol problems.
Samples of particulate matter were obtained on fluoro-
pore and glass-fiber filters, using a Nissan and an Opel
diesel powered automobile on the 1975 FTP. An air dilution
aerosol handling system-CVS identical in design to the EPA
system previously described was used to obtain the samples.
Conditions for the tests, fuel properties and analytical
methods for gaseous emissions are given in an SY/RI interim
report to QA'.VM on contract PH-22-68-23, dated June, 197/t.
Filter samples were mailed to RTF, humidity conditioned,
and roweighed prior to analysis. Filter analysis procedures
on glass fiber samples included automated carbon, hydrogen,
and nitrogen analysis and extraction with methylene chloride,,
followed by evaporation and weighing the extract. Fluoro-
pore filter samples were analyzed by X-ray fluoresence
spectroscopy and by an automated barium chloranilate pro-
cedure.
236
-------
RESULTS Aim DISCUSSION:
Table 1 presents mass emissions and fuel economy data
from SvVRI for 3 diesel cars, compared with similar data from
Exxon on a GM "75 prototype using high sulfur fuel. Hydro-
carbons, CO and NOx from the diesels compare favorably with
the catalyst cars and particulates are only slightly higher
for high sulfur fuels. For lower fuel sulfur content, the
catalyst car is considerably better with respect to parti-
culate emission.rate. Catalyst car particulate matter is
composed of sulfuric acid-water droplets,i while diesel
particles are.mainly elemental carbon. Consequently, the
trade-off between these tv/o control options is not all that
clear cut.
Fuel economy considerations are really one-sided as
Table 1 shov/s. These diesel cars in the 3500 Ib. class
had exceptional fuel economy, far exceeding any recently
reported for gasoline powered passenger cars in this v/eight.
It should also be remembered that diesel engines burn middle
distillate fuel oil fractions rather than energy-expensive
high octane gasoline.
Analysis of filter samples is shown in Table 2. Carbon
clearly makes up the bulk of the material, together with
lesser amounts of organic material, possibly adsorbed on
carbon particles. Only small amounts of metallic components
(iron, copper, and zinc), probably from wear of engine and
exhaust components, were found. In a few cases phosporous,
possibly derived from the lubricant, was detected. Lead
was also found in traces in the Opel samples.
Sulfur compound emissions were relatively low and did not
appear to be sulfate.
237 :
-------
oonsequentiy the form of this su^^..r emission is of con-
siderable interest. It is possible that sulfur-bearing fuel
components are emitted with the heavy organics. Therefore,
sulfur analysis of the heavy organics is planned. It is also
possible that some of the SOp in the exhaust is adsorbed on
carbon partic""es and is consequently retained in the parti-
culate matter. Sulfite determinations are also planned to
settle this point.
Nitrogen values are especially high. This may be an
artifact frora interaction of N02 with the glass-fiber to
produce nitrate. It is not as yet known whether there are
significant amounts of organic nitrogen compounds ir the
exhaus t.
Only two extractions have been made to date. One with
a 7.5'hot start run on the Opel- gave 10.5% extractable.
With the Nissan only 2.0fo was extractable. This difference
can be confirmed by comparing -the filter weight gain with the
sum of carbon, nitrogen and water, assuming all the hydrogen
is present as water. In the case of the Nissan samples, the
C, N, ILjO sun was 95-98^ of the filter weight gain. In the
case of the Opel samples this sum is 115-135?* of the filter
gain. Clearly the hydrogen can not be mainly in the form of
water with the Opel samples, and the organic content is rela-
tively higher.
It is clear that the main hazard from diesel exhaust
would be from toxic organics in the exhaust. Consequently,
the main thrust of the current year's contract program should
be tov/ards characterization of this material.
("•.^ITC'T TT ~7rv.
Q >, 1 I O - ' 1 xj — I . I •
The current year's OAY/M program at Southwest relies
238
-------
heavily on analytical technology developed by previous C?B
efforts in the heavy duty diesel field. V/e plan to coordi-
nate OI?D and OAV/M efforts in cooperative experiments, such
as this one, to get maximum benefit for the Government's
contract dollar. Thus, 02D is supplying rcethodology for im-
proved gas analysis for SOXp and SO-,, detailed hydrocarbons,
odor components, and aldehydes. Analysis for particulate
sampling, PNA, metals, and organics in filterable particu-
late also result from CRD programs. OAY/M supplies engineering
guidance for vehicle and engine choice, noise, fuel economy,
and regulated emissions testing, as well as a wealth of
background information on diesel technology. Current year
plans include integration of bioassay techniques by ORD-
SBL to help guide the characterization program. The efforts
in this field are mutually supportive and represent a high
degree of cooperative by all concerned.
