EPA-460/3-76-015
August 1976
MEASUREMENT
OF SULFATE
AND SULFUR DIOXIDE
IN AUTOMOTIVE EXHAUST
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Mobile Source Air Pollution Control
Emission Control Technology Division
Ann Arbor, Michigan 48105
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EPA-460/3-76-015
MEASUREMENT
OF SULFATE
AND SULFUR DIOXIDE
IN AUTOMOTIVE EXHAUST
by
Melvin N. Ingalls and Karl J. Springer
Southwest Research Institute
8500 Culehra Road
San Antonio, Texas 78284
Contract No. 68-03-2118
EPA Project Officer: Richard Lawrence
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Mobile Source Air Pollution Control
Emission Control Technology Division
Ann Arbor, Michigan 48105
August 1976
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This report is issued by the Environmental Protection Agency to report technical
data of interest to a limited number of readers. Copies are available free
of charge to Federal employees, current contractors and grantees, and nonprofit
organizations - in limited quantities - from the Library Services Office (MD35),
Research Triangle Park, North Carolina 27711; or, for a fee, from the National
Technical Information Service, 5285 Port Royal Road, Springfield, Virginia
22161.
This report was furnished to the Environmental Protection Agency by Southwest
Research Institute, San Antonio, Texas, in fulfillment of Contract No. 68-03-2118.
The contents of this report are reproduced herein as received from Southwest
Research Institute. The opinions, findings, and conclusions expressed
are those of the author and not necessarily those of the Environmental Protection
Agency. Mention of company or product names is not to be considered as
an endorsement by the Environmental Protection Agency.
Publication No. EPA-46Q/3-76-015
11
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ABSTRACT
This report describes the testing of four different groups of cars
for sulfates and sulfur dioxide. The collection and analytical techniques
used to obtain the sulfate and sulfur dioxide emission rates are described.
Sulfate and sulfur dioxide emissions rates in grains per kilometre are pre-
sented for a variety of test cycles including the light duty Federal Test
Procedure (FTP), the Highway Fuel Economy Test (HFET), and the Sulfate Emis-
sions Test number 7 (SET-7). In addition to sulfates and sulfur dioxide,
the usual gaseous emissions of hydrocarbons(HC), carbon monoxide (CO) and
oxides of nitrogen (NOX) were measured and reported in grams per kilometre.
Total particulate weight on the sulfate filter was determined for tests on
two of the groups of cars. In addition, for these same two groups of cars,
the sampling tunnel residue from each test car was examined by X-ray fluor-
escent techniques for content of various elements.
The first of the four groups of cars was tested to characterize sulfate
emissions from eight automobiles. Four of these were gasoline powered
catalyst cars, three were gasoline powered noncatalyst cars, and one was
diesel powered. The second group, consisting of four catalyst cars, were
operated for 80,500 km (50,000 miles) to determine the effect of distance
accumulation on sulfate emissions. The third group, two 1975 production
catalyst cars, was tested in support of the EPA effort to develop a sulfate
test procedure. The last group, consisting of eight cars, was part of the
EPA sulfate baseline. Of these eight cars, six were production 1975 models
(including one diesel), and two were experimental cars with three-way cata-
lysts.
iii
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FORWARD
This project was conducted for the U.S. Environmental Protection
Agency by the Department of Emissions Research of Southwest Research
Institute. The laboratory testing phase of the project began in July
1974 and was completed in May 1976. This project was conducted under
EPA Contract No. 68-03-2118 and was identified within Southwest Research
Institute as Project 11-4015. The baseline testing reported in Section
VII of this report was conducted under Task Order Contract No. 68-03-2196,
Task 2, and reported here as specified in that contract.
The EPA Project Officer for this project was Mr. Richard D. Lawrence of
the Characterization and Control Branch, Emission Control Technology Divi-
sion, Office of Mobile Source Pollution Control, EPA, Ann Arbor, Michigan.
Mr. Karl J. Springer, Director, Department of Emissions Research at SwRI
served as Project Manager. The project was under the supervision of Mr.
Melvin N. Ingalls, Senior Research Engineer, as Project Leader. Mr. Harry
E. Dietzmann, Senior Research Chemist, supervised the development and ap-
plication of the chemical analysis. Although a number of SwRI personnel
assisted in the laboratory testing, key individuals included J. T. Jack,
lead technician, A. J. Winfield, technician, and D. J. Bynum, laboratory
assistant. Among others, key personnel involved with the chemical analysis
were J. H. Herrington, lead technician, D. L. Milligan, technician and
W. M. Saegert, laboratory assistant.
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TABLE OF CONTENTS
Page
ABSTRACT 111
FOREWORD iv
LIST OF FIGURES vii
LIST OF TABLES xii
SUMMARY 1
1. Sulfate and Sulfur Dioxide Emission Measurement 1
2. Test Cycle Development 1
3. Sulfate Emissions 2
4. Sulfate Emission Variation with Distance Traveled 3
5. Sulfate Storage by Catalysts 4
6. Relationship of Net Filter Weight to Sulfate Weight 4
7. Analysis of Sulfate Tunnel Residue 4
I. INTRODUCTION 5
A. Objectives 5
B. Report Organization 5
C. On-Site Project Reviews 5
D. Project Reviews - Ann Arbor 6
II. EMISSIONS MEASUREMENT PROCEDURES AND EQUIPMENT 7
A. General Procedures 7
B. Sulfate Collection and Analysis 7
C. Sulfur Dioxide by Pulsed Fluorescence 11
D. Sulfur Dioxide Procedure Using Bubblers and
BCA Analysis 13
E. EPA Method 8 Tests 13
III. SULFATE EMISSIONS CHARACTERIZATION 17
A. Purpose 17
B. Cars Tested 17
C. Fuels Used 17
D. Test Sequence 21
E. Test Results 24
IV. EFFECTS OF DISTANCE ACCUMULATION 47
A. Purpose 47
B. Cars Tested 47
C. Fuel Used 47
D. Vehicle Maintenance 50
E. Test Sequence 50
F. Test Results 55
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TABLE OF CONTENTS (Cont'd)
Page
V. SULFATE REGULATION STUDIES 125
A. Background 125
B. Purpose 125
C. Cars Tested 125
D. Fuel Used 125
E. Test Schedule and Procedures 128
F. Test Results 131
VI. BASELINE TESTING 143
A. Background 143
B. Purpose 143
C. Cars Tested 143
D. Fuel Used 143
E. Test Sequence and Procedure 145
F. Test Results 146
LIST OF REFERENCES
APPENDICES
A. Speed Versus Time Listing of SET-7 Driving Cycle
B. BCA-Sulfate Procedure and Interference Checks
C. Summary of Pulsed Fluorescence Analyzer Interference
Checks and Exhaust Recovery Tests
D. SwRI SO^-BCA Procedure and Validation Tests
E. Method-8 Determination of Sulfuric Acid Mist and
Sulfur Dioxide Emissions from Stationary Sources
F. Analysis of Fuels Used
G, Results from Individual Tests of Sulfate Characteri-
zation Cars
H. Supporting Information for Distance Accumulation Cars
I. Supporting Information for Procedural Development Study
J. Supporting Information for Baseline Studies
VI
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LIST OF FIGURES
Figure page
1 Emissions Collection and Analysis Equipment 8
2 Speed vs Time Traces of FTP, HFET and SET-7 Driving
Cycles 9
3 Schematic of Sulfate Sample Collection System 10
4 Components of Sulfate Collection and Analysis
System 12
5 SO2-BCA Flow Schematic 14
6 Photographs of SO2 Sample Collection System 15
7 Method 8 Impingers in Place During a Test 16
8 Non-Catalyst Sulfate Characterization Cars 19
9 Catalyst Equipped Sulfate Characterization Cars 20
10 Regulated Gaseous Emissions From 1975 FTP Tests of
Eight Cars 26
11 Gaseous Emission in gAm From Tests at 48 km/hr on
Eight Cars 27
12 Gaseous Emissions in g/km From Tests at 96 km/hr
on Eight Cars 28
13 Sulfuric Acid and Sulfur Dioxide Emissions From
1975 FTP Tests on Eight Cars 29
14 Sulfuric Acid and Sulfur Dioxide Emissions From
Tests at 48 km/hr on Eight Cars 30
15 Sulfuric Acid and Sulfur Dioxide Emissions From
Tests at 96 km/hr on Eight Cars 31
16 Percent of Fuel Sulfur Recovered in Vehicle Ex-
haust as Sulfuric Acid and Sulfur Dioxide for FTP
Tests on Eight Cars 34
17 Percent of Fuel Sulfur Recovered in Vehicle Ex-
haust as Sulfuric Acid and Sulfur Dioxide for
48 kph Steady State Tests on Eight Cars 35
18 Percent of Fuel Sulfur Recovered in Vehicle Ex.-
haust as Sulfuric Acid and Sulfur Dioxide for
96 kph Steady State Tests of Eight Cars 36
vii
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30 Sulfate and Sulfur Dioxide Emissions from Accel-
eration to 96 kph Tests at Distance Intervals on
Pour Cars
32 Sulfate Emissions from FTP Tests as a Function
of Distance Traveled for Four Cars
33 Sulfate Emissions from SET-7 Tests as a Function
LIST OF FIGURES (cont'd)
Figure
19 Comparison of Method 8 and BCA SO2 and Sulfate
Results in mg/km for 48 and 96 kph Steady State
Tests for Two Non Catalyst Cars 40
20 Comparison of Method 8 and BCA Results as Percent
of Fuel Sulfur Recovered for Two Non Catalyst Cars 42
21 Comparison of Filter Weight and Sulfate Weight
Per Filter by BCA Analysis for Three Cars 44
22 Emissions from FTP Tests at Distance Intervals
on Four Cars 59
23 Emissions from SET-7 Tests at Distance Intervals
for Four Cars 6Q
24 Emissions from HFET tests at Distance Intervals
for Four Cars g^
25 Sulfate and Sulfur Dioxide Emissions from FTP
Tests at Distance Intervals for Four Cars 71
26 Sulfate and Sulfur Dioxide Emissions from SET-7
Tests at Distance Intervals for Four Cars 72
27 Sulfate and Sulfur Dioxide Emissions from HFET
Tests at Distance Intervals for Four Cars 73
28 Sulfate and Sulfur Dioxide Emissions from Accel-
eration to 48 kph Tests at Distance Intervals
for Four Cars 74
29 Sulfate and Sulfur Dioxide Emissions from 48 kph
Steady State Tests at Distance Intervals for Four
Cars
75
76
31 Sulfate and Sulfur Dioxide Emissions from 96 kph
Steady State Tests at Distance Intervals on Four
Cars 77
81
of Distance Traveled for Four Cars or,
Of.
viii
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LIST OF FIGURES (cont'd)
Figure
34 Sulfate Emissions from HFET Tests as a Function
of Distance Traveled for Four Cars 83
35 Sulfate Emissions from Acceleration to 48 kph
Tests as a Function of Distance Traveled for
Four Cars 84
36 Sulfate Emissions from 48 kph Steady State Tests
as a Function of Distance Traveled for Four Cars 85
37 Sulfate Emissions from Acceleration to 96 kph
Tests as a Function of Distance Traveled for Four
Cars 86
38 Sulfate Emissions from 96 kph Steady State Tests as
a Function of Distance Traveled for Four Cars 87
39 Exhaust Sulfur Recovery from FTP Tests at Distance
Intervals for Four Cars 95
40 Exhaust Sulfur Recovery from SET-7 Tests At
Distance Intervals for Four Cars 96
41 Exhaust Sulfur Recovery for HFET Tests at Distance
Intervals for Four Cars 97
42 Exhaust Sulfur Recovery for Acceleration to 48 kph
At Distance Intervals for Four Cars 98
43 Exhaust Sulfur Recovery for 48 kph Steady State
Tests at Distance Intervals for Four Cars 99
44 Exhaust Sulfur Recovery for Acceleration to 96 kph
Tests at Distance Intervals for Four Cars 100
45 Exhaust Sulfur Recovery for 96 kph Steady State
Tests at Distance Intervals for Four Cars 101
46 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-1 at 0 and 3200 km 106
47 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-1 at 8050 and 16,100 km 107
48 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-1 at 24,100 km 108
49 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-2 at 0 and 3200 km 109
ix
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LIST OF FIGURES (cont'd)
Figure ES3S.
50 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-2 at 8050 and 16,100 km 110
51 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-2 at 24,100 km li:L
52 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-3 at 0 and 3200 km 112
53 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-3 at 8050 km 113
54 Cumulative Sulfur Recovered in Exhaust as a Function
of Sulfur Consumed, EM-3 at 16,100 and 24,100 km 114
55 Cumulative Sulfur Recoveries in Exhaust as a Function
of Sulfur Consumed, EM-4 at 0 and 3200 km 115
56 Cumulative Sulfur Recoveries in Exhaust as a Function
of Sulfur Consumed, EM-4 at 8050 km 116
57 Cumulative Sulfur Recoveries in Exhaust as a Function
of Sulfur Consumed, EM-4 at 16,100 and 24,100 km 117
58 Net Filter Weight Versus BCA Sulfate Weight as Ammon-
ium Sulfate for all Non FTP Test on Non Air-Injected
Cars 119
59 Net Filter Weight Versus BCA Sulfate Weight as Ammon-
ium Sulfate for all Non FTP Tests on Air-Injected Cars 120
60 Net Filter Weight Versus BCA Sulfate Weight as Ammon-
ium Sulfate for All FTP Tests on Non Air-Injected Cars 121
61 Net Filter Weight Versus BCA Sulfate Weight as Ammon-
ium Sulfate for FTP Test on Air-Injected Cars 122
62 General Views of Cars and Test Equipment 127
63 Catalyst Temperature over San Antonio Version of
Ann Arbor Road Course for AMC Hornet No. D50-36 132
64 Catalyst Temperature over San Antonio Version of
Ann Arbor Road Course for AMC Hornet No. D50-34 133
65 Sulfate Emissions from Part I of Procedural Develop-
ment Study 136
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LIST OF FIGURES (cont'd)
Figure Page
66 Sulfate Emissions from Repetitive Tests of
Various Test Cycles -^Q
67 Sulfate Emissions for Baseline Test Sequence
from Eight Baseline Cars ^48
xi
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LIST OF TABLES
Table Page
1 Description of Sulfate Characterization Cars 18
2 Fuels Used in Sulfate Emissions Characterization
Studies 22
3 Test Sequence for Sulfate Characterization Cars 23
4 Exhaust Emissions Summary of Cars Tested for
Sulfate Characterization Project 25
5 Summary of EPA Method 8 Test Results 38
6 Comparison of Filter Weights and Sulfate Weights
Per Filter by BCA Analysis for Three Cars 45
7 Results of X-Ray Fluorescent Analysis of Sulfate
Sampling Tunnel Particulate Residue for Sulfate
Characterization Cars 46
8 Cars Tested in Distance Accumulation 48
9 Fuel Batches used in Distance Accumulation Study 49
10 Test Sequence for 0 and 3200 kilometre Tests 51
11 Test Sequence for 8,050 kilometre Test on All
Cars and 16,100 kilometre Test on cars EM-1 and
EM-2 52
12 Test Sequence for 24,100 kilometre Tests on all
Cars and 16,100 kilometre Tests on Cars EM-3 and
EM-4 53
13 Test Sequence for Tests at 32,200 kilometres,
48,300 kilometres, 64,400 kilometres and 80,500
kilometres for all cars 54
14 Average Hydrocarbon Emissions by Test Type for
Distance Interval Tests on Four Cars 56
15 Average CO Emissions by Test Type for Distance
Interval Tests on Four Cars 57
16 Average NOX Emissions by Test Type for Distance
Interval Tests on Four Cars 58
17 Sulfur Dioxide and Sulfate Emissions at Distance
Intervals - Car EM-1 1975 Federal Plymouth Gran
Fury, Monolithic Catalyst, without Air Pump 63
xii
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LIST OF TABLES (cont'd)
Table Page
18 Sulfur Dioxide and Sulfate Emissions at Distance
Intervals - Car EM-2 1975 Federal Chevrolet Impala
Pelleted Catalyst, without air pump 65
19 Sulfur Dioxide and Sulfate Emissions at Distance
Intervals - Car EM-3 1975 California Plymouth Gran
Fury, Monolithic Catalyst, with air pump 67
20 Sulfur Dioxide and Sulfate Emissions at Distance
Intervals - Car EM-4 1975 California Chevrolet
Impala, Pelleted Catalyst, with air pump 69
21 Average Sulfate Emissions by Test Type from Distance
Interval test on Four Cars 80
22 Regression Analysis and Deterioration Factors for
SET-7 Tests at Distance Intervals on Four Cars 89
23 NOX and Sulfur Emissions from Selected Tests on
SwRI Car EM-3 92
24 Results of Emission Tests at 80 kph Steady State
On Four Cars with EGR System Operating Normally and
Disabled 93
25 Test Sequence Total Sulfur Recovery 118
26 Results of X-Ray Fluorescent Analysis of Sulfate
Sampling Tunnel Particulate Residue for Distance
Accumulation Cars 124
27 Description of Vehicles Tested for Procedural De-
velopment Studies 126
28 Comparison of AMC and SwRI Light Duty FTP Emissions
from Two 1975 Hornet Sportabouts 126
29 Sulfate Test Schedule, Part I 129
30 Part II Test Schedule 130
31 Summary of Emissions from Car EM-5 on Part I Test
Sequences 134
32 Summary of Emissions from Car EM-6 on Part I Test
Sequences 135
33 Statistical Summary of Emissions From Tests on Part II,
Test Sequence A, B, C and D 138
xiii
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LIST OF TABLES (cont'd)
Table Page
34 Statistical Summary of Sulfate Emission from
Repetitive SET-7 Tests, Part II, Sequence E 142
35 Sulfate Baseline Cars Tested at Southwest Research
Institute 144
36 Sulfate Baseline Test Sequence 146
37 Summary of Sulfate and SO- Emissions from Baseline
Tests at SwRI 147
xiv
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SUMMARY
Four groups of cars were tested for exhaust sulfate emissions in
separate phases of this study. Each group was tested for a different
purpose. However, the results from one group supplemented the results
from another group to give a more complete understanding of exhaust
sulfate emissions. Therefore, the developments, findings and conclusions
from this study will be presented by topic rather than by test phase.
1. Sulfate and Sulfur Dioxide Emission Measurement
This project proved the capabilities of a sulfate sampling
tunnel 21 cm (8.4 inches) in diameter and approximately 3 meters (10 feet)
in total length. This tunnel, while smaller than the 46 cm (18 inch)
diameter EPA dilution tunnel, has the advantages of being compact and
more compatible with existing 8.5 m^/min (300 CFM) constant volume sampling
(CVS) systems and automotive emissions test facilities. Because of the
successful use of the tunnel on this project, it has become the primary
candidate for use by EPA and by industry,
A TECO pulsed fluorescence (PF) SC>2 analyzer was originally
scheduled for use on the project to monitor dilute SC>2 continuously. How-
ever, when the PF unit was placed in service measuring S02 on dilute auto-
mobile exhaust, it greatly overstated the amount of SC>2 in the exhaust due
to some unknown interference. The effects of the interference were found
to be a function both of exhaust S02 level and fuel composition and sulfur
level.
To replace the PF analyzer, a wet chemistry method for SC>2 was
developed utilizing a sample collection procedure similar to EPA stationary
source Method 6. The amount of S02 collected was determined using the same
Barium Chloranilate (BCA) procedure that was used to determine the amount
of H2SO4 collected on the sulfate filters.
At the start of the project, some researchers felt that the sta-
tionary source Method 8 procedure might be acceptable for use in measuring
automotive exhaust sulfates and S02- In actual tests, the Method 8 pro-
cedure yielded lower SO2 values, higher sulfuric acid values and recovered
less of the total sulfur than the BCA procedure. It is felt that Method 8
is inferior to the BCA procedure for measuring automotive exhaust sulfates
because it gives erroneously high sulfate values.
2. Test Cycle Development
The work done on cycle development during this project was part
of the overall EPA effort to develop a standardized sulfate test pro-
cedure. As such, SwRl was one of four laboratories performing test cycle
development studies. The results contained in this report were based on
tests on two 1975 Federal AMC Hornet Sportabouts.
By the time the laboratory work had begun, the SET-7 driving
cycle had been chosen by EPA as the candidate driving cycle. Twenty
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repetitive SET-7 tests were run on each of the two Hornets to ascertain
the test-to-test variability. The coefficient of variation of the sul-
fate emissions was 26.6 percent on one car and 30.7 on the other car.
In an effort to reduce test-to-test variability, the SET-9 driving
cycle was developed by EPA and tested at SwRI, using 12 repetitive tests
These results were then compared with 12 repetitive SET-7 tests by the
same driver. The average sulfate emissions from the SET-9 tests were
approximately 16 percent higher than the sulfates from the SET-7 tests.
The coefficient of variation for the two types of tests were not sifnifi-
cantly different, being 3.99 for the SET-7 tests and 5.40 for the SET-9
tests. From these test series it appeared that the SET-9 did not offer
any real improvement in test-to-test repeatability over the SET-7. Tests
were also run to determine the effects of preconditioning and driver-to-
driver differences. The SET-7 has since been slightly modified (SET-7D).
This is the cycle which is known as the Congested Freeway Driving Schedule
(CFDS).
3. Sulfate Emissions
During the course of this project, exhaust sulfate emissions were
measured on a variety of test cycles including the FTP, SET-7, HFET, accel-
erations from 0 to 48 and 96 kilometres per hour (kph) (30 and 60 mph), and
from 48 and 96 kph cruise conditions. Sulfate emissions varied from less
than 0.01 mg/km for a non air-injected catalyst car (probably operating in
a storage mode) during an acceleration to 48 kph to 77.11 mg/km for an air-
injected catalyst car during an acceleration to 96 kph. A higher value of
97.30 mg/km was observed for one car after a prolonged (5 hours) precondi-
tioning at 56 kph.
The sulfate emissions also varied widely depending on the type of
car tested. In general, noncatalyst cars produce the least sulfates and
oxidation catalyst cars without air injection, slightly more sulfates. Odi-
dation catalyst cars with air injection in general produce the most sulfates.
One car equipped with a three-way (oxidation-reduction) catalyst without air
injection demonstrated sulfate levels on the same order of magnitude as non-
catalyst cars. Diesel cars are a special case. The diesel car tested con-
verted approximately the same percentage of fuel sulfur to sulfates as did
the noncatalyst cars and nonair-injected catalyst cars. However, because
of the high level of sulfur in the diesel fuel (average of 0.23 versus 0.04
weight percent for gasoline used in this project) the sulfate emissions in
mg/km were similar to air-injected catalyst cars.
One of the significant findings of the study was that some mal-
functions of the emission control system can affect sulfate emissions. It
was found, for instance, that disconnecting the fuel evaporative cannister
from the carburetor had no effect on the SET-7 sulfate emissions. However,
a leak in the air injection system on one of the catalyst cars tended to
lower the sulfate emissions on most test cycles. One of the most interesting
findings is that an inoperative EGR system will significantly increase sulfate
emissions on some cars, particularly air-injected catalyst cars.