239
-------
TABLE 1
1975 FTP - Lisht Duty Diesel Test Results
A. Emission-* Ua.tn. - e\t-n^/mile.
0 034
X 0-
tr- O.OCl
240
HC A 0
- o 01^ o.oi^ o."
CO x 1.35 O.SS3 g,3i -5 oi
ff~ " O.Xl O / *3l3k 0-
KCx x i.-53 i.^a 1.00
o- o US^ 0-OSO 0-C^q
o.cnio
"B Fael tccncrriNj — n
^•o ol^ • o a^S «3l IQ.
txxoN iJaWx
"• C.Ob-5 c/c Fael
b 0. llV% fuel
-------
SnvrV
Frp
ii ns i.ai s. si
f'8*" 0.43 8-
-------
Appendix B2.12
Status Report
Characterize Rotary Emissions as a Function
of Lubricant Composition and Fuel/Lubricant Interaction
Report:
Attempts to arrange this work as a grant-program in 1974 were
unsuccessful. No reasonable acceptable grant proposals were received.
It is planned to reprogram this project to a contract status and issue
a new RFP. Since rotary engines are not likely to represent a substantial
number of cars, only the potential increased PNA, and metal?, emissions
are worthy of significant additional study. This will not be funded in
FY75.
242
-------
Appendix B2.13
Status Report
ROAP 26AAE
Task 017
Emissions --A1 tern ate
Power Systems (Rotary)
Report:
This task will be adequately covered under Task 13. It is planned
to reprogram the funds to diesel and stratified charge engine exhaust
characterization studies.
This reprogramming is based upon our current view that rotary
power plants will np_t constitute an increasing alternate automotive
power source in the U.S. in this decade while diesel and stratified
charge engine likely will become more prevelant.
243
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i r
LPORT NO *•
EPA-600/3-75-010 c
J TITl E AND SUBTITLE
ANNUAL CATALYST RESEARCH PROGRAM REPORT
Appendices, Volume II
7 AUTHORIS)
Criteria and Special Studies Office
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Health Effects Research Laboratory
Office of Research & Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
17.
Ib
16.
17
i
SPONSORING AGENCY NAME AND ADDRESS
Same as above
1. nECIPII-.MTT' ACCESSION-NO.
5. REPORT DATE
September 1975
6. PERFORMING ORGANIZATION CODE '
0. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1AA002
11. CONTRACT/GRANT NO.
13 TYPE OF REPORT AND PERIOD COVC RLD
Annual Program Status 1/74-9/7'
14 SPONSORING AGENCY CODE
EPA-ORD
SUPPLEMENTARY NOTES
This is the Summary Report of a set (9 volumes plus Summary).
See EPA-600/3-75-010a,010b, & OlOd thru OlOj. Report to' Congress.
ABSTRACT
This report constitutes the first Annual Report of the ORU Catalyst Research
Program required by the Administrator as noted in his testimony before the
Senate PUblic Works Committee on November 6, 1973. It includes all research
aspects of this broad multi-disciplinary program including: emissions charac-
terization, measurement method development, monitoring, fuels analysis,
toxicology, biology, epidemiology, human studies, and unregulated emissions
control options. Principal focus is upon catalyst-generated sulfuric acid
and noble metal particulate emissions.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Catalytic converters
Sulfuric' acid
Desulfurization
Catalysts
Sul fates
Sulfur
Health
UIST maun ON STATEMENT
Available to public
li IDENTIFIERS/OPEN ENDED TERMS <-. COSATI 1 lUd/l .riilip
Automotive emissions
Unregulated automotive
emissions
Health effects (public)-
10 SECURITY CLASS ( 1 liu Hi ror<> 21. NO OF PAGES
Uncl assifi-ed. 25°
aoSJETtURTtY CLASS (rin, pafei 22. PRICE
Unclassified
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