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4. Sulfate Emission Variation with Distance Traveled
The sulfate emissions also varied with distance accumulated on
the car. The change in sulfate emissions with distance traveled was
measured on four catalyst cars. The variation in sulfate emissions was
found to be dependent upon both the driving cycle and the type of car.
For example, as shown on the graph below, on the SET-7 tests, there was
almost no change in sulfate emissions over 80,500 km (50,000 miles) for
the nonair-injected cars. For the air-injected cars, the sulfate emissions
decreased significantly in an exponential fashion from 8,050 km (5,000 miles)
to 80,500 km (50,000 miles).
60 r
50
40
o*
W
CO
n>
ra
3
W
•P
05
w
30
20
10
0
**
O EM-1
O EM-2
^ EM-3
O EM-4
* Air injection leak
** EGR system failed
10 20 30 40 50 60 70 80
Distance Traveled, kilometres
90
100
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5. Sulfate Storage by Catalysts
From the testing of catalyst cars during this project, it appears
that whether a given vehicle operating condition is a sulfur storage or
release mode, is dependent not only on what the condition is, but also the
distance accumulated on the vehicle. Whether a given operating condition
is a storage or release mode also varies from vehicle to vehicle. Three
of the four cars tested to 80,000 Km, stored sulfur during some of the
test cycles and released sulfur during other test cycles. However, one
car, EM-4, (pellet w/air) apparently stored sulfur during all test cycles
except for the acceleration to 96 kph at the 24,100, 32,200 and 48,300 km
test points.
Except for car EM-4, the acceleration from 0 to 96 kph (0-60 mph)
always exhibited the largest release of sulfur, while the 48 kph (30 mph)
cruise condition showed the largest storage of sulfur compounds. The total
sulfur recoveries from the tests performed varied from 10.7 percent at 48
kph (30 mph) cruise on a nonair-injected catalyst car with 32,000 km accumu-
lated use, to 335 percent during an acceleration from 0 to 96 kph (0-60 mph)
on a nonair-injected catalyst car at essentially zero kilometres traveled.
6. Relationship of Net Filter Weight to Sulfate Weight
For two of the test phases, the filters used to collect the ex-
haust sulfates were weighed before and after the test on which they were
used. On one phase of the project, the filters were weighed with the sul-
fate in the form in which it was collected, sulfuric acid. No consistent
relationship between net filter weight and sulfate weight were shown by
these tests even though the filters were weighed in a controlled-humidity
chamber after a stabilization period. During a later phase of the project,
the filters were subjected to an ammonia atmosphere after the test but
prior to the "after-test" weighing. This converted the sulfuric acid to
ammonium sulfate releasing the water vapor. When treated in this manner,
there was a good linear relationship between weight of particulate col-
lected on the filter and weight of sulfate from the BCA analysis for all
cars on all tests except the 1975 FTP. The FTP tests exhibited a different
slope and considerably more scatter.
7. Analysis of Sulfate Tunnel Residue
For two phases of this project, the sulfate tunnel was swept out
at the end of each test series on each car. The particulate residue was
collected and quantitatively analyzed for various elements using X-ray
fluroescence. The analysis was for platinum (Pt), palladium (Pd), aluminum
(Al), nigfcel (Ni), iron (Fe), sulfur (S), lead (Pb), zinc (Zn), copper (Cu)
and tin (Sn). Of these 10 elements, no platinum, palladium, nickel, copper
or tin was found in any of the samples. Chromium, silicon, and manganese
were found in some of the samples. The largest part of each sample was iron.
From a visual inspection of the samples, it appears that rust, probably from
the exhaust system, is the major constituent of the residue. The other ele-
ments were found in much smaller quantities and their origin is not certain.
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I. INTRODUCTION
In 1971 and 1972 EPA sponsored studies at Dow Chemical Company (1'2)*
showed that catalyst equipped cars emitted a larger mass of particulate emis-
sions than noncatalyst cars. The additional particulate mass was shown to
be sulfuric acid . * '
EPA studies have been conducted since that time to determine the level of
sulfuric acid emissions from automobile exhaust. (4,5,6) Tne voy:k covered
in this report is one of these studies.
A. Objectives
The original objective of this project was to provide data on the emis-
sions of sulfate (measured as sulfuric acid) and sulfur dioxide (SO2) from
passenger cars powered by gasoline and diesel engines. These data could then
be used to compare different type engines and catalysts. Two additional ob-
jectives were to determine the change in sulfate emissions with mileage ac-
cumulation, and to investigate the phenomenon of sulfate storage where possible,
As the project progressed the need by the EPA for further information
on sulfate emissions led to the inclusion of two additional studies in the pro-
ject. One of these studies was in support of the EPA effort to produce a
"Notice of Proposed Rule Making" (NPRM) for sulfates. The other study was
the SwRI contribution to the EPA sulfate baseline project.
B. Report Organization
This report has a separate section for each of the study areas; charac-
terization, NPRM, baseline and mileage. Each section covers the objective,
test schedule and test results for the study area. Test procedures and equip-
ment common to all areas of investigation are covered in one section.
C. On-Site Project Reviews
Five project reviews at SwRI by the EPA Project Officer occurred during
the testing phase of the project. On September 17, 1974, Mr. Joseph H.
Somers and Mr. Richard D. Lawrence of the EPA visited the Department of
Emissions Research at SwRI for an inspection and discussion of the project.
Several items of procedure were discussed. It was decided that the test
gasoline would have a sulfur level of 0.04 percent and the test diesel fuel
a sulfur level of 0.25 percent. On January 24, 1975, Mr. Richard Lawrence,
EPA Project Officer, again visited SwRI to review the project. It was de-
cided at that time to proceed with the test schedule using the SwRl-BCA
procedure for S02- On October 27 and 28, 1975, Mr. Lawrence visited the
Department of Emissions Research at SwRI to review the status of both Con-
tract 68-03-2118 and Task 2 of Contract 68-03-2196. Specific items dis-
cussed included reviewing the data obtained from the four mileage accumu-
lation cars, a discussion of the lower than expected emissions on Car EM-4
a review of the future test schedule, a discussion of the final report out-
*Superscript numbers in parentheses refer to the List of References at
the end of this report
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line, and a discussion of the proposed extension of the distance accumu-
lation to 80,500 km on each of the four cars. During the visit all of
the baseline cars were at the laboratory. A brief inspection of the cars
was made and the test schedule and results discussed.
On April 15 and 16, 1976, Mr. Richard Lawrence visited the Department
of Emissions Research to review the status of the project and discuss the
outline and contents of the final report. As a result of these discussions,
it was decided to run the back-to-back 50 mph tests to determine the effect
of an inoperative EGR system on sulfate emissions at the conclusion of the
80,500 km tests.
D. Project Reviews - Ann Arbor
In addition to these visits to SwRI by the Project Officer, two meet-
ings were held at the EPA facility at Ann Arbor, Michigan to discuss the
results of testing done under this contract. Mr. Melvin Ingalls attended
these meetings representing the Department of Emissions Research at SwRI.
The first meeting was held on July 15, 1975, in Ann Arbor, Michigan,
with all four laboratories working on sulfate testing in support of the
sulfate regulation studies present. As a result of this meeting, the test
schedule for the Part II testing was changed. The testing requested of
SwRI was outlined in an EPA memo from J. H. Somers to J. P. DeKany, dated
July 18, 1975.
The second meeting was hald on August 19, 1975, in Ann Arbor, with
representatives from all four laboratories again in attendance. The
results of each laboratory's testing^ in support of a sulfuric acid test
procedure were discussed. In addition, the EPA presented their analysis
of the data from all four labs.
-------
II. EMISSIONS MEASUREMENT PROCEDURES AND EQUIPMENT
This section covers the measurement procedures and equipment used
to obtain and analyze the gaseous exhaust emissions and exhaust sulfates
in the form of sulfuric acid.
A. General Procedures
All exhaust emission tests performed during this study were on cars
under 6,000 pounds GVW. The 1975 light duty Federal Test Procedure (FTP)
without evaporative emissions, was followed in terms of procedure and
equipment as much as possible for all tests. It is assumed that the
reader is familar with this test procedure. If not, it can be found in
40 CFR Part 85, Subpart A. The latest recodification was published in
the Federal Register, Volume 40, Number 126, dated June 30, 1975.
The gasoues emissions of hydrocarbons (HC), carbon monoxide (CO), and
oxides of nitrogen (NOX) were collected and analyzed using the procedures of
the light duty FTP. The tests were performed on a Clayton chassis dynamometer
with the vehicles manually driven. A Constant Volume Sampler (CVS)fwith a
nominal capacity of 350 CFM was used. To collect the sulfate sample, the
usual CVS system was modified by inserting a three meter long tunnel approxi-
mately 21 cm in diameter between the CVS room air filter box and the entrance
to the CVS heat exchanger. Figure 1 shows various views of the test area,
' CVS system and the analysis instruments for the bagged gaseous emissions.
There were three main driving cycles used during this project. The first
was the driving cycle used in the light duty FTP, known as the LA-4 cycle or
the Urban Dynamometer Driving Schedule (UDDS). The second was the Highway
Fuel Economy Test (HFET) cycle. The third cycle was developed specifically
as a sulfate test cycle and is identified as Sulfate Emission Test 7 or SET-7.
The speed time traces of these three cycles are shown in Figure 2. A complete
speed versus time listing for the SET-7 is contained in Appendix A. In addition
to the driving cycles, tests were run at constant 48 kph (30 mph) and constant
96.5 kph (60 mph) conditions during the characterization studies.
At the conclusion of the characterization tests on each car, the sulfate
tunnel was swept out with a fine bristled brush. The resulting particulate
matter was analyzed using an X-ray fluorescense analyzer for a variety of
elements.
B. Sulfate Collection and Analysis
The exhaust sulfates were collected as sulfuric acid on 47 mm Fluoropore*
membrane filters with 0.5 ym pore size. The samples were obtained isokinetically
using a pitot type probe centered in the 21 cm diameter tube. Figure 3 is a
schematic of the collection system.
For some parts of the study, the filters were weighed before and after
*Fluoropore is a registered trademark of the Millipore Corporation.
Fluoropore filters are made of PTFE (Polytetrofluorelthylene) bonded
to polyethylene net.
7
-------
General View of Test Area
Dilution Air Filter Box
and Sulfate Tunnel
Vehicle Exhaust Connection
to CVS System
Emission Analyzers for
Bagged Gaseous Emissions
FIGURE 1. EMISSIONS COLLECTION AND ANALYSIS EQUIPMENT
8
-------
I
60
40 •
20 .
60
40
20
0
Q
100 200
300 400
Seconds
50Q 600 7QQ 800
FTP
100 200 300 400 5QQ
6QQ 700
Seconds
800 900 1000 1100 1200 1300 1400
100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400
FIGURE 2. SPEED VS. TIME TRACES OP FTP, HFET AND SET-7 DRIVING CYCLES
-------
CVS
Unit
Flow Meter
14. 7 litres/min for
Isokinetic Sample
H
Suction
Pump
Molecular Sieve
Dryer
47mm Fluoropore Sulfate
Collection Filter
<*/-<).
.775 cm ID
281 m/min |
10m3/min 21.cm
46cm.
2 metres
To
Atmosphere
Dilution
Air
Filter
Pack
Heaters
J__[
10. 7cm
Car
Exhaust
FIGURE 3. SCHEMATIC OF SULFATE SAMPLE COLLECTION SYSTEM
-------
use, using a Mettler microgram balance located in a temperature and humidity
controlled chamber. After the test and weighing of the used filter (when
required) the filters were leached in a 10 ml solution of 60 percent isopropyl
alcohol and 40 percent distilled water (IPA solution). A portion of the
mixture was injected into a liquid chromatograph system using a flow through
cell in a Model 25 Beckman UV visible spectrophotometer set at 310 nm. A
high pressure liquid chromatograph sampling valve and one ml loop was employed.
to insure sample injection repeatability.
Once injected, the sample passed through a strong cation exchange resin
column to remove possible interfering cations and to convert ammonium sulfate
to sulfuric acid. The solution then passed through a column packed with
barium chloranilate. The barium combines with the sulfate in the sample to
form barium sulfate, releasing chloranilic acid. The concentration of the
released chloranilic acid, which is proportional to the amount of sulfate in
the sample, is measured by the UV spectrophotometer. This method of sulfate
determination is commonly called the barium chloranilate (BCA) procedure for
sulfates. It was developed by Dr. Silvestre Tejeda of the EPA at their Re-
search Triangle Park, N.C., facility. Figure 4 contains photographs showing
the various components of the sulfate collection and analysis system. A
complete description of the analytical procedure is contained in Appendix B.
Part way through the project, an improvement in filter handling was
recommended by the EPA at Research Triangle Park and subsequently put into
practice. This improvement involved exposing the used filters to ammonia gas
to convert the sulfuric acid on the filters to ammonium sulfate which is a
solid and hence should be more stable. In addition, it is not hydroscopic,
so that moisture from the air is not taken up on the filter to add to the
filter weight.
The first car tested in the project was run on leaded fuel. During the
test preparations the question arose as to whether the cation exchange column
could remove all the lead in the sample. More importantly, it was questioned
whether the chloride and bromide ions from the ethylene dichloride and ethylene
dibromide in the leaded fuel (which would be anions like sulfate) would inter-
fere in the BCA procedure. A series of tests were run to answer these questions.
The results indicated that the BCA procedure could not be used with leaded fuel.
A detailed presentation of the results of these tests is included in Appendix B.
The BCA procedure has recently been modified to eliminate these interferences.
C. Sulfur Dioxide by Pulsed Fluorescence
Originally it was planned that a TECO Model 40 Pulsed Fluorescent (PF)
SO2 Analyzer would be used to measure the exhaust S02 emissions. Considerable
work was done investigating interferences and the instrument's ability to
measure SO2 in dilute automobile exhaust at fuel sulfur levels on the order
of 0.04 percent.
The interference tests essentially showed that in an air-rich sampling
system such as the CVS, the interferences from CO, CO2. NQX ^nd ^t least two
of the aromatic hydrocarbons would be negligible. However, when the PF unit
was placed in service measuring SO2 during tests on an actual car running on
0.05 percent sulfur fuel, it greatly overstated the amount of SO2 in the
11
-------
Sulfate Filter Holder on Probe
Sample Collection System
With Total Flow Meters
UV Spectrophotometer
BCA Column, Cation Exchange
Column and Sample Loop
FIGURE 4, COMPONENTS OF SULFATE COLLECTION AND ANALYSIS SYSTEM
12
-------
exhaust. The exhaust SC>2 reading on the instrument was found to be a
function of both exhaust SO2 level and composition of the fuel. Complete
details of both the interference checks and the actual car tests are con-
tained in Appendix C.
Almost three months of effort were expended in trying to adapt the PF
unit for SO, determination on CVS tests of automobiles without success. It
was felt that more than enough effort had been expended and that an alter-
nate method would have to be used for SO2 determination.
D. Sulfur Dioxide Procedure Using Bubblers and BCA Analysis
The procedure developed to replace pulsed fluorescent measurement of
SO2 involved bubbling a sample of the exhaust gas through a 3 percent solu-
tion of hydrogen peroxide (H^C^). A schematic of the sample collection equip-
ment is shown in Figure 5. A sample of the exhaust gas was drawn through the
glass probe and a 0.5 ym Fluoropore filter to remove any sulfuric acid, then
in series through two impingers filled with 25 ml of 3 percent solution of
H2O2 where the S02 is oxidized to SO4= and stays in the solution. The second
bubbler serves only as a back-up to insure that all the SO2 is collected.
After the test, the 25 ml of hydrogen peroxide solution was evaporated to
10 ml. Several drops of ammonium hydroxide solution (1M) were then added to
convert the mixture to ammonium sulfate and the sample evaporated to dryness.
The remaining white residue of ammonium sulfate was dissolved in a 60-40 per-
cent IPA solution and analyzed using the barium chloranilate procedure used
to analyze the filters. Several photographs showing various parts of the col-
lection and analysis systems are contained in Figure 6. A complete descrip-
tion of the analytical procedure called the SwRI SO2-BCA procedure is con-
tained in Appendix D.
Extensive experiments were conducted to validate the sampling and ex-
traction procedures. The experiments were conducted in both areas of the pro-
cedure; the sample acquisition and the sample analysis. The detailed de-
scription and results of these tests are also listed in Appendix D. The
validation experiments proved that the SC^-BCA method gave satisfactory sulfur
recoveries on non-catalyst vehicles. These sulfur recovery levels were orders
of magnitude better than the TECO PF analyzer and an improvement over what
others had reported using titration or gravimetric analysis of hydrogen per-
oxide SO2 collection systems.
E. EPA Method 8 Tests
At the start of the project, it was felt by some researchers that
the EPA stationary source Method 8 test might be an acceptable procedure
for use in determining automotive exhaust sulfates and SO2. Consequently,
some of the characterization cars were scheduled to use the Method 8
sampling procedure concurrently with the sulfate filter tests.
Method 8 is a wet chemical procedure utilizing four impingers. The first
impinger contains 80 percent isoproponal and is used to entrain the sulfuric
acid in the sample. A filter is placed between the first and second impinger
to prevent any sulfuric acid carryover to the second impinger. The second and
13
-------
Note: All tubing in sample train up to the impingers is glass or teflon.
teflon union w/SS
frit insert
glass probe
dilution tunnel
pump
wet test
meter
midget impingers
FIGURE 5. S02-BCA FLOW SCHEMATIC
thermocouple
flowmeter
-------
FIGURE 6. PHOTOGRAPHS OF SO2 SAMPLE COLLECTION SYSTEM
15
-------
third impinger contain a solution of 3 percent hydrogen peroxide to trap the
C f*\ -\ -r\ +• V» /^ o a Tr>r~\ 1 f* rpVi «-\ -F ^^ -i i -v- 4- V. -I »«•»--. -I « ^^.-, -^- __-i
SO2 in the sample.
The fourth impinger contains silica gel
The analysis for sulfuric acid is performed using the solution from the
first impinger; the analysis for SO2, using the solution from the second
and third impinger. The analytical procedure uses the barium-thorin titration
method. A complete description of Method 8, as given in the Federal Register
is contained in Appendix E. Figure 7 is a photograph of the Method 8 impingers
in place during a test.
FIGURE 7. METHOD 8 IMPINGERS IN PLACE DURING A TEST
16
-------
III. SULPATE EMISSIONS CHARACTERIZATION
This section covers the sulfate emission testing of eight cars
selected under the origiinal scope of the project.
A. Purpose
The purpose of this phase of the project was to provide data on
the emissions of sulfate (804=) expressed as sulfuric acid (H2SO4) and
sulfur dioxide (SO2) from various types of passenger cars powered by both
gasoline and diesel engines. The primary use of the data is to permit
comparisons between different type engines and catalyst systems.
B. Cars Tested
To meet the objective of this phasa of the project, a variety of en-
gines and catalysts were selected for testing. Since sulfate emissions
were thought to be a problem when catalysts were used in the exhaust system,
a noncatalyst 1972 car was chosen as a baseline. At the time this work was
done , the sulfate detection procedure could not be used with leaded fuel.
Therefore, it was necessary to choose a baseline car that was manufactured
with the capability to run on unleaded gasoline.
To test sulfate emissions from catalyst cars, it was considered de-
sirable to have both pelleted and monolithic catalysts. It was also desired
to have each of the catalyst types with and without air injection systems.
Current model non catalyst cars were also included to characterize
sulfate emissions from cars which met the then current standards wihout
catalysts. Three cars were chosen in this category. One was powered by a
conventional spark-ignition engine without a catalyst but calibrated to
meet the 1975 standards. Another of these cars was powered by the Honda
compound vortex controlled combustion(CVCC) engine. The remaining car was
powered by a diesel engine. Table 1 lists the eight cars together with a
brief description of engine and exhaust systems. Figures 8 and 9 are
pictures of the cars tested.
The cars were obtained from various sources. The 1972 Plymouth is owned
by SwRI and used as a general transportation car by the Department of Emis-
sions Research. The Honda Civic CVCC and Mercedes 240D cars were government-
provided emission test cars. The Ford Granada was obtained from an auto-
mobile dealership where it had been operated on long term lease service. The
four catalyst cars were leased new for this project to study the effects of
mileage on sulfate emissions from catalyst cars.
C. Fuels Used
Three different: fuels were used for this part of the project, a leaded
gasoline for one series of tests on the 1972 Plymouth, an unleaded gasoline
for all other tests of both catalyst and non catalyst cars, and 2-D diesel
fuel for the diesel car.
17
-------
TABLE 1. DESCRIPTION OF SULFATE CHARACTERIZATION CARS
00
Make
Plymouth
Honda
Ford
Plymouth
Chevrolet
Plymouth
Chevrolet
Mercedes
Model
Fury
Civic
CVCC
Granada
Gran Fury
Impala
(Federal)
(Federal)
Gran Fury
Impala
240D
(Calif)
(Calif)
Model
Year
1972
1974
1975
1975
1975
1975
1975
1975
Engine
CID
360
90
351W
360
350
360
350
147
Engine Cycle
Conventional
gasoline
Strat. Charge gasoline
Conventional
Conventional
Con vent iona 1
Conventional
Conventional
Conventional
gasoline
gasoline
gasoline
gasoline
gasoline
diesel
Catalyst
Type
None
None
None
Monolith
Pelleted
Monolith
Pelleted
None
Air
Pump
None
None
Yes
No
No
Yes
Yes
No
-------
1972 Plymouth
1975 Honda CVCC
v
1975 Ford Granada
1975 Mercedes 240D
FIGURE 8. NON-CATALYST SULFATE CHARACTERIZATION CARS
L9
-------
1975 Federal Plymouth Gran Fury
1975 Federal Chevrolet Impala
1975 California Plymouth Gran Fury
1975 California Chevrolet Impala
FIGURE 9. CATALYST EQUIPPED SULFATE CHARACTERIZATION CARS
21
-------
The leaded fuel used was a base stock, a Phillips unleaded gasoline
which was obtained by EPA, Research Triangle Park, in a large batch for
use in several emissions projects. Sufficient tetraethyl lead in the form
of "motor mix" was added to this fuel at SwRI to bring the lead concentra-
tion to 3 g/gallon. This gasoline meets the EPA specifications for leaded
FTP emissions test fuel except for the 50 percent distillation point of
199°F and the Reid Vapor Pressure (RVP) of 10.2.
The unleaded gasoline was locally obtained Gulf Crest gasoline as sold
at local retail stations. This gasoline meets the EPA specifications for
unleaded FTP emissions test fuel except for Research Octane Number (RON)of
92.0 and the 10, 90,and 100 percent distillation points of 119°F, 352°F and
420°F respectively.
The diesel fuel used was a commercially-available Gulf 2D diesel fuel.
This fuel was chosen rather than a diesel fuel blended to meet the EPA
specifications for emissions test fuel. The emission test fuel is higher
in sulfur and aromatics than normal diesel fuels.
From the Bureau of Mines Gasoline Survey available at the time for
leaded gasoline, the national average sulfur content was estimated to be
0.04 percent. It was decided to use 0.04 percent sulfur level in all
gasoline fuels. Later Bureau of Mines surveys available after the project
had begun, which contained more information on unleaded gasoline, showed
the average fuel sulfur level for unleaded fuel to be approximately 0.03
percent. However, it was decided not to change the fuel sulfur level in
the middle of the project. From similar Bureau of Mines surveys of diesel
fuel, it was decided to use 0.23 percent sulfur in the diesel fuel.
Thiophene was added to increase the sulfur levels of the gasoline stock
to the required percentage. Ditertiary butyl disulfide was added to the
diesel fuel to obtain the required sulfur percentage.
The list of fuels used is shown in Table 2, together with the actual
weight percent sulfur in the fuel. A complete analysis of each fuel is
included in Appendix F.
D. Test Sequence
After receipt of the vehicles, the engines were checked to insure that
timing, idle speed and dwell were within manufacturers specification and
that the engine was running properly. A visual inspection was made for
loose vacuum lines, spark plug wires, etc. The car was tuned as necessary,
so that the items checked were within specifications prior to testing. The
test sequence for both non catalyst and catalyst cars is shown in Table 3.
Unfortunately, this test series was planned, and for the most part conducted,
before the sulfate test cycle (SET-7) had been developed; thus, it is con-
spicuously absent from the test series.
21
-------
TABLE 2. FUELS USED IN SULFATE EMISSIONS CHARACTERIZATION STUDIES
to
(VJ
SwRI Fuel
Code...
1. EM-208F
3. EM-246F
..Description
Base Stock
Source
leaded gasoline unleaded Phillips
EPA Contract
68-02-1122
2. EM-212F unleaded gasoline Gulf Crest
2D diesel
Gulf- 2D
Local
'Additives
Thiopene &
Motor Mix
Thiophene
Ditertiary
Butyl
Disulfide
Fuel Sulfur
Percent
0.051
0.041
0,23
Cars Using
Fuel
'72 Plymouth
Honda CVCC,
'75 Ford Granada
4 catalyst cars
Mercedes 240D
-------
TABLE 3. TEST SEQUENCE FOR SULPATE CHARACTERIZATION CARS
A. Test sequence for the Non Catalyst vehicles.
1. Check vehicle specifications and tune as required.
2. Condition vehicle on modified AMA route for 200 miles.
3. Soak vehicle for 10 hours. (Do not run "hot start LA-4"
following 200 mile conditioning).
4. Run 1975 FTP, 30 and 60 mph.
5. Repeat "3 - 4" once.
B. Test sequence for the catalyst equipped vehicles
1. Check vehicle specifications (timing, dwell, idle speed, etc.)
Tune as required.
2. Condition vehicle on modified AMA route for 500 miles.
3. Soak vehicle for 10 hours. (Do not run "hot start LA-4"
following the 500 mile conditioning).
4. Run 1975 FTP, 30 and 60 mph.
5. Repeat "2 - 4" above once.
23
-------
Both gaseous emissions (including S02) and sulfates were measured
during the test series. The regulated gaseous emissions were obtained
using the standard CVS procedures, except that the 1975 FTP was run as
two complete 23 minute cycles, rather than as a 23 minute cycle and a
hot 505 second cycle. The emissions from the two complete cycles were
then added, weighting the cold cycle 43 percent and the hot cycle 57 per-
cent. If it is assumed that the emissions from the stabilized portion
of the cold and hot 23 minute cycle are the same, then it can be shown
mathematically that the two 23 minute cycles will give the same results as
the regular three bag '75 FTP.
Sulfur dioxide and sulfates were obtained on all cars using the BCA
method explained in the Test Procedure section. For the FTP, one filter
was obtained for each 23 minute cycle. The sulfates from each filter were
then added in the same manner as the gaseous emissions. The EPA stationary
Method 8 procedure, also explained in the Test Procedure section, was used
to obtain S02 and sulfates from the 1972 Plymouth using both leaded and un-
leaded fuels, and the 1975 Honda CVCC.
It should be pointed out that the cars were not all tested on the same
base fuel. Six of the seven gasoline powered cars were tested using a nominal
0.04 percent sulfur fuel. The fuel for the 1972 Plymouth contained 0.05 per-
cent sulfur.
After the test series was completed on a car, the sulfate tunnel was
carefully swept out with a fine bristled brush. Any particulates deposited
in the tunnel during the test were thus collected for analysis using X-ray
fluroescence techniques.
The sulfate filters were weighed prior to processing by the BCA method.
During the project, a filter ammoniation technique was developed at EPA
Research Triangle Park, to provide a more stable form of sulfate on the
falters and sharper peaks during analysis. This technique was adopted at
SwRI during the project. Thus, some filters were weighed with the sulfate
as H2S04 and some with the sulfate as ammonium sulfate, (NH4)2SO4.
E. Test Results
The test results from the eight cars tested under this part of the
project fell into four different classifications and are covered in the
following four subsections.
Gaseous and BCA Sulfate Test Results
A summary of the gaseous emissions and the sulfate emissions using the
BCA procedure is given in Table 4. The emission standards in grams/kilo-
metre for a 1975 FTP type test are also included for reference. Figures
10 to 12 show the emissions results in the form of histograms for the re-
gulated emissions at the three test conditions. The two sulfur emissions
(S02 and sulfate) are shown in Figures 13 to 15 for each test type. For
the detailed data on individual tests see Appendix G.
Figure 10 shows that all cars met their respective NOX standard except
24
-------
TABI£ 4. EXHAUST EMISSIONS SUMMARY OF CARS TESTED FOR SULFATE CHARACTERIZATION PROJECT
Exhaust. Emissions
Barium Chloranilate
Vehicle Make
1
1
2
3
4
5
6
7
8
1
1
2
3
4
j 5
n 6
7
a
i
i
2
3
4
5
6
7
8
Note:
1972
1972
Plymouth
Plymouth
Honda CVCC
1975
1975
1975
1975
1975
1975
1972
1972
Granada
49S Ply.
49S Chev.
Cal. Ply.
Cal. Chev.
Mercedes
Plymouth
Plymouth
Honda CVCC
1975
1975
1975
1975
1975
1975
1972
1972
Granada
49S Ply.
49S Chev.
Cal. Ply.
Cal. Chev.
Mercedes
Plymouth
Plymouth
Honda CVCC
1975
1975
1975
1975
1975
1975
Results
Granada
49S Ply.
493 Chev.
Cal. Ply.
Cal. Chev.
Mercedes
from Vehicles
Test
Type
1975 FTP
1975 FTP
1975 FTP
1975 FTP
1975 FTP
1975 FTP
1975 FTP
1975 FTP
1975 FTP
48 kph
48 kph
48 kph
48 kph
48 kph
48 kph
46 kph
48 kph
48 kph
96 kph
96 kph
96 kph
96 kph
96 kph
96 kph
96 kph
96 kph
96 kph
Fuel
leaded
unleaded
unleaded
unleaded
unleaded
unleaded
unleaded
unleaded
diesel 2
leaded
unleaded
unleaded
unleaded
unleaded
unleaded
unleaded
unleaded
diesel 2
leaded
unleaded
unleaded
unleaded
unleaded
unleaded
unleaded
unleaded
diftapl. 2.
Fuel %
s
0.051
0.051
0.041
0.041
0.041
0.041
0.041
0.041
O.~230
0.051
0.051
0.041
0.041
0.041
0.041
0.041
0.041
0.230
0.051
0.051
0.041
0.041
0.041
0.041
0.041
0.041
0.230
Catalyst
none
none
none
none
mono w/o air
pel w/o air
mono w/air
pel w/air
none
none
none
none
none
mono w/o air
pel w/o air
mono w/air
pel w/air
none
none
none
none
none
mono w/o air
pel w/o air
mono w/air
mono w/air
none
HC
2.89
2.63
0.71
1.01
0.32
0,40
0.26
0.44
0.09
1.51
1.21
0.07
0.22
0.03
0.03
0.03
0.07
0.02
1.08
0.98
0.02
0.17
0.02
0.01
0.03
0.02
0.01
CO
55.04
51.30
2.43
5.77
7.27
9.59
3.23
7.89
0.47
28.93
32.00
1.08
1.15
0.04
0.06
0.06
0.04
0.15
6.75
7.40
0.56
1.79
1.62
0.85
0.05
0.02
0.36
gAm
NOy
3.19
3.45
0.55
2.07
1.41
1.25
0.75
1.01
0.10
0.41
0.38
0.37
0.49
0.83
0.25
0.62
0.19
0.53
3.63
3.66
1.40
1.62
0.57
0.75
0.38
0.62
1.08
SO2-BCA
0.14
0.16
0.05
0.10
0.09
0.06
0.24
0,06
0.34
0.08
0.08
0.04
0.06
0.01
0.01
0.02
0.01
0.15
0.08
0.08
0.04
0.06
0.12
0.15
0.03
0.02
0.37
H7SO4-BCA
___ —
2.1
0.4
0.5
0.3
0.1
6.2
8.9
10.1
___-
0.1
0.2
0.1
2.4
8.3
4.8
32.2
3.4
1.8
0.9
0.2
0.3
0.2
43.7
17.9
13.3
4 to 7 are for 2000 mile tests.
FTP Standards in terms of g/km and 1975
Year
1972
1975
1975
HC
1.S5
Fed. 0.9
Cal. 0.6
CO
17.25
9.3
5.6
NCL.
X
1.9
1.2
- cold/hot procedure
% Fuel S
as SO?
89.5
99.8
81.7
90.0
58.8
45.8
120.9
44.1
96.0
91.9
89.0
113.0
82.6
17.3
13.8
30.7
13.5
79.0
103.7
88.0
105.4
98.8
174.2
157.4
41.
28.
124,9
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FIGURE 11. GASEOUS EMISSION IN g./km PROM TESTS
AT 48 km/hr ON
27
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FIGURE 12. GASEOUS EMISSIONS IN q/km PROM TESTS
AT 96 ktn/hr ON EIGHT CARS
28
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FIGURE 13. SULFURIC ACID AND SULFUR DIOXIDE EMISSIONS
FROM 1975 FTP TESTS ON EIGHT CARS
29
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FIGURE 15. SULFURIC ACID AND SULFUR DIOXIDE EMISSIONS FROM
TESTS AT 96 kft/hr ON EIGHT CARS
31
-------
for the 1975 Federal Ford Granada. The 1972 Plymouth, the 1975 Federal
Chevrolet and the 1975 California Chevrolet did not meet their respective
CO standards. The 1972 Plymouth and the 1975 Federal Ford Granada did
not meet their respective HC standards. In general, however, the cars
were considered close enough to their standards that they could be con-
sidered typical of their respective model.
The HC and CO emissions at 48 and 96 kph (30 and 60 mph) constant speed
conditions are significantly lower than the FTP emissions for all cars. It
is particularly interesting to compare the CO emissions for the 1972 Plymouth
and the four catalyst cars (cars 4 through 7) at the 48 kph constant speed
condition. The catalyst car CO emissions are approximately 2 percent of
the 1972 car CO emissions at this condition. The NOX emissions at 48 kph are
less than the FTP NOX emissions. The 96 kph NOX emissions are approximately
the same as the FTP emissions for all cars, except for the Honda CVCC and the
1975 Federal Plymouth.
The sulfate emissions, shown in Figures 13 to 15, are somewhat more
difficult to compare since the percent sulfur in the fuel is not the same
for all cars. Since it is not certain that the sulfate emissions are directly
proportional to the amount of sulfur in the fuel for a given car, no attempt
will be made to adjust the emissions in mg/km to a single fuel sulfur level.
The sulfate emissions from the gasoline fueled, non-catalyst cars are in
general agreement with those seen by other researchers. The 30 and 60 mph
sulfate levels are in good agreement with the Ford and Exxon data summarized
in Reference 7. The 1975 FTP sulfate levels of the 1972 Plymouth are approxi-
mately one and a half times the levls obtained by EPA-RTP on similar non-
catalyst cars.* it should also be mentioned that the sulfate levels from
the 1972 Plymouth are approximately 10 times the sulfate emissions seen from
1975 FTP tests of a 1972 Chevrolet engine tested on a special engine dyna-
mometer by the Department of Emissions Research at SwRI.<8)
A careful comparison of the test data from these two different "vehicles"
indicates that this difference is real. The 1972 Plymouth had been operated
for approximately 30,000 miles on leaded fuel prior to being tested with un-
leaded fuel in this program. It is possible that despite efforts to ensure
that the lead "motor mix" components were purged from the exhaust system
prior to testing for sulfate, some artifacts of leaded fuel operation remained
in the exhaust system contaminating the sulfate samples. See Appendix B for
a discussion of the interferences to the BCA system caused by lead, bromine
and chlorine compounds.
It is likely, considering that the car was operated for 500 miles to
purge the motor mix compounds, that the FTP sulfate emission level from this
car is real. The large percentage variation in noncatalyst FTP sulfate ends
sions that would result from comparing this car with others is largely due to
the small absolute magnitude of the noncatalyst FTP sulfate emissions.
The 48 kph steady state sulfate emissions in g/km are the lowest of the
three test conditions. This is not surprising since sulfate emissions for
a given noncatalyst vehicle tend to be a function of the amount of fuel used
and the 48 kph condition uses the least fuel. It is interesting to note
32
-------
that the Honda has higher sulfate emissions at the 48 kph and 96 kph condi-
tions than the Granada, despite the fact the Honda has considerably lower
fuel consumption.
The sulfate emissions from the catalyst cars were also in general
agreement with those found by other researchers . (.7) AS can be seen in
Figures 13 to 15, catalyst cars equipped with air injection and calibrated
to meet the 1975 California standard of 0.6 g/km HC, 5.6 g/km CO and 1.3
g/km NOX, in general, have higher sulfate emissions than catalyst cars with-
out air injection and calibrated to meet the 1975 Federal Standard of 0.9
g/km HC, 9.3 g/km CO and 1.9 g/km NOX.
For the catalyst cars without air injection (cars 4 and 5), the 48
kph cruise condition produced the largest amount of sulfates in terms
of mg/km. The catalyst cars equipped with air injection systems (cars
6 and 7)- do not show the same results. Car 6 produces the most mg/km of
sulfates at 96 kph and the least mg/km of sulfates at 48 kph. Car 7
produces the most sulfate at 48 kph and the least during the FTP test.
The diesel car sulfate emissions in mg/km are in good agreement with those
seen on single car tests at GM and EPA(1^0 considering the size of the
car tested in each case. The GM and EPA tests were on smaller cars. The
GM test on a "small diesel-powered car" gave 9.94 g/km by a 1972 FTP using
No. 2 diesel fuel with 0.39 percent sulfur. The EPA baseline test on a
prototype diesel-powered VW Rabbit gave 5.3 g/km on a 1975 FTP using No. 2
diesel fuel with 0.27 percent sulfur. The sulfate emissions from the diesel
car are probably a function of the fuel consumed since the lowest sulfate
emissions are at 48 kph and the highest at 96 kph. While the diesel car
has the highest sulfate emissions of any of the noncatalyst cars, it should
be kept in mind that the test diesel fuel contained approximately six times
the sulfur contained in the test gasoline.
Since the cars were run on fuels with three different sulfur levels, it
is instructive to compare the cars in terms of percentage of fuel sulfur con-
verted to sulfuric acid. This is done in Figures 16 to 18. The noncatalyst
gasoline powered cars had total sulfur recoveries between 82 percent and 114
percent for the three different test types. This range should probably be
considered the range of values obtainable for complete sulfur recovery using
the SO2-BCA method. There is apparently no temporary storage and release of
sulfur compounds associated with the noncatalyst cars. Less than 1.5 per-
cent of the fuel sulfur was converted to exhaust sulfuric acid for any of the
three test conditions run on the three non catalyst cars (cars 1 to 3).
The catalyst cars without air injection had total recoveries of approxi-
mately 45 to 59 percent for the FTP and approximately 19 to 21 percent for the
48 kph test. These total sulfur recoveries indicate that there is a net sul-
fur storage in the catalyst during these tests. The total sulfur recoveries
for these two cars from the 96 kph tests were approximately 175 and 159 per-
cent, indicating a net sulfur release from the catalyst for this test. The
highest percentage of fuel sulfur converted to exhaust sulfuric acid for the
test series run on the catalyst cars without air injection was 7.3 percent.
This occurred on the 48 kph test of car number 5. It is interesting that on
both these cars the highest fuel sulfur conversion to sulfuric acid occurred
at 48 kph; the test condition with the smallest total sulfur recovery.
33
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FIGURE 17. PERCENT OF FUEL SULFUR RECOVERED IN VEHICLE EXHAUST
AS SULPURTC ACID AND SULFUR DIOXIDE FOR 48 kph STEADY STATE TESTS OF EIGHT CARS
35
-------
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FIGURE 18. PERCENT OF FUEL SULFUR RECOVERED IN VEHICLE EXHAUST AS
SULFURIC ACID AND SULFUR DIOXIDE FOR 96 kph STEADY STATE TESTS OF EIGHT CARS
36
-------
The results from catalyst cars with air injection (cars 6 and 7) are
again, harder to interpret. Examining the total sulfur recoveries from the
FTP it appears that car 6 had a net release of sulfur and car 7 a net storage
of sulfur during this test. Both cars definitely stored sulfur during the
48 kph run as evidenced by their total recoveries of approximately 36 percent
for car 5 and 39 percent for car 7. Unlike the catalyst cars without air
injection, cars with air injection (6 and 7), did not release sulfur during
the 96 kph test. Car 6 may have had some storage, but the sulfur recovery
data indicates essentially complete recovery of the fuel sulfur. Car 7
definitely stored sulfur during the 96 kph test.
For car 6, more of the fuel sulfur was converted to sulfuric acid (42
percent) at 96 kph than at any other test condition. Car 7, like the two
non-air injected cars converted the largest amount of fuel sulfur to sulfuric
acid (20 percent) during the 48 kph test.
The diesel car had total recoveries ranging from approximately 80 to
128 percent for the three tests. It is felt that this range of recoveries
represents complete fuel sulfur recovery for each test, with no storage or
release of sulfur. The maximum percent of fuel sulfur converted to sulfuric
acid for any of the diesel car tests was 2.9 percent at the 96 kph condition.
The conversion percentage is similar to the non-catalyst gasoline cars. This
indicates that the relatively higher diesel mg/km sulfate emissions are
caused by the diesel fuel sulfur levels being higher than the gasoline levels
(0.23 versus 0. 04 ).
Results of Method 8 Tests
As explained in Section II of this report, at the beginning of the
project, it was felt by some researchers that EPA stationary source
Method 8 test might be an acceptable procedure for determining automobile
exhaust sulfates and S02- To determine the Method's applicability, steady
state tests at 48 and 96 kph were run on the 1972 Plymouth, with leaded
and unleaded fuel, and on the 1975 Honda CVCC. The results of these tests
are presented in Table 5. The top part of the table contains the results
of the tests with leaded and unleaded fuel on the 1972 Plymouth. The
lower part of the table contains the test results from the 1975 Honda CVCC.
The S02 levels from the leaded fuel 48 and 96 kph tests on the 1972
Plymouth using Method 8 were 0.07 and 0.08 g/km, respectively. No sulfate
was detected from leaded fuel tests of this car using Method 8, even after
sampling for 90 minutes at 48 kph and 60 minutes at 96 pkh. This does not
necessarily mean that no sulfuric acid was formed in the exhaust, it merely
indicates that it was not detected by the sampling method. The problem was
one of obtaining a definite end-point for the sulfate analysis procedure of
Method 8. In the analysis of the leaded fuel tests, the solution from the
first (sulfate) bubbler did not turn a bright yellow when the thorin indi-
cator was added as it did in the unleaded fuel tests and in the S02 bubblers
from both unleaded and leaded fuel tests. The color produced was a dirty
orange-yellow that did not change regardless of the amount of barium per-
chlorate added during the titration. Thus, it is uncertain what the leaded
fuel test results demonstrate. It may be that there is no sulfate present,
37
-------
TABLE 5. SUMMARY OF EPA METHOD 8 TEST RESULTS
Test
Date
Test
Type
Test
Duration
min
S02, H2S04,
g/km Ms/ km
1972 Plymouth With
Leaded Fuel, (0.
10/22/74
11/7/74
11/18/74
2/17/75
2/18/75
A
Average
11/8/74
11/8/74
11/18/74
11/21/74
Average
48 kph
48 kph
48 kph
48 kph
48 kph
4.8 . kph
96 kph
96 kph
96 kph
96 kph
96 kph :
90
90
90
90
90
90
70
60
60
60
0.074
0.062
0.080
0.050
0.067
0.067
0.070
0.080
0.082
0.076
0.077
Unleaded Fuel (0.
1/27/75
1/28/75
Average
1/29/75
1/29/75
Average
48 kph
48 kph.
48 kph
96 kph
96 kph
96 kph
90
90
90
60
60
60
1975 Honda
0.065
0.065
0.065
0.074
0.071
0.073
Civic With a
Unleaded Fuel, (0
2/10/75
2/19/75
Average
2/6/75
2/10/75
Average
48 kph
48 kph
48 kph
96 kph
96 kph
96 kph
90
90
90
60
60
60
0.027
0.027
0.027
0.036
0.036
0.036
Percent Percent Percent
Fuel S Fuel S Fuel S
as SO? as H?SOA Recovered.
360 C1D Engine
051%
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5.52
4. 28
4.97
3.73
3.31
3.52
Sulfur)
80.2
78. 5
88.1
52.9
73.5
74.5
69.6
84.1
78 0
t \J * \s "
71 3
1 A •
-------
or it may be that the lead in the exhaust reacts with the thorin indicator
giving the color observed.
Thus for the leaded fuel tests, only the fuel sulfur converted to SC>2
was measured in the exhaust. The percentage of fuel sulfur recovered in
this manner was approximately 75 percent for both the 48 and 96 kph tests.
For the tests of the 1972 Plymouth using unleaded fuel, the Method 8
SO2 levels for 48 and 96 kph averaged 0.06 g/km and 0.07 g/km, respectively.
Note that the SC>2 emissions from the unleaded fuel show good agreement with
the SC>2 emissions from the leaded fuel tests.
The unleaded fuel sulfate emissions using the Method 8 procedure averaged
5.0 mg/km of H2SO4 at 30 mph and 3.5 mg/km of H2SO4 at 60 mph. The Method 8
sulfate results are questionable since no definite pink end-point occurred for
the sulfate sample in the titration procedure. During the titration proce-
dure, the sulfate sample color turns from a bright yellow to a dirty-orange-
yellow very gradually with no sharp end-point. The Method 8 SC^ samples do,
however, have a reasonably good pink end-point.
The total sulfur recovery for the unleaded fuel tests on the 1972 Ply-
mouth was approximately 76 percent for the 48 kph tests and 83 percent for
the 96 kph tests. Note that these recoveries are in close agreement with
the leaded fuel tests. The sulfate emissions expressed as percent of fuel
sulfur averaged 3.6 for the 48 kph tests and 2.6 for the 96 kph tests.
The S02 emissions from tests on the Honda CVCC were 0.03 g/km for the 48
kph tests and 0.04 for the 96 kph tests, as shown in the lower part of Table 5.
These S02 emissions are lower than the Plymouth S02 emissions as would be ex-
pected since fuel used on the Honda tests has a lower sulfur level and the
Honda used less fuel.
The total sulfur recovery for the Honda was somewhat better than the
total recovery for the Plymouth. The Honda had a total sulfur recovery of
86 percent at 48 kph and 94 percent at 96 kph. The percent of fuel sulfur
recovered as sulfuric acid was 3.2 percent at 48 kph and 6.8 percent at
96 kph. As was the case with the sulfate samples from the Plymouth, there
was no distinct end-point in the titration of the sulfate samples from the
Honda CVCC.
The Method 8 test results and the BCA test results in mass units per
kilometre are compared in Figure 19. As can be seen in the figure, the SC>2
emissions by Method 8 are always lower than the SO2 emissions by BCA. How-
ever, they are generally within 0.015 g/km of the BCA SC>2 emissions. The
Method 8 SO2 emissions at 48 kph averaged about 22 percent less than the
BCA-SC-2 emissions. At 96kph, the Method 8 SC>2 emissions averaged about 8 less
than the BCA-SO2 emissions.
Recall that for leaded fuel tests of the Plymouth, sulfate was mea-
sured using Method 8 only. The barium chloranilate procedure for analyzing
sulfate on filters was not useable with leaded fuel because of the inter-
ferences from the scavengers used with the lead. Therefore, there is no com-
parison data available for the leaded fuel tests on the Plymouth. For the
remainder of the tests, Method 8 sulfate results in mg/km Were from 2 to 50
39
-------
3 -
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(leaded)
(unleaded)
48 kph
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96 kph
FIGURE 19. COMPARISON OF METHOD 8 AND BCA SO? AND SULFATK RESULTS
IN mg/km FOR 48 AND 96 kph STEADY STATE TESTS FOR TWO NON CATALYST CARS
40
-------
times higher than the BCA sulfate results.
Figure 20 shows the comparison of Method 8 and BCA results in terms
of percent of fuel sulfur recovered as S02 and sulfuric acid. At 48 kph,
the total recovery by the BCA procedure averaged 98 percent, while the
total recovery by Method 8 averaged 79 percent. At 96 kph, the total
recovery by the BCA procedure averaged 100 percent, while the total re-
covery by Method 8 averaged 84 percent. In all cases the total recovery
by BCA was greater than the total recovery by Method 8. The BCA values
were closer to the desired 100 percent recovery. The percentage of fuel
sulfur recovered as sulfuric acid was less for the BCA procedure for all
tests.
In summary, the Method 8 procedure yielded lower SO^ values, higher
sulfuric acid values, and recovered less of the total fuel sulfur than the
BCA procedure. It is felt that the Method 8 procedure as outlined in the
Federal Register for stationary sources is inferior to the BCA procedure
because of the problem of obtaining a definite titration end-point for the
sulfate sample. Apparently, Method 8 can yield accurate results at higher
sulfate levels that are more free from interferences such as may be the
case for stack samples, but is not as satisfactory for sulfate in automobile
exhaust.
Of course, there are improvements that could be made to Method 8, such
as passing the sample through a cation exchange column prior to titration
and the use of automatic titration equipment. However, at the conclusion
of these three sets of tests, it was felt that there was no need to develop
the Method 8 procedure further. The BCA procedure for analyzing sulfate
filters was entirely satisfactory and there was no pressing need for an
alternate method. Therefore, the use of Method 8 was discontinued.
Filter Particulate Weights
As mentioned in the introduction, sulfuric acid emissions from catalyst
cars were originally confirmed during studies of particulate emissions from
gasoline-powered automobiles. There was some interest as to how much of the
total particulate mass collected on a filter was sulfuric acid. It should
be mentioned that although the 21 cm tunnel is adequate for sulfate, no
claim was made that the 21 cm diameter sulfate sampling tunnel is an
adequate tunnel for total particulate sampling. No checks were run to
determine its ability to collect particulate matter over the range that
might be seen in automobile exhaust. Thus, no claim is made that a repre-
sentative sample of all exhaust partioulates were collected on the sulfate
filter. Nevertheless, each sulfate filter was weighed on a microgram
balance before and after use.
The three noncatalyst gasoline-powered cars were tested prior to the
initiation of the filter ammoniation procedure, thus the sulfate on the
filter is in the form of sulfuric acid when weighed. Since sulfuric acid
is hydroscopic, there is also some amount of water associated with the
sulfuric acid on the filter. The amount of water is dependent in part, on
the amount of sulfuric acid and the humidity of the environment to which it
has been exposed. Thus, it is not unreasonable to expect a varying amount
of water from filter to filter. This makes interpretation of the net filter
41
-------
-n
v
M
01
>
o
0)
3
Pn
-------
woiqht: difficult. This variability is not due to conditions under which
the filter was weighed since the temperature and humidity were rigidly main-
tained.
Table 6 contains the net filter weights obtained from the microgram
balance together with the sulfate, as sulfuric acid, per filter from the
BCA analysis. Figure 21 is a plot of these data. As can be seen from
the figure there is no simple relationship between the net balance weight
and the BCA sulfuric acid weight.
Starting with the four catalyst cars, the sulfate laden filters were
exposed to ammonia gas prior to the after test weighing. This exposure
converted the sulfuric acid to ammonium sulfate. This compound has the
advantage of not being hydroscopic, thus eliminating the problem of absorbed
water on the filter.
The sulfate characterization tests were only a small part of the sul-
fate testing done on the four catalyst cars. Since the report section of
distance accumulation includes a discussion of the relationships between
filter weight and BCA sulfate weight for all tests on these cars, those
results will not be covered here.
Elemental Analysis of Tunnel Sweepings
There has been some concern that catalysts may emit, as particulate
matter from the exhaust, amounts of the noble metals used in the catalyst.
To investigate this problem as well as to try and identify, on an elemental
basis, any difference in exhaust particulate emissions from several car types
the sulfate tunnel particulate residue was analyzed by X-ray fluorescence
techniques.
After the test series was completed on each gasoline-powered car, the
Sulfate sampling tunnel was swept out with a fine bristle brush. The tunnel
residue from the diesel car tests was not collected. The special problem of
diesel engine particulate is currently being researched at SwRI^11^ in a far
more rigorous and complete manner than could be done with the amount of effort
allotted to the examination of tunnel residue.
Elemental analysis of the tunnel residue for each car, as percent of
sample by weight, is shown in Table 7. The analysis was requested for platinum
(Pt), palladium (Pd), aluminum (Al), nickel (Ni), iron (Fe), sulfur (S), lead
(Pb), zinc (Zn), copper (Cu), and tin (Sn). Of these 10 elements, no plati-
num, palladium, nickel, copper or tin was found in any of the samples. Chrom-
ium, silicon, and manganese were found in some of the samples and are included
in Table 7. The detection limits for the 10 elements requested are also shown
in Table 7.
Examination of Table 7 indicates that the largest part of each sample was
iron. From a visual inspection of the samples, the iron is apparently in the
form of rust, probably from the exhaust system. The other elements were found
in much smaller quantities. It is thought that the silicon may be from traces
of the glass SC>2 probe which was broken rather frequently during test prepara-
tions. The genesis of the other elements is open to speculation.
43
-------
2500
2000
1500
O
D O
A
1000
700
O
en 600
•H
I
•H
t,
-P
0)
O
500
D
Symbol
O
D
O
A
Test
Cold FTP
Hot FTP
48 KPH
96 KPH
400
300
200
100
A
20
40
60
80
100
120
140
160
BCA Sulfate as H2SO4,
FIGURE 21. COMPARISON OF FILTER WEIGHT AND SULFATE WEIGHT
PER FILTER BY BCA ANALYSIS FOR THREE CARS
44
-------
Date
TABLE 6. COMPARISON OF FILTER WEIGHTS AND SULFATE WEIGHTS
PER FILTER BY BCA ANALYSIS FOR THREE CARS
Test
Balance
Filter No. net yg/f liter
BCA
BCA
as H2SO4
1973 PLYMOUTH, UNLEADED FUEL
1/28/75
1/28/75
1/27/75
1/29/75
1/29/75
1/29/75
1/28/75
1/29/75
FTP Cold
FTP Hot
48 kph
96 kph
FTP Cold
FTP Hot
48 kph
96 kph
47-FH-122
47-FH-123
47-FH-121
47-FH-128
47-FH-126
47-FH-127
47-FH-125
47-FH-129
2363
1297
663
2763
1370
432
118
1285
55.63
39.58
10.19
151.78
47.26
19.21
6.66
65.10
56.80
40.41
10.40
154.97
48.25
19.61
6.80
66.47
1975 HONDA CIVIC CVCC
2/11/75
2/11/75
2/10/75
2/10/75
2/12/75
2/12/75
2/19/75
3/12/75
FTP Cold
FTP Hot
48 kph
96 kph
FTP Cold
FTP Hot
48 kph
96 kph
47-FH-146
47-FH-147
47-FH-142
47-FH-143
47-FH-148
47-FH-149
47-FH-152
47-FH-210
62
178
189
281
155
161
205
197
9.95
7.65
8.58
34.57
8.40
4.44
8.38
67.02
10.16
7.81
8.76
35.30
8.58
4.53
8.55
68.43
1975 FORD GRANADA
3/10/75
3/10/75
3/06/75
3/06/75
3/07/75
3/07/75
3/07/75
3/07/75
FTP Cold
FTP Hot
48 kph
96 kph
FTP Cold
FTP Hot
48 kph
96 kph
47-FH-189
47-FH-190
47-FH-177
47-FH-178
47-FH-179
47-FH-180
47-FH-181
47-FH-182
578
53
100
128
127
55
41
17
7.81
6.37
7.38
16.90
11.92
6.37
5.66
12.83
7.97
6.50
7.53
17.25
12.17
6.50
5.78
13.10
45
-------
TABLE 7. RESULTS OF X-RAY FLUORESCENT ANALYSIS OF SULFATE
SAMPLING TUNNEL PARTICULATE RESIDUE FOR SULFATE CHARACTERIZATION CARS
Car
en
72 Plymouth
(Leaded fuel)
72 Plymouth
(Unleaded)
75 Honda CVCC
75 Ford Granada
EM-1 2000 mi
EM-2 2000 mi
EM-3 2000 mi
EM-4 2000 mi
Detection limits, yg
Detection limit,
wt % of 1000 yg
sample
2.316
1.
1.
.629
,285
0.113
0.053
0.163
0.051
0.019
2.46
1.75
2.47
.43
,36
.16
1.31
1.46
1.
1.
2.
AJL
0.3
0.2
0.4
0.2
0.4
0.2
1.0
Fe
13.7
18.3
30.2
21.0
29.3
24.2
28.1
21.8
1.0
S_
0.7
0.6
0.1
0.9
0.2
0.3
0.5
0.2
1.0
PB An
2.5
— __
2.6 0.4
12.5 1.0
Cr
0.3
0.2
0.2
0.1
Si
0.2
0.3
0.1
0.9
0.4
0.1
0.9
0.1
Mn
0.3
0.2
0.4
0.1
0.1 0.1
1.25
Note: Detection limit for Pt, Ni, Cu, Sn and Pd are all 1.0 yg or 0.1% of 1000 yg sample.
-------
IV. EFFECTS OF DISTANCE ACCUMULATION
This section covers the sulfate emission testing of four catalyst
cars at regular intervals during an accumulation of approximately 80,500
kilometres on each vehicle.
A. Purpose
The purpose of this portion of the project was to measure HC, CO,
NOX, SO2 and sulfates on four catalyst equipped cars to determine the
behavior of sulfate emissions with distance accumulation. Where possible,
the conditions of storage and release of sulfur compounds from the catalyst
were to be identified.
B. Cars Tested
To meet the objectives of this part of the project, four popular full
size, 1975 passenger cars were selected for testing. Two of the cars were
Chevrolet Impalas equipped with pelleted catalysts. The other two cars were
Plymouth Gran Furys equipped with monolith catalysts. One of each of the
models was manufactured to meet 1975 California emission standards and was
equipped with an air injection system upstream of the catalyst. Table 8
gives a complete description of the four cars. Pictures of the four cars
are shown in Figure 9 of Section III.
C. Fuel Used
Initially the cars were scheduled to complete the distance accumulation
program at 24,100 km. One 15,000 litre batch of fuel was felt to be suf-
ficient for the testing scheduled. As the project progressed, additional
tests were added to the test sequence consuming the fuel at a faster rate
than planned. Just prior to the 16,000 km test on all cars, a new 15,000
litre batch of fuel was obtained from the same supplier. After the 24,100
km tests, the distance accumulation was extended to 80,500 km. Because avail-
able tankage had already been committed to other projects, it was not possible
to secure one batch of fuel for the 24,100 to 80,500 km distance accumulation.
Thus, two additional batches of fuel were required to complete the 80,000 km
accumulation on all four vehicles.
The base fuel used was Gulf Oil company's "Gulf Crest" brand of unleaded
gasoline. This fuel was chosen because of its low sulfur content as delivered
and its commercial availability, since it was desired to operate the cars on
a typical retail gasoline. As mentioned in the characterization section, a
sulfur level of 0.040 percent was chosen based on Bureau of Mines gasoline
surveys of leaded fuels in the early 1970's. Thiophene, a sulfur compound
occurring naturally in gasoline, was used to increase the fuel sulfur level
to a nominal 0.040 percent.
Table 9 lists the four fuel batches used and the sulfur content of each
batch after addition of thiophene. Also shown are the test sequences for
which each fuel batch was used. Complete analyses of the fuels designated
EM-212F, EM-250F and EM-254F and the sulfur analysis of all four fuels are
contained in Appendix F. "
47
-------
TABLE 8. CARS TESTED IN DISTANCE ACCUMULATION
SwRI Car Number
Manufacturer
Model
Model Year
Applicable Emission Std.
Date Manufactured
Veh. Ident. No.
Engine Size, litres
Arr. & No. of Cyl.
Engine Serial No.
Transmission
Catalyst Type
Catalyst Serial No.
Air Injection
Carburetor Mfgr.
No. of Carb. Barrels
Car. Serial No.
Ignition System
Tires
EM-1
EM-2
EM-3
EM-4
Plymouth
Gran Fury
1975
'75 Fed.
9/74
PH41K5D-
114692
5.90
V-8
5E114692
Automatic
Monolith
NO
Holley
2
R7226A-
3830563 2494
Breakerless
Electronic
Radial
GR78-15
Chevrolet
Impala
1975
'75 Fed.
3/75
1L69H5S-
137797
5.73
V-8
15S137797-
VO312CMJ
Automatic
Pelleted
009454
NO
Rochester
2
22-5-TH-
7045114
Breakerless
Electronic
Radial
HR78-15
Plymouth
Gran Fury
1975
'75 Calif.
3/75
PH41J5D-
209866
5.90
V-8
5E2 09866
Automatic
Monolith
YES
Carter
4
Breakerless
Electronic
Radial
GR78-15
Chevrolet
Impala
1975
•75 Calif.
4/75
1L69L5J-
216102
5.73
V-8
15J21602-
VO411CMM
Automatic
Pelleted
094546
YES
Rochester
4
7045504-
TM0505
Breakerless
Electronic
Radial
HR78-15
48
-------
TABLE 9. FUEL BATCHES USED IN DISTANCE ACCUMULATION STUDY
Fuel*
Pet. Sulfur
Used: From
To
Used for Distance
Accumulation on
EM-1
EM-2
EM-3
EM-4
Used for tests on:
EM-1
EM-2
EM-3
EM-4
EM-212-F
0.0415
11/26/74
9/15/75
to approx. 16,000 km
to approx. 16,000 km
to approx. 16,000 km
to approx. 16,000 km
to 8,050 km
to 8,050 km
to 8,050 km
to 8,050 km
EM-243-F
0.0420
9/15/75
12/30/75
16,000 to 32,200 km
16,000 to 32,200 km
16,000 to 32,200 km
16,000 to 32,200 km
16,000, 24,100, 32,200 km
16,000, 24,100, 32,200 km
16,000, 24,100, 32,200 km
16,000, 24,100, 32,200 km
EM-250-F
0.0405
12/30/75
2/25/76
32,200 to 55,000 km
32,200 to 60,000 km
32,200 to 48,000 km
32,200 to 56,000 km
48,300 km
48,300 km
48,300 km
48,300 km
EM-254-F
0.0410
2/25/76
5/15/76
55,000 to 80,500 km
60,000 to 80,500 km
48,300 to 80,500 km
56,000 to 80,500 km
64,400, 80,500 km
64,400, 80,500 km
64,400, 80,500 km
64,400, 80,500 km
*Base fuel for all fuel batches was Gulf Oil Company "Gulf Crest" brand unleaded gasoline.
-------
D. Vehicle Maintenance
The vehicles were maintained according to the maintenance schedule
provided by the car manufacturer. Basically, the Plymouths, cars EM-1
and EM-3, received scheduled maintenance at approximately 8,000 kilometre
intervals; the Chevrolets, cars EM-2 and EM-4, at approximately 12,000
kilometre intervals. The complete maintenance schedule for each car is
included in Appendix H.
Engine oil level was checked daily (usually this was equivalent to
650 kilometres) and added as needed. Brake linings were also replaced as
needed. Tires were replaced on all four cars between the 48,300 and 64,400
kilometre tests with tires of the same size and type as those being replaced.
There were several items of unscheduled maintenance. On car EM-3,
the EGR system vacuum amplifier was found to have failed sometime after
the 24,100 kilometre test and prior to the 32,200 kilometre test. It was
replaced after the 32,200 km test. Also, on this car, a valve guide insert
was installed on the exhaust valve of the number one cylinder at approxi-
mately 50,000 kilometres to correct a low compression problem in that
cylinder. The transmission on car EM-4 failed and was rebuilt at approxi-
mately 33,500 kilometres. A leak in the catalyst air injection system on
car EM-4 was discovered and corrected at 19,000 kilometres. From test data
on the car, it is assumed that this leak started sometime between the 3,200
and 8,050 kilometre tests.
E. Test Sequence
The test plan called for emission tests in factory new condition (i.e.,
less than 150 kilometres) and at 3,200, 8,050, 16,100 and 24,100 kilometres.
During the test program the distance was extended to 80,500 kilometres with
emissions tests at 32,200, 48,300, 64,400 and 80,500 kilometres. The dis-
tance was accumulated by driving the cars over a modified MVMA durability
schedule per MSAPC Advisory Circular 37, dated December 20, 1973 for 55 mph
top speed. A copy <5f this procedure is contained in Appendix H, together
with a description of the actual route driven. In addition, all wide-open
throttle accelerations were eliminated from the schedule to prevent inad-
vertent purging of -stored sul fates.
The "zero" kilometre and 3,200 kilometre test sequence is shown in
Table 10. The time period during which the cars were accumulating 24,100
kilometres was one of rapid change in sulfate test cycles and scheduling
philosophy. As a result of this, the 8,050 mile tests on all cars incor-
porated the SET-7 test and the Highway Fuel Economy Test (HPET), as shown
in Table 11. This test sequence was also used for the 16,100 kilometre
tests of EM-1 and EM-2. The test sequence was changed again to that shown
in Table 12 for the 16,100 kilometre tests of EM-3 and EM-4 and the 24,100
kilometre test on all four cars.
The test sequence for tests up to and including the 24,100 kilometre
test were run twice with approximately 500 kilometres of durability driving
between each test sequence. For tests following the 24,100 kilometre test,
the test sequence shown in Table 13 was run only once, except for the 80,500
50
-------
TABLE 10. TEST SEQUENCE FOR 0 AND 3200 KILOMETRE TESTS
TEST DESCRIPTION
1 Cold start LA-4 cycle
10 minute soak
2 Hot start LA-4 cycle
Soak 10 min. or as required
while preparing SOX sampling
equipment, but not over one
hour
3 Start vehicle, accelerate to
48 kph in about 15 seconds,
then 48 kph cruise for 20
minutes, sampling from "key on"
4 Cruise at 48 kph for 30 minutes
Soak 10 min, or as required
while preparing SOX sampling
equipment, but not over one hour
5 Start vehicle, accelerate to 96
kph in about 30 seconds then 96
kph cruise 20 minutes, sampling
from "key on"
6 Cruise at 96 kph 20 minutes
51
-------
TABLE 11. TEST SEQUENCE FOR 8 050 KILOMETRE TEST
ON ALL CARS AND 16,100 KILOMETRE TEST ON CARS EM-1 AND EM-2
TEST DESCRIPTION
1 Cold start LA-4
10 minute soak
2 Hot start LA-4
Soak 10 minutes*
3 SET-7 test
Soak 10 minutes*
4 SET-7 test
Soak 10 Minutes*
5 HFET test
Soak 10 minutes*
6 HFET test
Soak 10 minutes*
7 Start vehicle, accelerate to 48 kph
in about 15 seconds, then 48 kph cruise
for 20 minutes, sampling from "key on"
8 Cruise at 48 kph for 30 minutes
Soak 10 minutes*
9 Start vehicle accelerate to 96 kph in
about 30 seconds, then 96 kph cruise for
20 minutes, sampling from "key on"
10 Cruise at 96 kph for 20 minutes
*or as required while preparing SOX sampling equipment,
but not over one hour
52
-------
TABLE 12. TEST SEQUENCE FOR 24,100 KILOMETRE TEST
ON ALL CARS AND 16,100 KILOMETRE TESTS ON CARS EM-3 AND EM-4
TEST DESCRIPTION
1 1975 light duty FTP (single sulfate
and SO2 sample)
10 minute soak*
2 SET-7 test
10 minute soak*
3 SET-7 test
10 minute soak*
4 HFET test
10 minute soak
5 SET-7 test
10 minute soak
6 SET-7 test
10 minute soak
7 Start vehicle, accelerate to 48 kph in
about 15 seconds, then 48 kph cruise for
20 minutes, sampling from "key on"
8 Cruise at 48 kph for 30 minutes
Soak 10 minutes
9 Start vehicle, accelerate to 96 kph in
about 30 seconds, then 96 kph cruise for
20 minutes, sampling from "key on"
10 Cruise at 96 kph for 20 minutes
*or as required while preparing SOX sampling equipment,
but not over one hour
53
-------
TABLE 13. TEST SEQUENCE FOR TESTS AT 32,200 KILOMETRES,
48,300 KILOMETRES, 64,400 KILOMETRES AND 80,500 KILOMETRES FOR ALL CARS
TEST DESCRIPTION
1 1975 FTP (single sulfate and S02 sample
5 minute idle^
2 SET-7 test
5 minute idle
3 SET-7
5 minute idle
4 HFET test
5 minute idle
5 SET-7 test
5 minute idle
6 SET-7 test
5 minute idle
7 Accelerate to 48 kph in about 15
seconds, then 48 kph cruise for 20
minutes
8 Cruise at 48 kph for 30 minutes
5 minute idle
9 Start vehicle, accelerate to 96 kph in
about 30 seconds, then 96 kph cruise for
20 minutes
10 Cruise at 96 kph for 20 minutes
*No preconditioning following mileage accumulation on modified AMA cycle.
^All idles are 5.0 ± 0.5 minutes.
Sulfate, S02, HC, CO, NOx and CO2 emissions are taken during all test
modes except idle.
54
-------
kilometre test which was run in duplicate. The replicate 80,500 km tests
or cars EM-1 and EM-2 were not averaged as was done for cars EM-3 and EM-4
because of the erratic emissions results obtained from cars EM-1 and EM-2.
The test data from these two cars was thoroughly checked for possible
errors which might have caused the erratic emission results. Since no
errors were found, it is concluded that the variation in emissions is due
to vehicle operation. Because 48,300 kilometres was a major maintenance
point for all cars, the test sequence was run before maintenance and after
maintenance plus 500 kilometres durability driving.
It is emphasized that in the discussions to follow, the tests identi-
fied as "acceleration to 48 kph" and "acceleration to 96 kph," include not
only the actual acceleration from 0 to the indicated speed, but also a
portion of time at the stabilized speed.
P. Test Results
The test results from the four cars tested under this phase of the pro-
ject fell into four different classifications and are covered in the fol-
lowing four subsections; 1. Gaseous and BCA Sulfate Emissions, 2. Storage
of Sulfur Compounds, 3. Particulate Weights, and 4. Analysis of Tunnel
Residue.
1. Gaseous and BCA Sulfate Emissions
A summary of the average gaseous emissions is given for each test
type on all four cars at each distance interval in Tables 14 through 16 for
HC, CO, and NOX emissions, respectively. To aid in determining any trends
with distance, this information has been plotted as Figures 22 to 24. Results
for each individual test are contained in Appendix H. Figure 22 shows the
HC, CO and NOX emissions from the FTP tests on all four cars at each distance
interval test. For comparison purposes, the 1975 Federal and 1975 California
emission standards in terms of grams/kilometre are shown on the plots. As
can be seen from this figure, the HC emissions were generally within the appli-
cable standard throughout the 80,500 kilometres on all cars. The exceptions
being car EM-4 at 8,050 and 16,100 kilometres, EM-3 at 48,300 and 80,500
kilometres, and the second test of EM-2 at 80,500 kilometres. The high HC
emissions from car EM-4 at 8,050 and 16,000 kilometres are attributed to a
leak in the air injection system. In fact, the high HC emissions helped lead
to the discovery of the leak shortly after the 16,000 kilometre test. There
was a general tendency for HC emissions from all cars to increase from the
48,300 km test to the 80,500 km test.
The CO emissions from the FTP were generally above the applicable
standard. EM -1 had CO emissions below the 1975 Federal CO standard of
9.3 g/km for 4 of the 10 tests and CO emissions from EM-2 were below the
standard 2 of 10 times. The CO emissions from EM-3 were below the 1975 Cali-
fornia CO standard of 5.6 g/km 6 of 10 times. The CO emissions from car
EM-4 were never below the 1975 California CO standard. The general trend of
CO emissions was increasing after the 3,200 km test for all cars, with the
largest increases after the 48,300 km tests. This increase in both HC and
CO emissions after 38,300 km may be an indication of catalyst deterioration.
55
-------
TABLE 14. AVERAGE HYDROCARBON EMISSIONS BY TEST TYPE FOR
DISTANCE INTERVAL TESTS ON FOUR CARS
FTP
SET-7
FET
Accel to 48 kph
48 kph
Accel to 96 kph
Car
Number
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
96 kph EM-1
EM-2
EM-3
EM-4
* air injection system leak
**EGR system inoperative
***Duplicate Tests on Cars EM-1 and 2 not averaged
See explanation page 55.
HC Emissions g/km
0 km
0.39
0.49
0.56
0.37
<•••<•
v — — •
K — — V
0.14
0.06
0.04
0.12
0.03
0.08
0.03
0.04
0.06
0.09
0.03
0.08
0.04
0. 01
0.02
0.03
3200 km
0.32
0.40
0. 26
0.44
- _ - -
....
- .--
- - — i-
0.11
0.07
0.04
0. 16
0.03
0.03
0.03
0.07
0.08
0.03
0.05
0. 14
0.02
0.01
0.03
0.02
8050 km
0.30
0.42
0.48
1.12*
0. 12
0.07
0.04
0.95*
0.09
0.04
0.03
0.35*
0.09
0. 11
0. 07
0.21*
0.02
0.03
0.05
0. 10*
0.06
0.04
0.04
0. 15*
0.03
0.03
0.03
0.01*
16100 km
0.32
0. 34
0.49
1.68*
0.11
0.11
0.03
1.18*
0.06
0.05
0.03
0.39*
0.09
0.04
0.04
0.21*
0.03
0.04
0.04
0.07*
0.05
0.02
0.04
0.02*
0.02
0.02
0.02
0.00*
24100 km
0.25
0. 35
0.44
0.42
0.09
0. 12
0.03
0.09
0.06
0.06
0.03
0.06
0.03
0.02
0.05
0.08
0.04
0.03
0.05
0.07
0.05
0.04
0.04
0.06
0.02
0.02
0.03
0.07
32200 km 48300 km
0.31
0.39
0.46**
0.27
0. 13
0. 12
0.06**
0.06
0.07
0.05
0. 04**
0.04
0.03
0.03
0. 09**
0. 11
0.03
0.03
0.09
0. 04**
0.03
0.05
0.04**
0.04
0.03
0.02
0.03**
0.03
B/A
0.49/0.44
0.36/0.24
0.64/0.41
0.43/0.47
0.28/0.39
0. 11/0.06
0. 17/0.06
0. 12/0. 14
0.26/0. 31
0.07/0.03
0. 19/0.07
0.07/0. 10
0. 12/0. 11
0.03/0.02
0. 18/0. 10
0. 16/0.40
0.05/0.04
0.03/0.02
0.24/0. 10
0.05/0.21
0.09/0. 12
0.05/0.05
0.20/0. 11
0. 10/0. 15
0. 15/0.04
0. 15/0.02
0. 12/0.09
0.06/0. 18
64400 km
0.63
0. 39
0.57
0.61
0. 51
0.27
0. 15
0. 18
0.41
0. 20
0.20
0. 13
0. 11
0.43
0.42
0.08
0.05
0.24
0.22
0.05
0. 19
0.08
0.15
0.08
0.68
0. 19
0.12
0.09
80500 km*
0.66/0.59
0.80/3.47
0.68
0.60
0.31/0.52
0.34/1.51
0.13
0.17
0. 19/0.38
0. 13/1.35
0.12
0.08
0.09/0. 17
0.05/0.21
0.53/0.09
0.26
0.06/0. 06
0.05/0.04
0.34/0. 10
0.24
0.08/0. 31
0.00/0.45
0. 16
0.05
0.09/0.81
0.06/0.02
0. 08
0. 06
FTP Standards:
B = Before Maintenance
A = After Maintenance
•75 Federal =0.9 g/km
'75 California =0.6 g/km
-------
TABLE 15. AVERAGE CO EMISSIONS BY TEST TYPE FOR
DISTANCE INTERVAL TESTS ON FOUR CARS
Teat
Type
FTP
SET-7
FET
Accel to 48 kph
48 kph
Accel to 96 kph
96 kph
Car
Number
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-Z
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
* air injection system leak
** EGR system inoperative
*** Duplicate Tests on Cars EM-1 t 2 not averaged,
See explanation page 55.
CO Emissions
0 km
9.73
13.42
7. 18
9.36
....
0.38
0.79
0.20
0.36
0.01
3.54
0.04
0.02
0.64
0.77
0.81
2.07
2.56
0.69
0.56
0.01
3200 km
7.27
9.59
3.23
7.89
_-._
....
— - . _
....
0.61
0.66
0.08
0.21
0.04
0.06
0.06
0.04
1.61
0.50
0.60
1.58
1.62
0.85
0.05
0.02
8050 km
8.16
10. 16
4.62
8.23*
7.44
3.07
0.48
5.35*
4.61
1.02
0.06
1.71*
1.06
0.74
0.20
0.47*
0.04
0.20
0.03
0.13*
0.92
0.34
0.11
1.78*
1.05
0.82
0.06
0.06*
16100 km
8.75
9.81
5.69
11.40*
4.32
4. 55
0.45
5.74*
1.77
1.76
0.09
1.38*
0.68
0. 18
0. 16
0.35*
0.06
0.34
0.22
0. 18*
0.70
0.08
0.24
0. 14*
1.33
0.35
0. 13
0.04*
24100 km
6.90
11.79
7.61
11. 11
2.59
5.97
0.85
3.22
1.30
2.07
0.07
1.02
0. 12
0.24
0.04
0.11
0.03
0.00
0.04
0.05
0. 14
1. 14
0.72
1. 14
0.09
1.46
0.03
0.07
g/km
32200 km
10.89
10.04
3.55**
7.97
5.74
5.93
0. 22**
0.87
4.91
1.42
0.08**
0. 11
0.06
0.20
0.17**
0.23
0.01
0.04
0.02**
0.02
0.76
2.38
0.08**
0.11
1.56
0. 54
0.03**
0.01
48300 km
B/A
12.57/11.03
9.61/5.22
6.72/5.07
9.03/10.37
11. 11/14. 57
4.68/1.69
0.67/0.72
3.01/4.03
11.56/12.26
3.08/0.67
0.69/0. 14
0.78/1.50
0.60/0.91
0. 11/0.04
0.27/0.21
1.00/0.65
0.00/0.00
2. 17/0.00
0.04/0.03
0. 01/0. 06
3. 17/3.45
2.28/1.22
1.76/1.62
1.75/2.63
9.45/1.72
16.07/1.10
0.05/0.04
0.08/0.05
64400 km
15.58
11. 91
5.52
12.92
18. 92
12.25
0.86
6.91
16.17
10.45
0.21
0.37
1.08
11.27
0.09
0.54
0.02
8.40
0.04
0.02
7.87
5.40
0.06
0.27
22.31
17.88
0. 04
0.23
80500 km***
11.77/15.25
14.74/24.43
8.43
11.43
10. 51/18.41
9. 14/9.44
1. 17
4.38
6.47/13.80
3. 56/3.00
0. 14
1.36
0.79/0.88
0.07/0. 57
0. 10/.08
0.23
0.01/0.00
0.00/0.02
0.03/0.02
0.04
2.70/10.97
0. 50/1.88
1.30
0. 18
20.86/23.70
3.73/0.08
0. 03
0. 18
B = Before Maintenance
A = After Maintenance
FTP Standards: '75 Federal =9.3 g/km
'75 California = 5. 6 g/km
-------
TABLE 16. AVERAGE NOX EMISSIONS BY TEST TYPE FOR
DISTANCE INTERVAL, TESTS ON FOUR CARS
OS
Test
Type
FTP
SET-7
FET
Accel to 48 kph
48 kph
Accel to 96 kph
96 kph
Car
Number
EM-1
EM-2
EM-3
EM-4
EM-1
EM-Z
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
NOV Emissions
0 km
1.08
0.96
0.68
0.85
- <• _ *
_-».*.
.. .-
_ — _ .
0.78
0.28
0.71
0.25
0.68
0.15
0.98
0.21
1.34
1.03
0.51
0.69
0.44
0.66
0.46
0.62
3200 km
1.41
1.25
0.75
1.01
- . - -
- -- -
- - --
« — - -
1.06
0.28
0.67
0.21
0.83
0.25
0.62
0.19
1.33
1.07
0.43
0.72
0.57
0.75
0.38
0.62
8050 km
1.40
1.29
0.66
1. 16*
1. 16
1. 19
0.55
0.96*
1.22
1. 10
0.48
0.77*
0.79
0.35
0.69
0. 19*
0.85
0.45
0.67
0.15*
1.96
1.08
0.51
0.76*
1.14
0.95
0.50
0.75*
16100 km
1.65
1.32
1.02
I. 11*
1.41
1. 12
0.77
0.78*
1.91
0.98
0.61
0.78*
0.95
0.46
0.55
0. 15*
0.80
0.36
0.53
0.13*
2.17
0.89
0.59
0.30*
1.24
1.22
0.54
0.30*
24100 km
1.80
1.49
1. 10
1. 14
1.73
1.34
0.86
1.00
1.77
1.32
0.75
0.89
0.67
0.40
0.88
0.20
0.65
0.58
0.80
0.17
1.94
1. 33
0.90
1.49
2.26
1. 17
0.95
1. 17
E/km
32200 km
2.69
2.62
3. 26**
i.25
2. 18
2.07
3.00**
1.28
2.47
1.99
3. 38**
1.16
1. 19
0.70
0. 92**
0. 15
1.19
0.68
0.98**
0. 18
2.58
2.49
4.22**
1.38
1.91
1.98
3.72**
1. 15
48300 km
B/A
1.79/2.02
1.91/1.60
1.07/0.93
1.81/0.99
1.45/2. 12
1.63/1.60
0. 81/0.80
0. 96/0.84
1.72/1.73
1.53/1.41
0.87/0.85
0.86/0.70
0. 94/0.82
0.56/0.61
0. 79/0.87
0.48/0. 26
0.98/0.75
0. 72/0.56
0.64/0.74
0. 34/0. 32
1.75/1.63
1.65/1.57
1. 15/1.04
0. 96/0.91
1.22/1.55
1.78/1.04
1. 17/0.96
0. 72/0.86
64400 km
1.70
1.99
1. 98
1.30
1.62
1. 50
1. 52
1.00
1.79
1.45
1. 11
1. 10
1. 09
0.63
1.07
0. 65
0.87
0. 79
0. 89
0.28
2.09
1.93
1.33
1.43
2.08
1.4S
1.93
1. 30
80500 km1
2.27/1.97
2.04/1.76
2.00
1.03
1.99/1.84
2.27/1.66
1.92
0.88
2.44/2.01
2.21/1.82
2.32
0.88
0.99/1.42
0.62/0.53
2. 14/1. 37
0.25
0.86/0.94
0.80/0.60
2.21/1.37
0.19
2.29/2. 12
2.26/1.64
2.77
0.93
2.20/2.22
1.74/1.49
2.79
0.96
* Air Ins Leak
** Inoperative EGR System
*** Duplicate testa on cars EM-1
See explanation page 55.
2 not averaged.
FTP Standards:
B = Before Maintenance
A = After Maintenance
75 Federal =1.9 g/km
75 Calif. =1.2 g/km
-------
**
s
_K
0
1.8
1.6
1.2
1,0
O EM-1
D EM-2
9 EM-3
O EM-4
* Air injection leak, EM-4
** EGR system failed, EM-3
D3.46
24.43
30 40 50 60
DISTANCE TRAVELED, KILOMETRES
FUU1RE 22. EMISSIONS FROM FTP TESTS
AT DISTANCE INTERVALS ON FOUR CARS
59
7.0
80
-------
X
o
5S
u
O EM-1
OEM-2
9 EM-3
OEM-4
* Air Injection Leak, EM-4
** EGR System Failed, EM-3
Distance Traveled, Kilometres
FIGURE 23. EMISSIONS FROM SET-7 TESTS AT DISTANCE INTERVALS FOR FOUR CARS
60
-------
0
.5
.4
.3
.2
.1
0
20
10
i
5
4
3
2
1
**
10
*
**
EM-1 O
EM-2 D
EM-:
EM-4
Air Injection leak, EM-4
EGR system failed, EM-3
4-3 9
4-40
20 30 40 50
Distance Traveled, Kilometres
60
1.35
6.47
70
80
FIGURE 24, EMISSIONS FROM HFET TESTS AT DISTANCE INTERVALS FOR FOUR CARS
61
-------
The NOX emissions from all cars were within their respective stan-
dards through the 24,100 kilometre test. Except for EM-4, the general
trend of NO emissions was increasing for the 80,500 km.
A
The vacuum amplifier in the EGR system of car EM-3 failed between
the 24,100 and 32,200 km tests, causing the large increase in NOx at the
32,200 km test. It was replaced after the 32,200 km test. The subsequent
test at 48,300 km showed a reduction in NO emissions. After this test,
the NOX emissions from EM-3 again increase! for the remaining two tests.
At the conclusion of the 80,500 km test, the tailpipe NOX emissions from
EM-3 were checked at 48 kph as tested at 80,500 km and with a spare (but
used) vacuum amplifier. The spare vacuum amplifier test resulted in NOX
emissions of 250 ppm compared with 380 ppm with the vacuum amplifier used
during the 80,500 km tests. The vacuum amplifier used during the distance
accumulation from 32,200 to 80,500 km was checked for proper operation and
it was ascertained that the diaphram had not failed. However, it is felt
that vacuum amplifier deterioration must be at least partially responsible
for the increase in NOX emissions from EM-3 following the 48,300 km test.
In general, the emissions from the SET-7 tests and HFET tests pre-
sented in Figures 23 and 24, show the same trends as the FTP tests. The in
crease in CO emissions from car EM-1 after the 24,100 km test, and from car
EM-2 after the 48,300 km test are more pronounced in both the SET-7 and
HFET tests than in the FTP test.
The SO2 and sulf ate emissions from each test type at each distance
interval are shown in Tables 17 to 20 for cars EM-1 to EM-4, respectively.
As an aid to understanding the comparative magnitudes and trends of the
emissions, these emissions in terms of m/km have been plotted as histograms
in Figures 25 to 31.
E*ch fi9ure shows the SO2 and sulf ate emissions at all distance
intervals for one test type on all four cars. This allows cars to be com-
pared on the basis of both catalyst type and whether or not there is air
injection.
In comparing the sulf ate emission results from these cars, it must
be kept in mind that several factors not measured in this study have been
shown(to have direct influence on the amount of sulfate produced by a cata-
lyst. These factors include amount of oxygen in the exhaust, cata-
S , ST £%a nd/PaCe v^°city of the catalyst system. Some conclu-
sions about effects of oxygen can be drawn by comparing the air-injected
n±Zir~ln^TlSyStemS: However' ifc WO«W be inappropriate to draw
conclusions about the relative sulfate producing ability of monolith or
pelleted catalyst without knowing the catalyst temperatures, oxygen levels
and space velocities of each system during each test type. Thus, in the
discussion that follows, where one car produced more or less sulfates than
another car, it is the total catalyst system operation that should be compared,
not Dust the form of the catalyst substrate.
results are presented in the order in which the tests were run
in the test sequence; i.e., FTP, SET-7, HFET, acceleration to 48 kph, steady
62
-------
TABLE 17. SULFUR DIOXIDE AND SULFATE EMISSIONS
AT DISTANCE INTERVALS - CAR EM-1
1975 Federal Plymouth Gran Fury
Monolithic Catalyst, Without Air Pump
Test Type
FTP
SET-7
FET
accel
*after maintenance
mg/km
Kilometers
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
8050
16100
24100
32200
48300
48300*
64400
80500
80500
8050
16100
24100
32200
48300
48300*
64400
80500
80500
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
S02
68
86
89
127
113
137
169
110
159
167
88
100
95
86
125
75
60
73
92
54
65
93
88
123
59
28
63
62
28
26
27
17
23
26
7
16
19
18
21
19
H2S04
0. 98
0. 27
0. 86
0. 82
2. 18
0. 69
1. 47
1. 80
2. 77
1. 80
1. 22
0.33
0.29
0.42
0.80
0.49
0. 59
0. 63
0.41
0.41
0. 25
0. 51
0. 54
0.99
0. 23
0.20
0.86
0.31
0. 19
0. 54
0.12
0.26
0.85
0. 37
O.OJl
0. 56
0.46
0.48
0. 15
0. 14
% Fuel
SO2
46.70
58.82
70. 70
98. 32
98.60
105. 36
125.43
79.96
120.93
126. 33
64.63
113. 13
108. 52
100. 13
137.84
78.95
62.91
72. 59
93.44
53.60
86.68
130.89
130.60
152. 95
75. 99
35.73
73. 52
74.94
32. 15
37.80
41.75
27. 18
39. 18
46.04
11. 15
27.96
32. 15
29. 25
35.66
32.70
"S" as
H2S04
0.45
0. 14
0.43
0. 41
1. 23
0. 36
0. 71
0. 86
1.37
0.89
0.58
0. 24
0. 22
0.32
0. 57
0. 34
0.41
0.41
0. 27
0.27
0. 23
0.48
0. 53
0.81
0. 19
0. 17
0.65
0.25
0. 15
0.54
0. 12
0. 11
0.97
0.43
0.00
0. 65
0. 51
0. 51
0. 17
0. 16
Total Sulfur
Recovery
47.20
58. 98
71. 14
98.72
99.83
105. 70
126. 14
80. 82
122. 30
127. 22
65.22
113.37
108.77
100.45
138.41
79.29
63. 31
73. 00
93.71
53. 87
86.91
131. 37
131. 13
153.76
76. 18
35. 90
74,29
75. 19
32.30
38.50
41.87
27.29
40. 15
46.47
11. 15
28.60
32. 66
29.76
35.83
32.86
63
-------
TABLE 17. (Cont'd.) SULFUR DIOXIDE AND SULFATE EMISSIONS
AT DISTANCE INTERVALS - CAR EM-1
1975 Federal Plymouth Gran Fury
Monolithic Catalyst, Without Air Pump
Test Type
48 kph S/S
96 kph accel
96 kph S/S
mg/km
kilometers SO2 H2SO4
0
3200
8050
16100
34100
32200
48300
48300*
64400
80500
80500
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
8
11
8
12
11
14
11
21
14
9
9
237
208
96
157
90
151
132
116
106
111
83
76
94
64
59
75
107
67
40
76
43
42
0.32
2.40
0. 34
0.83
1.39
1.07
1. 20
1. 20
0.75
0.67
0.51
13. 10
2.00
2.64
13.51
62.84
6.68
1.77
1. 39
2. 14
1. 11
.76
0. 18
0. 20
0.31
1.38
18.75
0.68
0. 24
0.21
0. 12
0. 16
0.08
% Fuel
S02
12.89
17.27
22.34
20.44
20. 03
24.07
19. 57
36.69
29.51
16.47
15.62
323.67
273.56
141. 12
267.77
143.80
185.03
173.85
155. 19
132. 19
150.39
102.31
109.83
131.06
94.16
103.39
121.23
133.,06
91.98
54.61
95. 16
52.51
53.01
"S" as
H2SO4
0.32
2.56
0.39
0.99
1.74
1.22
1.39
1.38
0.84
0.78
0.51
11.68
3.15
2.45
14.32
64. 11
5.36
1. 52
1.21
1.75
0.98
0.61
0.16
0. 18
0.29
1.56
15.83
0.55
0.22
0. 19
0.09
0. 13
0.07
Total Sulfur
Recovery
13.22
19.83
22.86
21.43
21.77
25.29
20. 97
38.07
25.35
17.25
16.20
335.35
276.71
145. 98
282. 10
207.92
190.39
175. 37
156.40
133.94
151.37
102. 92
109.99
131.25
96.76
104.96
137.06
133.61
92. 20
54.61
95.25
52.64
53.08
* after maintenance
64
-------
TABLE 18. SULFUR DIOXIDE AND SULFATE EMISSIONS
AT DISTANCE INTERVALS - CAR EM-2
1975 Federal Chevrolet Impala
Pelleted Catalyst, Without Air Pump
SET-7
HWFET
accel
mg/km
kilometers
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
8050
16100
24100
32200
48300
48300*
64400
80500
80500
8050
16100
24100
32200
48300
48300*
64400
80500
80500
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
SO2
56
101
86
105
123
107
78
115
120
170
117
92
87
97
115
105
115
102
126
110
87
96
130'
137
100
143
111
87
45
-
22
37
28
18
15
57
28
27
H2SO4
0. 58
0. 11
0. 13
1.00
1. 26
2.39
1.31
0. 78
0. 90
1. 13
1. 56
0.40
0.30
0.77
1. 18
1. 33
1.88
0. 52
1.89
1.09
1.51
0. 76
1.34
1.91
3. 03
2. 70
0. 83
1.03
1.64
0.44
0.44
0.09
0.04
0. 14
0..54
0.20
0.01
0.98
0.36
0.38
% Fuel "S" as
SO 2
45.84
80.19
66.31
82.46
95.42
80.93
63.45
88.86
89.94
122.61
130.60
100.40
96.47
102.78
120.16
117. 13
117.97
101.31
128.76
137.09
113.94
115.44
170.00
148.67
128.80
158. 10
126.58
9 8,. 94
60.62
30. 91
54.36
39.96
27. 20
23. 12
80. 35
38.83
41.24
H2SO4
0.27
0.06
0. 10
0.50
0.65
1.21
0.65
0.42
0.46
0. 55
0.73
0.29
0.22
0.56
0.81
0.90
1. 37
0. 35
1.24
0.73
1.24
0.63
1.03
1.63
2.15
2.28
0.60
0.77
1.22
0.31
0.36
0.08
0.04
0.14
0.51
0.20
0.01
0.89
0.33
0.37
Total Sulfur
Recovery
45.88
80.29
66.81
83. 10
96.63
81.58
63.87
89.31
90.49
123.34
130.89
100.62
97.03
103.59
121.06
118.50
118.32
102.55
129.49
138.33
114.51
116.47
171.63
150.82
131.08
158.70
127.35
100.16
61.08
30.95
54.50
40.47
27.40
23. 13
81.24
39.16
41.61
* after maintenance
65
-------
TABLE 18 (Cont'd.) SULFUR DIOXIDE AND SULFATE EMISSIONS
AT DISTANCE INTERVALS - CAR EM-2
1975 Federal Chevrolet Impala
Pelleted Catalyst, Without Air Pump
Test Type
48 kph S/S
96 kph accel
96 kph S/S
kilometers
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
0
3200
8050
16100
24100
32200
48300
48300*
64400
80500
80500
SO 2
_
10
18
35
10
16
6
10
57
13
17
-
119
140
116
115
169
177
145
209
130
77
-
119
138
115
73
137
113
123
105
28
65
mg/km
H2S04
0.09
8. 29
2. 93
3. 55
2.39
1.46
2.29
0.87
0. 10
0.96
0.28
6.23
4.28
5.50
8.01
34.30
12.07
16.01
23.05
2. 22
13.36
12.31
3. 16
1.82
4.41
4.59
5.47
3. 51
1.07
3. 01
0.26
1.53
5.58
% Fuel "S" as
S02
H2S04
0.07
13.75 7.32
12.05 2.97
51.92 3.42
15.67 2.44
19.46 1.18
8.49 2.16
16.50 0.93
83.53 0.10
19.58 0.99
26.04 0.28
4.62
160.32 5.73
177.93 4.63
142.37 6.59
145.10 27.78
186.39 8.72
208.81 12.37
186.02 19.26
249.52 1.74
152.19 10.25
101.86 10.63
2. 52
157.36 1-44
176.82 3.60
149.69 3.75
85.55 4.13
172.65 2.88
130.14 0.80
166.80 2.67
127.02 0.20
33.35 1.19
81.94 4.62
Total Sulfur
Recovery
21.05
15.02
55.34
18. 11
20.63
10.65
17.43
83.63
20.56
26.32
166.03
182.57
148.96
172.87
195.11
221. 18
205.28
251.25
162.44
112.49
158.80
180.42
151.89
89.68
175.53
130.95
169.46
127.23
34.55
86.56
* after maintenance
66
-------
TABLE 19. SULFUR DIOXIDE AND SULFATE EMISSIONS
AT DISTANCE INTERVALS - CAR EM-3
1975 California Plymouth Gran Fury
Monolithic Catalyst, With Air Pump
SET-7
HWFET
accel
kilometers
0
3200
8050
16100
24100
32200**
48300
48300*
64400
80500
8050
16100
24100
32200**
48300
48300
64400
80500
8050
16100
24100
32200**
48300
48300*
64400
80500
0
3200
8050
16100
24100
32200**
48300
48300*
64400
80500
80500
SO2
147
237
113
98
186
224
116
169
100
140
72
68
81
85
96
101
153
101
61
54
46
75
59
45
67
72
17
36
23
13
14
7
13
19
33
27
18
mg/km
H2SO4
1.61
6. 16
4.43
5.74
5.67
11.35**
2. 84
4. 12
4.37
6. 92
29.09
26.67
15.27
44. 59**
6.62
7.05
7.47
5.67
44. 59
51.92
38.01
45.08 **
12.93
14. 55
11.41
10. 34
0.23
0. 10
0.37
0.07
0. 17
0. 64**
0.40
0.37
3.18
4.90
0.25
% Fuel "S" as
SO2
93. 76
120.92
88.08
65. 02
121.62
178.76
83.31
122. 10
72. 75
91. 76
76.86
69.21
81. 18
95.88
101. 31
100.27
152.62
96.04
78.07
64.56
53. 60
99.88
70.75
54. 25
72.64
80.96
25. 10
56.89
36.90
22.01
21.46
11.82
22.43
33.35
40.33
32.46
30.74
H2SO4
0. 70
2.89
2.59
2. 50
2.44
5.91
1.33
1.94
2.08
2.95
20.23
17.81
9.91
33.01
4.55
4. 56
4.87
3.52
38.31
40.82
29.46
39.33
10.11
11.42
8. 14
7.60
0.22
0. 10
0.41
0.07
0. 17
0.68
0.46
0.42
2.55
3.87
0.27
Total Sulfur
Recovery
94.32
123.80
90.66
67.52
124.05
184.67
84.65
124.04
74. 83
94.71
97.09
87.02
91.09
128.89
105.86
104.83
157.49
99.56
116.38
105.38
83.06
139.21
80.87
65.67
80.79
88. 56
25.33
56.99
37.31
22.08
21.63
12.50
22,89
33.77
42.89
36.33
31.01
maintenance
system inoperative
67
-------
TABLE 19 (Cont'd.) SULFUR DIOXIDE AND SULFATE EMISSIONS
AT DISTANCE INTERVALS - CAR EM-3
1975 California Plymouth Gran Fury
Monolithic Catalyst, With Air Pump
mg/km % Fuel "S" as Total Sulfur
Test Type
48 kph S/S
96 kph accel
96 kph S/S
kilometers
0
3200
8050
16100
24100
32200**
48300
48300*
64400
80500
80500
0
3200
8050
16100
24100
32200**
48300
48300*
64400
80500
0
3200
8050
16100
24100
32200**
48300
48300
64400
80500
S02
13
19
17
10
15
24
16
22
29
33
22
135
151
106
65
110
69
82
88
53
89
24
28
24
22
26
25
30
-30
42
34
H2S04
8.43
4.42
3.42
1.75
2.63
8. 02 **
0.91
0.66
35.44
26.62
.1-17...
28.07
23.66
61.74
62.98
26.01
77. 11 **
24.80
7.25
49.32
18.44
20.01
43.65
27.99
46.11
24.83
32. 53 **
21.22
19.66
19. 76
14.83
SOz
20.25
30.69
29. 19
16.88
25. 36
38.69
27.71
39.56
36. 92
42.92
36.41
167.24
200.31
150.87
86.85
140. 12
94.43
111.41
118.92
64.85
107.87
30. 13
41.06
33.60
32.44
32.36
29.28
43.86
39.68
53.60
44.90
H2S04
8.76
4.78
3.86
1.94
2.96
8.38
1.04
0.77
29.68
22.29
1.29
23.04
20.44
57.29
54.82
19.90
68.69
22.00
6.43
39.72
14.65
16.77
41.96
26.26
43.70
20.68
33.97
20. 14
17.08
16.62
12.59
Recovery
29.00
35.46
33.05
18.82
28.32
47.07
28.75
40.33
66.60
65.20
37.69
190.27
220.75
208.16
141.67
160.02
163.11
133.41
125.35.
104.58
122.52
46.90
83.02
59.86
76.15
53.03
63.24
64.00
56.76
70.22
57.48
* after maintenance
**EGR system inoperative
68
-------
TABLE 20. SULFUR DIOXIDE AND SULFATE EMISSIONS
AT DISTANCE INTERVALS - CAR EM-4
1975 California Chevrolet Impala
Pelleted Catalyst, With Air Pump
m
g/km
% Fuel "S" as
Total Sulfur
Test Type
FTP
SET -7
HWFET
48 kph accel
kilometers
0
3200
8050**
16100**
24100
32200
48300
48300*
64400
80500
8050**
16100**
24100
32200
48300
48300*
64400
80500
8050**
16100**
24100
32200
48300
48300*
64400
80500
0
3200
8050**
16100**
24100
32200
48300
48300*
A440D
V Tt^V V
80500
SO2
120
59
105
140
106
56
103
72
137
116
79
78
77
58
70
66
97
75
60
53
60
64
62
58
90
48
22
20
68
13
11
31
26
19
7 O
28
H2SO4
2.42
8.89
0,52
0.72
3. 23
16. 15
11.08
7.58
6.27
2.80
1.01
2.33
9.63
26.9
16.93
10.88
8.34
6.80
4.19
4.48
9.75
16.41
13.83
14.81
12.87
2.79
4.72
13. 30
13.44
1.87
6.69
8.26
_
7.41
4.23
SO2
75.45
44. 14
78.83
95.93
72.40
41. 50
77.78
53.06
91.43
79.82
83.27
81.76
76.90
62.00
71.81
66.79
88.72
73.21
73. 55
63.03
67.30
79.75
73.53
67.72
91.91
45.65
22.08
23.44
82.06
16.09
12.69
41.36
39.47
28.21
34 20
«J~ • w v
35. 53
H2SO4
1.01
4.24
0. 33
0.32
1.45
7.87
5.48
3.64
2.73
1.28
0.69
1.59
6.35
18.93
11.38
7.14
4.99
4.45
3.39
3.51
7. 12
13.39
10.65
11.23
8.56
2.03
3. 10
10. 18
10.73
1.52
5.27
7.22
_
7. 30
3. 58
Recovery
76.45
48.37
79. 15
96.25
73.65
49.37
83.26
56.70
94. 15
81. 10
83.96
83.35
83.25
80.93
83.19
73.93
93.71
77.66
76.94
66.54
74.42
93.15
84.17
78.95
100.48
47,69
26. 16
33.61
92.79
17.60
17.96
48.58
_
35.50
•
39. H
* after maintenance
in air injection system
69
-------
TABLE 20 (Cont'd.) SULFUR DIOXIDE AND SULFATE EMISSIONS
AT DISTANCE INTERVALS - CAR EM-4
1975 California Chevrolet Impala
Pelleted Catalyst, With Air Pump
mg/km
Test Type
48 kph S/S
96 kph accel
96 kph S/S
lo meters
0
3200
8050**
16100**
24100
32200
48300
48300*
64400
80500
0
3200
8050**
16100**
24100
32200
48300
48300*
64400
80500
0
3200
8050**
16100**
24100
32200
48300
48300*
64400
80500
S02
20
11
26
9
14
29
16
16
12
18
60
56
65
60
71
50
103
72
78
36
63
22
53
53
46
17
70
62
65
40
H2SQ4
35.55
32.23
13.75
7.81
30.78
26.63
3.72
9.70
2. 92
10.70
17.03
27.77
16. 10
8.35
35.63
66.98
45.90
17.92
24.02
24.48
15.70
17. 87
10. 17
13.79
24.28
27. 20
17.85
18.70
8.74
9.10
% Fuel "S" as
S02
20.82
13.45
32.47
13.97
18.57
38.61
25.01
23.59
17.05
24.48
62.25
66. 27
81.58
77.76
75.95
55.57
124. 13
85.80
89. 15
42.99
71.71
28.71
68.95
72.90
52.93
21.73
86.57
75.64
75.05
48.04
H2S04
24.21
25.60
11.43
8.03
26.01
23.48
3.72
9.40
2.75
9.18
11.79
21.71
13.24
7.04
24.86
49.05
45.90
13.94
18.01
19. 11
11.84
15.99
8.76
12. 20
18. 23
22. 55
14. 50
15.02
6.63
7.36
Total Sulfur
Recovery
45.03
39.05
43.90
22.00
44. 58
62.08
28.74
32.99
19. 80
33.66
80.63
87.97
94.81
84.80
100.80
104.63
160.31
99.74
107. 16
62. 10
84.37
39.49
77.71
85.09
71. 16
44.28
101.06
90.66
81.68
55.39
* after maintenance
** Leak in air injection system
70
-------
150
0)
c
o
'w 100
w
D
D
50 -
•
Ml
G
f2
o
E
•*
o
0
fN
M
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E
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o
in
0
00
••M
O
o
iH
vO
i-H
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o
o
r-4
^J*
CN
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E
o
o
CN
CN
m
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0
o
0
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o
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n
00
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o
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<3
^
vfl
••
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X
O
0
in
o
00
••
E
o
o
m
o
oo
150
100
50 -
-
1
o
o
•(N
CO
Ji
O
tn
o
00
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B
X
o
0
H
10
r-t
•1
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CN
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o
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CN
CN
n
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1
o
0
n
00
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m*m
1
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0
ro
00
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I^B
1
O
0
^
•^
vO
••
X
O
0
ID
0
00
^m
&
X
O
0
to
o
00
EM-1
EM-2
**
200 r
150 -
|
CO
§
03
U)
3
cn
IH2S04
D
so-
* Air Injection Leak
** EGR System Failed
150
100 -
100 "
EM-3
EM-4
FIGURE 25. SULFATE AND SULFUR DIOXIDE EMISSIONS FROM
FTP TESTS AT DISTANCE INTERVALS FOR FOUR CARS
71
-------
I
tn
C
o
•H
w
w
150
100
50
0
—
HHMl
|
0
in
o
CO
••M
A:
I 16100
••Hi
e
\ 24100
•••
S
| 32200
g
I 48300
•H^
J
| 48300
•••
|
O
o
•HP
g
O
o
m
0
CO
—
e
j 80500
150 r
100 -
50 -
EM-1
-
1
0
in
0
CO
•Mi
J3
o
0
H
V0
H
MM«
1
O
o
iH
•<*
(N
•i
1
O
o
CN
-------
(n
B 100
en
c
0
•H
0)
to
•H
50
1 1
o
in
o
00
mmmm
B
o
0
iH
VD
i-t
mmmm
e
a
o
(N
mm]
e
a
o
(N
IN
E
o
o
n
CO
•a1
e
^
o
o
ro
CO
•••
e
a
o
_
|
0
o
m
o
00
e
o
o
in
o
CO
fi
150
100
50
0
-
1 i
••
E
A
o
m
o
CO
mm
1
O
O
1-1
VD
H
••
6
o
o
i-H
^*
(N
••
A:
0
o
CN
IN
ro
mm
|
o
o
m
CO
-------
150
150 r
100
100
U!
O
-H
1C
IB
•H
3
W
I III II11 III
O
O O O
o in rH
CM O VD
O ro 00 c-H
o o o
o o o
CM
CM
CN
fO
ro
03
o
o
ro
OD
o o o
o o o
^« in in
*t O O
(O 00 CO
50
50
0
o
o
CM
CO
O O
O O
CM
o o
O O
ro ro
00 CO
III
o o o
000
-a1 in in
Tf O O
vo co oo
fr
EM-l
EM-2
H2S04
Qso2
* Air injection leaK
** EGR system failed
150 r
150 r
100
100
mil iiiin
c
0
•H
in
If:
3
u-i
o o
o o o o
O in H rH
CN o vo ^j-
O rO 00 rH CN
a o o o o o
o o o o o o
CM ro ro ^r m in
CX 00 00 ^J1 O O
ro ^r *j" \o oo oo
50
50
Ltrafffh
III III I I
o o o o o
o o o o o o o
o in H H CN ro m
«N O *O ^" CN 00 O
OfOOOrHCMro ^ 00
EM-3
EM-4
FIGURE 28. SULFATE AND SULFUR DIOXIDE EMISSIONS FROM
ACCELERATION TO 48 kph TESTS AT DISTANCE INTERVALS FOR FOUR CARS
-------
w
c
o
H 100
tn
w
•H
w
in
3
3
w
50
150
B
6 g g g g g
x .* ,* A; x A:
g
Ai
„ oooooooo
go oo oo ooooo
^o miH rHCN roro^rmm
CN Ovfl ^TCN OOOOrJOO
100
50
rn-rrfTfl>n
s H SS5S
ll
oooooooo
goo ooo ooooo
(NO t£ "31 CN 00 00 «S" O O
EM-1
EM-2
H2S04
SO,
* Air Injection Leak
** EGR System Failed
150
I
CO
o
•H
Ul
in
W
100
50
150 r
„ _ g gg g e g e g
C C -^ An -V^ ^ t^ Q< i^t ^t
J^ ^ '^ *^ ^^ ' *"^
o oo ooooo
60000000000
MO mr-i HCN firo^rmin
CN CO ^0 ^* CN 00 00 ^* CO CO
oco oOr-i csin ^< <4< vo oo oo
100
50 -
ggggegg
ooo o o o o
goo ooo oooo
^oin i-t 1-1 CN nro'S'in
CNO VOfCN OOOO'S'O
O C'O 00 rH CN CO ^f ^J1 VC 00
EM-3
EM-4
FIGURE 29. SULFATE AND SULFUR DIOXIDE EMISSIONS FROM 48 kph
STEADY STATE TESTS AT DISTANCE INTERVALS FOR FOUR CARS
75
-------
250B|
"^
150
01
c
o
•H
1C
in
•H
B
en
100
50
210
211
150
CO
CO
100
cc
50
EM-1
EM-2
200
150
o
•H
(fl
V,
•H
i-H
3
100
50
D
**
*
**
H2S04
so2
Air injection leak
EGR system failed
150 -
100 .
50 -
EM-3
EM-4
FIGURE 30. SULFATE AND SULFUR DIOXIDE EMISSIONS FROM
ACCELERATION TO 96 kph TESTS AT DISTANCE INTERVALS ON FOUR CARS
76
-------
150
CO
c
o
M 100
CO
3
C/}
50
150
I
100
00
VO
50
00
cc
EM-1
EM-2
n
so.
* Air Injection Leak
** EGR System Failed
I
in
o
g
•H
150
50
150 r-
e e
g g BE g g g
o o o o o o o
g ooo o oo ooo
X O in rH iH CN co ro^m
CN O V£ ^* CM 00 00 ^ O
O COCOrH CM CO'd' ^vOOO
100
^^ggeeggg
C C Jyt \f C* j^ t> t,jt ty^
"^ 0000000
e ooooooo oo
,14 oinr-liHCMCOro ^ in
CN OVO'S'CNOOOO T O
O COCOrHfMrO'3l'31 IOCO
50
EM-3
EM-4
FIGURE 31. SULFATE AND SULFUR DIOXIDE EMISSIONS FROM 96 kph
STEADY STATE TESTS AT DISTANCE INTERVALS ON FOUR CARS
77
-------
state 48 kph, acceleration from 0 to 96 kph and steady-state 96 kph. For
the nonair-injected cars, the most sulfur emissions, regardless of specie,
n general were produced during the acceleration from 0 to 96 kph. The FTP
produces the next highest, then the SET-7, HFET, 96 kph steady-state, and
then the acceleration to 48 kph. The lowest sulfur emissions were from the
48 kph steady-state tests.
The rank order for the air-injected cars was somewhat different.
For these two cars, the highest sulfur emissions were from the FTP. The
acceleration from 0 to 96 kph produced the next highest emissions, then the
SET-7, HFET test, 96 kph steady-state, and the 48 kph steady-state. The
lowest sulfur compound emissions were from the acceleration to 48 kph.
It is interesting to note that the 48 kph steady-state sulfur emis-
sions were either the lowest or next lowest sulfur emissions. In fact, the
total sulfur emissions at 48 kph (30 mph) were on the order of one-tenth of
the total sulfur emissions from the FTP.
For the FTP tests, cars EM-1 and EM- 3 produced, on the average,
more total sulfur emissions than EM-2 and EM-4. The air-injected monolith
catalyst (EM-3) appeared to produce more total sulfur emissions during the
FTP tests than the nonair-injected monolith (EM-1) . The air-injected pel-
leted catalyst (EM-4) appeared to produce approximately the same total sulfur
emissions as the nonair-injected pelleted catalyst (EM-2).
A comparison of average SET-7 total sulfur emissions for the non-
air-injected cars shows that car EM-2 produced somewhat more total sulfur emis-
sions than car EM-1. For the air-injected cars, EM-4 produces less total
sulfur than EM-3. The air-injected monolith (EM-3) appeared to produce
somewhat more total sulfur emissions during the SET-7 test than the non-
air-injected (EM-1). However, the air-injected pelleted catalyst (EM-4)
produced less total sulfur emissions than the nonair-injected pelleted
catalyst (car EM-2.) The comparisons between the various catalyst config-
urations made for the SET-7 tests also hold for the HFET tests.
A* v v *Th! t0tal sulfur emissions from the acceleration to 48 kph and the
48 kph steady-state were too low to make meaningful comparisons; however,
^ CSr EM~4 hSd ^ h±heSt t0t -
ditions t0tal SUlfur ^is^ns at both con
v- », 4. Theifulfur emissions from the acceleration from 0 to 96 kph were the
highest of all tests for the nonair-injected cars. It is not surprising
then, that at this condition, the nonair-injected cars produced more total
™ f1* e™T°n5 ^o ^ air-in3ected cars, comparing like models (i.e.,
EM-1 to EM-3 and EM-2 to EM-4) . When the total sulfur emissions from the
nonair-inuected cars are compared, the pelleted system (EM-2) had greater
emissions than the monolith system (EM-1). However, when the air-injected
car sulfur emissions are compared, the pelleted system had lower emissions
than the monolith system.
approximately the same total sulfur emissions. The
78
-------
pelleted catalyst car (EM-2) produced greater total sulfur emissions than
the air-injected pelleted catalyst car (EM-4).
The main purpose of this study, of course, is to investigate the
exhaust sulfate emissions. While the histograms provide a good means to
visualize the fraction of the sulfur emissions emitted as sulfuric acid,
they provide only a gross comparison of sulfate emissions between tests and
cars. This is because for some of the tests, the sulfate emissions from the
non air-injected cars were too small to be represented accurately on the
scale used for the histograms. Therefore, the sulfate emissions for each
test type were averaged over the 80,500 km and presented in Table 21.
As can be seen from the table, the highest average sulfate emission
from all cars is 33.6 mg/km from the acceleration from 0 to 96 kph for EM-3,
the smallest average sulfate emission is 0.31 mg/km from the acceleration
to 48 kph for EM-2. However, the rank order of sulfate emissions by test
type is different for each car. This is a somewhat curious finding since
sulfate emissions might reasonably to expected to be a function of the type
of driving. Apparently, there are enough differences in the operations of
the total emission control system on each car to cause these differences in
rank order. The SET-7 test fell in the middle of the sulfate emission ranking
for all four cars. Table 21 also shows that air-injected cars (EM-3 and EM-4)
produced more sulfate emissions from each test type than the nonair-injected
cars (EM-1 and EM-2).
From the tables, large variations in sulfate emissions from car-to-
car for each type of test may be noted. The largest variation is for the
96 kph steady-state test where the highest average sulfate value is approx-
imately 76 times the lowest. The acceleration to 96 kph test has the smallest
variation, the highest sulfate value being 3.2 times the lowest value. Car
EM-1 had the lowest average sulfate emissions for 5 of the 7 test types.
Car EM-2 had the lowest average sulfate emissions from 2 of the test types.
The highest sulfate emissions for each test type were more evenly divided
between cars EM-3 and EM-4, with EM-3 having the highest emissions on 4 of
the test types and EM-4 on 3 of the test types.
As mentioned before, the scale of the histograms in Figures 25 to
31 makes it difficult to determine the changes in sulfate emissions with
distance accumulation. Therefore, the sulfate emissions in mg/km have been
plotted versus distance traveled in kilometres and presented in Figures 32
to 38 for each test type. As explained, emissions control system malfunctions
occurred during certain tests of EM-3 and EM-4. These malfunctions were cor-
rected as discovered. However, for the tests at which the malfunctions
occurred, the sulfate emissions were affected. This fact should be taken into
consideration when evaluating the results presented in Figures 32 to 38. In
the case of EM-4, which had an air-injection system leak at the 8,050 km and
and 16,100 km tests, it appeared that this leak may have affected the sulfate
conditioning of the catalyst, causing lower sulfates at the 24,100 km test
than would have been seen had the air-injection system not leaked at all.
As a general rule, the sulfate emissions from the nonair-injected
cars showed little change over the 80,500 km distance accumulation. The
79
-------
TABLE 21. AVERAGE SULFATE EMISSIONS BY TEST TYPE
FROM DISTANCE INTERVAL TEST ON FOUR CARS
Sulfate Emissions
Test Type
FTP
SET-7
HFET
Accel to
48 kph
48 kph
Accel to
96 kph
96 kph
EM-1
mg/km
1.35
0.49
0.45
0.36
0.97
9.81
2.03
Rank
Order
3
5
6
7
4
1
2
EM-2
mg/km
1.01
1.04
1.63
0.31
2.11
12.49
3.13
Rank
Order
6
5
4
7
3
1
2
EM- 3**
mg/km
4.65
13.98
26.25
1.00
8.55
33.59
26.26
Rank
Order
6
4
3
7
5
1
2
EM-4*
mg/km
7.30
13.25
11.74
19.03
17.43
7.49
28.42
Rank
Order
7
4
5
2
3
6
1
*excluding 8050 and 16100 km tests with leaking air injection system
**excluding 32200 km test with failed EGR
80
-------
O EM-1
Q EM-2
^ EM-3
y\ EM-4
* Air injection leak(EM-4)
** EGR system failed (EM-3)
10
20
30 40 50 60 70
Distance Traveled, kilometres
80
100
FIGURE 32. SULFATE EMISSIONS FROM FTP TESTS AS A
FUNCTION OF DISTANCE TRAVELED FOR FOUR CARS
81
-------
60
50
40
to
(8
tfi
d)
•P
id
U-l
H
3
W
30
.
20
10
O EM-1
D EM-2
^ EM-3
O EM-4
* Air injection leak (EM-4)
** EGR system failed (EM-3)
10 20 30 40 50 60 70
Distance Traveled, kilometres
80
90
100
FIGURE 33. SULFATE EMISSIONS FROM SET-7 TESTS AS A
FUNCTION OF DISTANCE TRAVELED FOR FOUR CARS
82
-------
60
o
CO
CN
a
M
ra
U-l
co
50
40 -
O
D
EM-1
EM-2
A EM-3
O EM-4
* Air Injection leak (EM-4)
** EGR system failed (EM-3)
10
20 30 40 50 60 70 80
Distance Traveled, kilometres
90
100
FIGURE 34. SULFATE EMISSIONS FROM HFET TESTS AS A
FUNCTION OF DISTANCE TRAVELED FOR FOUR CARS
83
-------
CM
33
tfi
a
U5
0)
4J
a
3
en
2 -
O EM-1
D EM-2
£ EM-3
O EM-4
* Air Injection leak
** EGR system failed
(EM-4)
(EM-3)
0-10 20 30 40 50 60 70 80
Distance Traveled, kilometres
90
100
FIGURE 35. SULFATE EMISSIONS FROM ACCELERATION TO 48 KPH TESTS
AS A FUNCTION OF DISTANCE TRAVELED FOR FOUR CARS
84
-------
60
OEM-I
OEM-2
A EM-3
OEM-4
* Air injection leak (EM-4)
** EGR system failed (EM-3)
10
20
30 40 50 60 70 80
Distance Traveled, Kilometres
100
FIGURE 36. SULPATE EMISSIONS FROM 48 KPH STEADY STATE TESTS
AS A FUNCTION OF DISTANCE TRAVELED FOR FOUR CARS
85
-------
80
70
O EM-1
Q EM-2
& EM-3
O EM-4
* Air injection leak(EM-4)
** EGR system failed (EM-3)
10
20
30 40 50 60 70
Distance Traveled, Kilometres
80
90 100
FIGURE 37. SULFATE EMISSIONS FROM ACCELERATION TO 96 KPH TESTS
AS A FUNCTION OF DISTANCE TRAVELED FOR FOUR CARS
86
-------
O EM-1
Q EM-2
AEM-3
0EM-4
* Air injection leak (EM-4)
** EGR system failed (EM-3)
10 20 30 40 50 60 70 80
Distance Traveled, Kilometres
90
100
FIGURE 38. SULFATE EMISSIONS FROM 96 KPH STEADY STATE TESTS
AS A FUNCTION OF DISTANCE TRAVELED FOR FOUR CARS
87
-------
exception is the acceleration to 96 kph. The sulfate emissions from this
test for all cars varies widely over the 80,500 km. The sulfate emissions
for car EM-1 from the 24,100 km test at 96 kph, were considerably higher
than any of the other kilometre test points at 96 kph. It is felt, how-
ever, that this is a valid value considering that it is from replicate tests.
It is also interesting to note that the CO emissions from EM-1 are much lower
for the 96 kph test at this kilometre point. This is perhaps an indication
of a higher oxygen feed level to the catalyst during this particular test.
What would have caused this higher oxygen level is not known.
The sulfate emissions from the two air-injected cars, EM-3 and EM-4,
do not follow similar patterns with distance. As mentioned previously, this
may be caused by the emission control system malfunctions at various points
in the distance accumulation of the two cars.
For car EM-3, the higher speed tests (SET-7, HFET, accel to 96 kph,
and 96 kph steady-state) show a similar pattern of sulfate emissions. As
the distance traveled increases from 0 to between 8,000 and 16,000 km, the
sulfate emissions increase. Thereafter, as distance traveled increased from
16,000 km to 80,500 km, the sulfate emissions decreased. For the FTP, the
sulfate emissions from EM-3 increased as distance increased to about 3,200
km. From 3,200 km to 80,500 km, the sulfate emissions were essentially con-
stant. The sulfate emissions from the acceleration to 48 kph and the 48 kph
steady-state tests were essentially constant at a level corresponding to the
nonair-injected cars to a distance of approximately 50,000 km. From 50,000
km to 80,000 km the sulfate emissions increased, then abruptly decreased to
the pre-50,000 km level during the replicate 80,500 km test.
The sulfate emissions for EM-4, from all tests except the accelera-
tion to 48 kph and 48 kph steady-state tests, increased between 0 and 32,000
km, then decreased between 32,000 km and 80,500 km. It is possible that the
peak sulfate emission level might have been reached prior to 32,000 km if
the air injection system had not been leaking between approximately 6,000 km
and 19,000 km. For the acceleration to 46 kph and the 46 kph steady-state
tests of EM-4, the sulfate emissions apparently reached their peak within
the first 3,000 km of operation, and decreased continuously thereafter.
Since the SET-7 test cycle represents the driving mode where the
highest level of sulfate would be expected, the sulfate emissions from the
SET-7 deserve special attention. A regression analysis was performed on
the SET-7 sulfate emissions for each car separately. First, a linear re-
gression equation was obtained and a deterioration factor calculated using
the procedure for light duty certification deterioration factors<14) from
the equation values at 8,050 and 80,500 km. The linear equations and de-
terioration factor calculated from these equations together with the co-
efficient of determination (r2) for each equation are shown in Table 22.
Also shown are the minimum, maximum and average value of the SET-7 sulfate
emissions for each car with indications at which distance test point the
minimum and maximum occurred.
From this table, it can be seen that both EM-1 and EM-2 have de-
terioration factors greater than 1.0, indicating the SET-7 emissions in-
creased with distance. However, the r2 values for the regression equations
88
-------
TABLE 22. REGRESSION ANALYSIS AND DETERIORATION FACTORS
FOR SET-7 TESTS AT DISTANCE INTERVALS ON FOUR CARS
Car
EM-1
EM-2
EM-4(2)
Distance
Used
3200 to 80500
3200 to 80500
8050 to 80500
32200 to 80500
Linear Regression: Sulfate in mg/km = a -f b (km)
0.40
0.46
27.96
35.48
+2.24xlO-6
+13.02x10-6
-337.85xlO-6
-392.98x10-6
Coeff. of Determination
0.106
0.342
0.794
0.775
Car
EM-3U)
EM-4<2)
Distance
Used
8050 to 80500
32200 to 80500
Exponential Regression: Sulfates in mg/km =a
a b Coeff. of Determination (r2)
30.79
57.37
-24.23x ID'6
-28.14x10-6
0.858
0.866
Average SET-7 Sulfates, mg/km
Car Minimum
EM-1 0.29(16100 km)(3)
EM-2 0.30(16100 km)
EM-3U) 5.67(80500 km)
EM-4<2) 6.80(80500 km)
Maximum
Mean
0.80(32200 km) 0.49
1.89(80500 km) 1.04
29.09(8050 km) 13.98
26.90(32200 km) 13.25
Linear
Deterioration
Factor
Exp.
Deterioration
Factor
1.384
2.677
0.030
0.119
0.173
0.130
(1' excluding failed EGR test at 32200 km
(2) excluding tests with leaking air injection system
' ' numbers in parentheses are distances at which
max or min occurs
89
-------
of these two vehicles indicate that the data fit the equation poorly.
This fact and the consideration of low absolute levels of the sulfate emis-
sions themselves, should be considered when drawing conclusions from these
deterioration factors. The deterioration factors for cars EM-3 and EM-4
are less than 1.0, indicating that the SET-7 sulfate emissions decreased
with distance traveled. Examination of Figure 33, the plot of SET-7 sulfate
emissions versus distance, indicates that an exponential curve might fit the
SET-7 sulfate emissions from EM-3 and EM-4 better than a linear equation.
An exponential regression analysis was performed, on these sulfate emissions
using an equation of the form y = aeb:'. The results of the analysis are
also shown in Table 22. Comparing the coefficients of determination of the
exponential curve with those obtained from the linear regression, it can be
seen that the exponential equation does indeed give a better fit (r2 closer
to 1.0 for the exponential equations). A new deterioration factor was then
calculated using the 8,050 and 80,500 km values from the exponential equa-
tions for each car. These deterioration factors are also shown in Table 22.
Apparently then, SET-7 sulfate emissions from nonair-injected cars
changed little, if any, during 80,500 km of distance accumulation. SET-7
sulfate emissions from air-injected cars decreased significantly in an ex-
ponential fashion from 8,050 km {5,000 miles) to 80,500 km (50,000 miles).
It should be remembered that in the above analysis, certain data
from EM-3 and EM-4 were not used because of malfunctions in the emission con-
trol of the car during those certain tests. While it was not one of the pur-
poses of this study, one of the significant findings is that emission control
system malfunctions have a definite effect on sulfate emissions.
Once the fact that the air-injected catalyst cars had higher sulfate
emissions than non air-injected cars was established, it was obvious that
any leak in the air injection system would lower the sulfate emissions. This
is what happened at the 8,050 and 16,100 km test points on EM-4. In fact,
the lower sulfate emissions were one of the causes of the investigation for a
leak. Another malfunction that affects sulfate emissions was not so obvious.
After the 32,200 km test of EM-3, a check of the NOX emissions indicated a
malfunction of the EGR system. As explained earlier, this malfunction was
caused by a failure of the vacuum amplifier in the EGR system. The sulfate
emissions were also high, but the two facts were not connected at the time,
since except for the FTP and SET-7 tests, sulfate emissions at the same, or
higher, levels had been observed on previous tests.
It was not until a similar situation occurred during the 48,300 km
"after maintenance" tests on EM-3 that the two facts were connected. While
reviewing the NOX emissions as each test was completed, it became obvious
that the EGR system was not functioning. The EGR system had been visually
inspected prior to testing and appeared to be operational. However, after
th<- t-.ost each lino war. traced to insure thoro were no leaks. Finally, an
almost inaccessible connection to a Holunoi.l in I In- »yal-.«m wan fouml lo be-
loose. It is perhaps fortunate that the leak developed since it revealed an
unexpected relationship between EGR and sulfate emissions.
The hose was connected and proper operation of the EGR system veri-
90
-------
fied. The car was operated for 500 km on the modified AMA cycle and then
retested. It is this test series on February 19, 1976, that is reported
as the "after maintenance" tests for the 48,300 kilometre test point.
The sulfate filters from the tests with the inoperative EGR were
processed to compare sulfate emissions with and without EGR. Table 23
shows the NO and sulfur emissions from both the 48,300 km after maintenance
FTP, SET-7 and FET tests, together with the NOX and sulfur emissions from
the*24,100 and 32,200 km tests for comparison. Note that for 5 of the 6
tests, when the EGR system was inoperative, the sulfate emissions were con-^
siderably higher than the sulfate emissions from tests with the EGR function-
ing. Thus, while the results are not 100 percent consistent, it does appear
that an EGR system failure increases sulfate emissions as well as NOX emis-
sions.
To further investigate this phenomenon, a series of two tests were run
on each car at the conclusion of the 80,500 km tests. The test series con-
sisted of two 80 kph steady-state tests, 10 to 15 minutes long. For one of
the two tests, the EGR system was disabled by disconnecting the vacuum actua-
tion line at the EGR valve. The other test was run with the EGR system
functioning normally. On car EM-4, a third test was run with the vacuum line
disconnected and plugged. With the line unplugged, there was a vacuum leak ,
as well as an inoperative EGR system; with the line plugged, the integrity
of the vacuum system was preserved and only the EGR system was inoperative.
Table 24 shows the results of these tests. In addition to the usual
gaseous emission and sulfates, the temperature at the inlet to the catalyst
and the oxygen level at the exit of the catalyst are also shown. For each
car, the test with the EGR valve disabled showed an increase in NOX. This
increase varied from approximately 10 percent for EM-1 to approximately 200
percent for EM-4. The sulfate emissions also increased for the EGR disabled
test except for car EM-1. Thus, the changes in sulfate emissions ranged
from negligible for car EM-1 to approximately 170 percent for the test with
the vacuum line plugged on car EM-4.
For 3 of the 4 cars, when the EGR system was disabled, the exhaust
gas temperature into the catalyst decreased. On two of the cars, the O2
content at the exit of the catalyst decreased when the EGR was disconnected,
one one car there was no change and on one car the oxygen increased. It has
been shown in several studies(12» 13) that decreasing catalyst temperature
increases the amount of sulfates formed. Thus, it is not surprising that the
car with the largest temperature decrease, (EM-4), also had the largest sulfate
increase.
This series of tests was not intended to be a thorough investigation
of this phenomenon. Rather, they were to be a verification that a malfunc-
tioning EGR system could lead to increased sulfate emissions. It is felt
that the test accomplished this purpose and has defined an area that requires
further study.
To summarize the sulfate emissions results from the four distance
accumulation cars, the air-injected catalyst cars have significantly higher
sulfate emissions than the nonair-injected catalyst cars for all test cycles.
The reason for this cannot be stated with certainty, since as explained pre-
viously, some important parameters were not measured. However, it is felt
91
-------
TABLE 23. NOX AND SUJLFUR EMISSIONS FROM
SELECTED TESTS ON SwRI CAR EM-3
V0
Ni
Miles
15,000
20,000
30,000
30,000
30,000
15,000
20, 000
30,000
30,000
30,000
15,000
20,000
30,000
30, 000
30, 000
Date(s)
11/3, 11/5/76
12/19/75
2/6/76
2/18/76
2/19/76
11/3, 11/5/75
12/19/75
2/6/76
2/18/76
2/19/76
11/3, 11/5/75
12/19/75
2/6/76
2/18/76
2/19/76
Test
Type
FTP
FTP
FTP
FTP
FTP
SET-7
SET-7
SET-7
SET-7
SET-7
FET
FET
FET
FET
FET
EGR
Operative?
Yes
No
Yes
No
Yes
Yes
No
Yes
No
Yes
Yes
No
Yes
No
Yes
g/km
NOX
1. 10
3.26
1.07
2.46
0. 93
0.86
3.00
0.81
2.67
0.80
0.75
3.38
0.87
2.87
0.85
S02
0. 186
0.224
0. 116
0.086
0. 169
0.081
0.085
0.096
0.063
0. 101
0.046
0.075
0.059
0.040
0.045
mg/km
H2S04
5. 67
11.35
2.84
3.66
4. 12
15.27
44; 59
6.62
49.09
7.05
38.01
45.08
12.93
62.79
14.55
% Fuel
S as
H2S04
2.44
5.91
1.33
1.89
1. 94
9.91
33.01
4.55
35.46
4.56
29.46
39.33
10. 11
55.93
11.42
% Fuel
S as
S02
121.62
178.76
83.31
68.33
122. 10
81. 18
95.88
101.31
69.89
100.27
53.60
99.88
70.75
54.79
54.25
Total
Recovery
124.05
184.67
84.65
70.23
124.04
91.09
128.89
105.86
105. 35
104.83
83.06
139.21
80.87
110.72
65.67
Note: SET-7 is average of 4 sets
-------
TABLE 24. RESULTS OF EMISSION TESTS AT 80 kph STEADY STATE
ON FOUR CARS WITH EGR SYSTEM OPERATING NORMALLY AND DISABLED
Test
No.
11
12
11
12
11
12
11
12
13
Car
No.
EM-1
EM-1
EM- 2
EM-2
EM- 3
EM-3
EM-4
EM-4
EM-4
Operative
EGR
yes
no <"
yes
no
yes
no
yes
no
no (2)
g/km
HC
0.06
0.05
0.03
0.04
0.07
0.06
0.02
0.01
0.02
CO
0.21
0.27
0.12
0.11
0.02
0.02
0.02
0.03
0.04
3.03
3.31
1.36
2.33
1.58
4.36
0.42
1.24
1.28
S02
0.054
0.079
0.033
0.042
0.020
0.019
0.030
0.022
0.020
mg/km
H2S04
0.01
0.01
1.27
1.59
44.16
55.60
10.72
17.15
29.28
% Fuel
as
H2SO4
0.00
0.00
1.15
1.41
46.74
60.72
9.12
16.35
27.36
% fuel
as
S02
81.49
123.86
45.33
57.09
32.13
31.56
38.83
32.55
28.68
Total
Recovery
81.50
123.86
46.48
58.50
78.87
92.27
47.95
48.90
56.04
Avg.Cat.
Inlet
Temp °F
888°
939°
1143°F
881°F
831°F
1081°F
974°F
976°F
02 %
Out Of
Cat.
1.00%
.75%
1.13%
0.83%
6.00%
6.00%
5.50%
6.00%
6.13%
Notes:
Except where noted when EGR system is inoperative,
the vacuum line to the EGR valve was disconnected,
but not plugged.
For this test vacuum line to EGR valve was dis-
connected and plugged.
-------
that the higher oxygen level in the air-injected catalyst was the cause of the
higher sulfates. For the air-injected catalyst cars, the sulfate emissions
from the SET-7 test increased as distance traveled increased from 0 to be-
tween 8,000 and 16,000 km. The SET-7 sulfate emissions then decreased
exponentially as distance traveled increased to 80,500 km. The reason for
this decrease is only speculative, but one possibility is that the catalyst
efficiency is decreasing, so that along with its decreasing ability to
oxidize CO and HC, it also decreases in ability to oxidize S02 to SO3- The
SET-7 sulfate emissions from the non air-injected catalyst cars showed little
change with distance traveled for the entire 80,500 km.
The smallest sulfate emission observed during this study was less than
0.01 mg/km. This occurred on the accelerations to 48 kpm during the 32,000
km test series on EM-1. The largest sulfate emission observed was 77.11 mg/km.
This occurred on the acceleration to 96 kpm during the 32,200 km test series
on EM-3. The highest sulfate emissions from each car occurred during the
acceleration to 96 kph test. The lowest occurred during the acceleration to
48 kph test for three of the four cars. Sulfate emission variations were
hated til with whether or not air was injected, (2) with distance traveled,
and (3) with test cycle. These findings indicate that there are large dif-
ferences in sulfate emissions from cars in actual operation on,the road.
2. Storage, of Sulfur Compounds
One of the obj ectives of this study was to investigate, where possible,
the storage and release of sulfur compounds from the catalyst systems. This
storage and release of sulfur on a test cycle basis can easily be seen if
the exhaust sulfur emissions are expressed in terms of percent by weight of
the sulfur consumed with the fuel. If there is no net storage or release of
sulfur from the catalyst, the exhaust sulfur emissions should equal 100 per-
cent of the fuel sulfur consumed during the test. Recovery of sulfur in the
exhaust in excess of 100 percent indicates a net release of sulfur during the
test. A recovery of less than 100 percent indicates a net storage during the
test. For purposes of these discussions, the term "total recovery" means the
sum of the exhaust sulfur in SO2 expressed as percent of fuel sulfur and the
exhaust sulfur in sulfate (as H2SO4) expressed as percent of fuel sulfur.
Tables 17 to 20 contain the values of sulfur in SO2 as percent of fuel
sulfur, sulfur in sulfate as percent of fuel sulfur, and total recovery for
each test type at all distance intervals for each of the four cars. This
information is plotted by test type in Figures 39 to 45 to aid in interpreting
the data. The results from all four cars are shown in each figure to facili-
tate comparison between cars.
An examination of the figures shows that the storage or release of sul-
fates is not necessarily the same for. all cars on a particular test. There
are also apparent changes in storage with distance traveled for some cars
on some tests.
Before discussing the sulfate storage, of each car on each test cycle,
it should be pointed out that the SO2 collection procedure is a wet chemistry
procedure that requires considerable sample handling and thus is more prone
to errors than the other emission measurements made during this study. Thus,
94
-------
150
o
o 100
-P
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50
-
mmm
1
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ro
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EM-1
EM-2
200
150
O
u
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C
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100
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**
n
10
CM
% Fuel S as H2SO4
| [ % Fuel S as S02
* Air Injection Leak
** EGR System Failed
150
rsi
00
100
VO
50
EM-3
EM-4
FIGURE 39. EXHAUST SULFUR RECOVERY FROM FTP TESTS
AT DISTANCE INTERVALS FOR FOUR CARS
95
-------
150 r
o
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.p
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(1)
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EM-1
EM-2
D
H2S04
SO,
* Air injector leak
** EGR system failed
150
100
50
150 .-
100
50
**
00
EM-3
EM-4
FIGURE 40, EXHAUST SULFUR RECOVERY FROM SET-.7 TESTS
AT DISTANCE INTERVALS FOR FOUR CARS
96
-------
200 r
150
-------
150
o
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o
n
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100
50
150
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150
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EM-2
H2S04
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so2
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EGR system failed
150
150
0
U
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4-1
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U
VH
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I II I II
100
100
OOOOOOOO
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50
50
j^jj fj ^3 ^1 ^^
o o o o o o o
ooo ooo ooo
oncor-i
EM-3
EM-4
FIGURE 43. EXHAUST SULFUR RECOVERY FOR 48 kph STEADY STATE
TESTS AT DISTANCE INTERVALS FOR FOUR CARS
99
-------
335
323
200 T
150
a1
o
o
c
-------
150
0
o
-p
0)
o
100
50
200
150
100
EM-1
50
EM-2
D
SO-
* Air Injector leak
** EGR system failed
150
III I I II II I
o o o o o o o
oooo ooooo
o in t-t I-H CN ro PI «sr in
CM O VO
-------
SC>2 differences between two tests of less than ±10 percent may not be
significant. However, if the data for each car is considered over the
complete 80,500 km distance accumulation, the trend and total recovery
level should be sufficiently valid to draw correct conclusions.
For the FTP tests, car EM-1 apparently stored sulfur compounds at
a decreasing rate as distance traveled increased. At zero kilometres
EM-1 had a net storage of about half of the sulfur consumed with fuel.
As distance traveled increased, the net storage decreased. After ap-
proximately 50,000 km, there was an apparent release of sulfur compounds
from the catalyst during the FTP test. Car EM-2 showed the same trend,
except that it apparently was just at the equilibrium condition (no net
storage or release) by the end of the 80,500 km accumulation. Thus,
both the non air-injected cars stored sulfur during the FTP at zero kilo-
metres, but by the time 80,500 km had been accumulated, they were no
longer storing sulfur during the FTP test.
As was pointed out earlier, the data from the replicate tests of
80,500 km of cars EM-1 and EM-2 were not averaged because of the erratic
emissions results obtained. This is most obvious in total sulfur recovery
from the three nonsteady-state tests (FTP, PET, and SET-7) on car EM-1.
The test data was checked throughly for errors, but none were found. While
the catalyst was obviously storing more sulfur during the replicate tests,
the reasons for this are not known.
The total recovery for car EM-3 was close enough to 100 percent for
the total distance accumulated (neglecting the test with failed EGR) to
indicate that there is no net storage or release of sulfur compounds during
the FTP and that there was no change with distance traveled. The FTP is
apparently a net storage test for car EM-4, since it never reached 100
percent "recovery (neglecting the two tests with air leaks) during the
entire distance accumulation. However, from 3,200 km to 80,500 km, there
is an increase in total recovery, indicating that less sulfur was being
stored as distance traveled increased. Just how the leak in the air in-
jection system affected the change in sulfur storage with distance traveled
is not known. The two air-injected cars then, displayed different sulfur
storage characteristics during the FTP tests.
For the SET-7 tests, car EM-1 had generally decreasing total recovery
over the 80,500 km. It may have actually been releasing a small amount
of stored sulfur at the 8,050 km accumulation, however by 80,500 km the
total recovery was approximately 50 percent. It should be noted that the
SET-7 results shown in Figure 40 are the average of all SET-7 tests run at
the particulate distance accumulation point. Both the number and sequence
of the SET-7 tests changed during the lower distances on all cars. However,
the test sequence was the same from 24,100 km onward for all cars. For car
EM-2, the total recovery never dropped below essentially 100 percent, it
can be concluded that the SET-7 test is one of net release of stored sul-
fates for car EM-2. Thus, for the SET-7 test, the two non air-injected cars
showed opposite trends with distance accumulation
The total recovery from car EM-3 in general' shown little variation
102
-------
from 100 percent over the oritiro HO, 300 km nccuim.ilnt.ion. If the tosts
with the failed EGR system are neglected, the average recovery for EM-3
is 106 percent. The total recovery for car EM-4 also shows little change
between 24,100 km and 80,500 km. The data 80,510 and 16,100 km are neg-
lected because of the leak in the air injection system at that time. How-
ever, the average total recovery of 84 percent indicates that EM-4 was
operating in a storage mode during the SET-7 tests.
The HFET tests have total recovery patterns that are somewhat
difficult to ascertain. The total recovery from car EM-1 appears to in-
crease from near 100 percent to around 154 percent between 8,050 km and
32,200 km. During this distance interval, car EM-1 was operating in a
net release mode during the HFET. After 32,200 km, the total recovery for
EM-1 dropped to between 30 and 70 percent by 80,500 km. In this distance
interval, EM-1 stored sulfur during the HFET. Car EM-2 exhibited a some-
what similar pattern of increasing then decreasing total recovery. How-
ever the total recovery was always over 100 percent indicating that EM-2
was always releasing stored sulfur during the HFET. Again for this test,
the two non air-injected cars have somehwat different patterns of total
recovery.
Car EM-3 operated in a release mode, with recoveries slightly over
100 percent for the 8,050 and 16,100 km tests. After that the car stored
sulfur during the HFET at a constant rate for the remaining tests to 80,500
km. The average total recovery (excluding the test with failed EGR) was
approximately 80 percent. It is difficult to determine, given the accuracy
of the SO, method, whether the total recovery from EM-4 remained constant
from 24,100 to 80,500 km or whether it decreased somewhat. In either case,
the total recovery was always at or below 100 percent, indicating that the
HFET was a storage mode for EM-4.
The acceleration to 48 kph test and the 48 kph steady-state test
are sulfur storage modes for all cars. However, there is no obvious
pattern with distance traveled for any of the four cars. For the accel-
eration to 48 kph, cars EM-1, EM-3 and EM-4 had average total recoveries of
approximately 35 percent. Car EM-2 had an average total recovery of ap-
proximately 45 percent. For the 48 kph steady tests, the two non air-
injected cars, EM-1 and EM-2 had average total recoveries of approximately
22 and 29 percent respectively. The air-injected cars, EM-3 and EM-4, had
somewhat higher total recoveries during the 48 kph steady state tests.
Both of these cars averaged approximately 40 percent recovery.
The acceleration to 96 kph test was definitely a sulfur release mode
for EM-1, EM-2 and EM-3. Cars EM-1 and EM-3 appear to have had declining
total recoveries as the distance traveled increased from 0 to 80,500 km.
However, even at the 80/500 km test the recoveries from both these cars
were above 100 percent, indicating that their catalysts were still releasing
stored sulfur. Car EM-2, while always operating in the release mode, had
increasing total recoveries from 0 to approximately 64,000 km. After this,
the total recovery apparently dropped. However, it was still above 100
percent at 80,500 km. Car EM-4 had a total recovery of 80 percent at the
?ero kilometre tests, indicating that it was storing sulfur at this time.
The total recovery for EM-4 continued to increase as distance traveled in-
103
-------
creased to 48,300 km. From approximately 24,100 km, the total recovery
was above 100 percent, indicating that the catalyst was releasing stored
sulfur. The total recovery for EM-4 decreased as distance traveled increased
from 48,300 to 80,500 km. At the 80,500 km test the recovery was approxi-
mately 60 percent, indicating that the catalyst was once again storing sulfur.
At 96 kph, the two nonair-injected cars, EM-1 andEM-2, exhibited
similar patterns of total recovery. Both cars had recoveries above 100
percent at zero kilometres indicating the release of stored sulfur. The
total recovery for EM-1 started to drop after 32,200 kilometers of distance
traveled. From the 48,300 km test on, the total recovery was below 100
percent indicating the storage of sulfur in the catalyst. While the total
recovery from car EM-2 started to decline at the 48,300 km test, it did not
go below 100 percent until the 80,500 km test.
The air-injected cars, EM-3 and EM-4, showed little change in total
recovery from the 96 kph test over the entire 80,500 km. The average
total recovery for EM-3 was 63 percent, indicating that 96 kph was a storage
mode for this car. The total recovery at 96 kph for car EM-4 varied con-
siderably from test to test, but there is no apparent pattern. The average
total recovery was 72 percent, indicating for this car also, 96 km was a
storage mode.
Throughout the tests, various patterns of storage and release have
been seen. In every case where the pattern changed abruptly in mganitude or
direction, the test data and vehicle were checked. Occasionally, as with
the air injection leaks on EM-4 and the failed EGR system on EM-3, a reason
for the change was found. For the remainder of the cases no errors or mal-
functions were found. The test plan did not provide for any more detailed
investigation of the causes of the storage and release phenomena.
In summary then, it appears that whether a given vehicle operating
condition is a storage or release mode, is dependent not only on what the
condition is, but also the distance accumulated on the vehicle. Cars EM-lr
2 and 3 stored sulfur during some test cycles and released sulfur during
other test cycles. However, EM-4 apparently stored sulfur during all test
cycles except for the acceleration to 96 kph test at 24,100, 32,200 and
48,300 km.
As mentioned earlier, the recoveries shown in Figures 39 and 45 are
often averages of repetitive test sequences. In the case of the SET-7
and HFET tests, they are also the average of repetitive tests within a given
test sequence. Thus, the histograms do not show if, for instance, a SET-7
has a different total recovery following an FTP, than it would following a
HFET. Nor do the histograms indicate whether there is a net storage or re-
lease of sulfur over the entire test sequence performed at each distance
interval.
As means of examining both of these cases, the cumulative exhaust
sulfur recovered from each test sequence was calculated to allow comparison
with the cumulative fuel sulfur consumed. This can be done, since, except
for 5 minute periods at idle conditions between tests, the exhaust was
104
-------
sampled during the entire test sequence. Plots of cumulative exhaust sulfur
as a function of cumulative fuel sulfur are shown in Figures 46 to 57 for
the test sequences through 24,100 km distance accumulation. The three
different test sequences used are shown for each car. The test sequences
after 24,100 km are not shown, since to do so would make it difficult to
follow any one test sequence due to a confusion of lines and data points.
The plots are presented without discussion, except to point out
that the total sulfur recovery for the entire test sequence is generally
within 80 to 120 percent except for EM-4. Car EM-4 shows the trend noted
earlier of continual net sulfur storage. Table 25 shows the total recovery
for each test sequence for all four cars.
3. Particulate Weights
One of the objectives of this study was to determine the relationship
between the total collected weight of particulates and the weight of sul-
fate from the BCA analysis on each of the filters. As part of the test
procedure, each filter was weighed on a microgram balance before and after
use and the increase in weight calculated. The weight of sulfates on the
filter from the BCA analysis was multiplied by 1.3757 to convert from
weight as sulfate ion (SO4=) to weight as ammonium sulfate, (NI^^SO^. This
was necessary since the sulfate on the filter at the time it was weighed
was in the form of ammonium sulfate.
Plots of the BCA sulfate weight versus the balance weight are shown as
Figures 58 to 61. Since a preliminary analysis indicated that there might
be a different relationship between the weighed and BCA sulfates for the
FTP tests than for the other tests, the FTP test results were plotted sep-
arately. In addition, the non air-injected cars have been separated from
the air-injected cars to examine any differences that might occur between
the two different types of catalyst systems.
From an examination of the plots, it is difficult to determine if there
is a difference in the correlation of the filter weight and BCA sulfate
weight between the air-injected and non air-injected cars on either the FTP
and non FTP tests. To better quantify the relationships between filter
weight and BCA weight and the differences between air-injected and non air-
injected cars, a linear regression was performed on each group. The re-
sulting regression equations are shown on each figure together with a plot
of the equation. The correlation coefficient is also shown for each equa-
tion.
While there is some scatter in the data, for the non-FTP tests, the
correlation coefficients are sufficiently high to indicate good linear fit.
The fit is slightly better for the air-injected cars than the non air-injected
cars. However, the intercepts and slopes of the two equations are close
enough to conclude that there is probably no difference in the balance weight-
BCA relationship for the two sets of cars. The FTP tests show considerable
scatter and corresponding poorer correlation coefficients. Also, the inter-
cepts and slopes of the air-injected and non air-injected groups are dif-
ferent enough to suspect there is a difference in the balance weight-BCA
relationship for the FTP tests on the two sets of cars. Thus, it appears
105
-------
Test No.
Test Type
CO
6
SO
i
4J
CO
I
w
0)
1
2
3
4
5
6
Cold LA-4
Hot LA-4
Accel to 48 kph
48 kph
Accel to 96 kph
96 kph
6 !:::£:^
1 2 3 4 5 6 7
Cumulative Fuel Sulfur, grams
1975 Federal Plymouth Gran Fury
Monolithic Catalyst, no air injection
0.0415% fuel Sulfur
FIGURE 46. CUMULATIVE SULFUR RECOVERED IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-1 AT 0 AND 3200 km
106
-------
Test No.
Test Type
1
2
3
4
5
6
7
8
9
10
Cold LA-4
Hot LA-4
SET-7
SET-7
HWFET
HWFET
Accel to 48 kph
48 kph
Accel to 96 kph
96 kph
2345678
Cumulative Fuel Sulfur, grams
1975 Federal Plymouth Gran Fury
Monolithic Catalyst, no air injection
0.0415% fuel Sulfur
FIGURE 47. CUMULATIVE SULFUR RECOVERED IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-1 AT 8050 AND 16, 100 km
107
-------
Test No.
Test Type
Test No.
Test Type
1
2
3
4
5
FTP
SET-7
SET-7
HWFET
SET-7
6
7
8
9
10
SET-7
accel to 48 kph
48 kph
accelto 96 kph
96 kph
5 6 7
Cumulative Fuel
8
Sulfur,
9 10
grams
11 12
1975 Federal Plymouth Gran Fury
Monolithic Catalyst, no air injection
0.0415% fuel Sulfur
FIGURE 48. CUMULATIVE SULFUR RECOVERED IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-1 AT Z4, 100 km
108
-------
Test No.
Test Type
1
2
3
4
5
6
Cold LA-4
Hot LA-4
Accel to 48 kph
48 kph
Accel to 96 kph,
96 fcph
(4
M
DO
CO
0
H
o>
>
*
a)
r-1
I
3
o
9
8
7
6
5
4
3
2
1
234 567
Cumulative Fuel Sulfur, grams
1975 Federal Chevrolet Impala
Pelleted Catalyst, no air injection
0.0415% fuel Sulfur
FIGURE 49. CUMULATIVE SULFUR RECOVERED IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-2 AT 0 AND 3200 km
109
-------
Test No.
Test Type
co
s
rt
bo
X
w
-------
Test No.
Test Type
1
2
3
4
5
FTP
SET-7
SET-7
HWFET
SET-7
Test No.
6
7
8
9
10
Test Type
SET-7
accel to 48 kph:
48 kph
accelto 96 kph
96 kph
45 6 7 8 9 10 11
Cumulative Fuel Sulfur, grams
1975 Federal Chevrolet Impala
Pelleted Catalyst, no air injection
0.0415% fuel Sulfur
FIGURE 51. CUMULATIVE SULFUR RECOVERED IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-2 AT 24, 100
111
12
-------
Test No.
Test Type
1
2
3
4
5
6
Cold LA-4
Hot LA-4
Accel to 48 kph
48 kph
Accel to 96 kph
96 kph
CQ
s
0)
O
5
4
(0 Q
i-H J
1
0
12 34 5678
Cumulative Fuel Sulfur, grams
1975 California Plymouth Gran Fury
Monolithic Catalyst, with air injection
0.0415% fuel Sulfur
FIGURE 52. CUMULATIVE SULFUR RECOVERED IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-3 AT 0 AND 3200
U2
-------
Test No.
Test Type
1
2
3 and 4
5 and 6
7
8
9
iO
Cold LA-4
Hot LA-4
SET-7
HWFET
Accel to 48 kph
48 kph steady
Accel to 96 kph
96 kph Steady
CO
2468
Cumulative Fuel Sulfur, grams
1975 California Plymouth Gran Fury
Monolithic Catalyst, with air injection
0.0415% fuel Sulfur
FIGURE 53. CUMULATIVE SULFUR RECOVERED IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-3 AT 8050 .-km
113
-------
Test No.
Test Type
Test No.
Test Type
1
2
3
4
5
FTP
SET-7
SET-7
HWFET
SET-7
6
7
8
9
10
SET-7
ace el to 48 kph
48 kph
accel to 96 kph
96 kph
345678
Cumulative Fuel Sulfur, grams
10 11
12
1975 California Plymouth Gran Fury
Monolithic Catalyst, with air injection
0.0415% fuel Sulfur
FIGURE 54. CUMULATIVE SULFUR RECOVERED IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-3 AT 16, 100 AND 24, 100 km
114
-------
Test No.
Test Type
1
2
3
4
5
6
Cold LA-4
Hot LA-4
Accel to 48 kph
48 kph
Accel to 96 kph
96 kph
CO
a
nt
it
oo
w
-------
Test No.
Test Type
1
2
3 and 4
5 and 6
7
8
9
10
Cold LA-4
Hot LA-4
SET-7
HWFET
Accel to 48 kph
48 kph Steady
Accel to 96 kph
96 kph Steady
10 n
to
g
">
3
nt
A
X
w
0)
I *
km
!•;••!
5;!( 8050 km )
FIGURE
24 6 8
Cumulative Fuel Sulfur, grams
1975 California Chevrolet Impala
Pelleted Catalyst, with air injection
0.0415% fuel Sulfur
56. CUMULATIVE SULFUR RECOVERIES IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-4 AT 8050 km
116
-------
Test No. Test Type
1
2
3
4
5
FTP
SET-7
SET-7
HWFET
SET-7
Test No.
6
7
8
9
10
Test Type
SET-7
accel to 48 kph
48 kph
accel to 96 kph.
96 kph
11 12
4 5 6 7 8 9
Cumulative Fuel Sulfur, grams
1975 California Chevrolet Impala
Pelleted Catalyst, with air injection
0.0415% fuel Sulfur
FIGURE 57. CUMULATIVE SULFUR RECOVERIES IN EXHAUST AS A
FUNCTION OF SULFUR CONSUMED, EM-4 AT 16, 100 AND 24, 100
117
-------
TABLE 25. TEST SEQUENCE TOTAL SULFUR RECOVERY
Distance Test Percent of Fuel Sulfur Recovered in Exhaust
Point
0 km
0 km
3200 km
3200 km
8050 km
8050 km
16100 km
16100 km
24100 km
24100 km
32200 km
48300 km
48300 km (after maint)
64400 km
80500 km
80500 km
EM-1
99
-
122
-
8V
81
107
112
10V
97
122
93
72
84
90
57
EM-2
163
141
138
98
117
-
104
_
-
82
119
119
118
133
92
105
EM-3
87
81
132
111
92
_
76
„
84
90
119
90
-
10V
88
8V
EM-4
58
54
46
84
75
76
_
71
_
73
89
-
.
—
60
Average 95 H8 96
118
-------
M \ I i ' ' i i ' i I ' ^ • l I
hj..; I.U;.. ,;..,;. J :J;JJ iu^J ,4_j-lU-1
-./iji^hi^ii'^iiiliS^!
!tr-r- S •: }•;•>••••••: ',•• !jv>;-,n-ja
FIQURE 58. NET FILTER WEIGHT VERSUS BCA SUL.FATE WEIGHT AS
AMMONIUM SULFATE FOR ALL NON" FTP TEST ON NON AIR-INJECTED CARS
.119
-------
FIGURE 59. NET FILTER WEIGHT VERSUS BCA SULFATE WEIGHT AS
AMMONIUM SULFATE FOR ALL NON FTP TESTS ON AIR-INJECTED CARS
WO
-------
-•- •;-:-<-'•" f: <.7j-,-.--:•;-. -I -|> ~M .-;•:,- ••-
' '• i'.- . • •", H- 'i • !' ; :ll!
, |, 1;,:.^ j .i: ,;.I:., : : : .: |.:.L. • :1,^R
. - .
i!-r:i .
" ! i hi'!1'-1 :,",:l!!;'!ilv|1.1
, • : ' , ! i I iI j , ; ' , : ! • I ' I ;i>Xp . i I , ' • • i ' I • : • I
- •'i:-ri-r-j-:^1-H-—r--p:T-:- -i- r •j^fTrrrrni^r•r"r~T"rqr
. ! ' I '.! :' 'l!: ' i ' ' 'iX^; i "i • , , ! :,: i ..'!:
i ' jX^ • ' I i • ! . ' ' . ' ^ , :
; -t-t^-1 rrrrr}-T'-H--rjr::T: T'K-^H
i *J*t • • , J ! ' . i . ] ' • s ' I I ' I . ' ' : . I , . . .
FIGURE 60. NET FILTER WEIGHT VERSUS BCA SULFATE WEIGHT AS
AMMONIUM SULFATE FOR ALL FTP TESTS ON NON AIR-INJECTED CARS
121
-------
FIGURE 61. NET FILTER WEIGHT VERSUS BCA SULFATE WEIGHT AS
AMMONIUM SULFATE FOR FTP TEST ON AIR-INJECTED CARS
122
-------
that weighing the filters does, for some tests, give an indication, though
not exact, as to the amount of sulfate on the filter. It is not recommended
that weighing replace the BCA analysis. However, weighing the filter can
provide a good quality control check. This check must be considered against
the extra time required to weigh the filter after the test. This usually
amounts to 8 to 12 hours since the filter must be conditioned in the same
temperature and humidity environment in which it was weighed before the test.
4. Analysis of Tunnel Residue
At the conclusion of each distance test sequence on each car, the
paraticulate residue in the sulfate tunnel was collected and qualitatively
analyzed for various elements using X-ray fluorescence.
The resulting elemental analysis, as a percent of sample by weight,
is shown in Table 26. The analysis was requested for platinum (Pt), pal-
ladium (Pd), aluminum (Al), nickel (Ni), iron (Fe), sulfur (S), lead (Pb),
zinc (Zn), copper (Cu) and tin (Sn). Of these 10 elements, no platinum,
palladium, nickel, copper, or tin was found in any of the samples. Chromium,
silicon, and manganese were found in some of the samples and are included in
Table 26.
As was the case when this same type of analysis was done on the
sulfate characterization cars, the largest part of each sample was iron.
This is not surprising, since from a visual inspection of the samples, it
appears that rust, probably from the exhaust system, is the major constituent.
The other elements were found in much smaller quantities and their origin is
not certain. The X-ray detection limits for various elements are included
in Table 7 in Section III.
123
-------
TABLE 26. RESULTS OF X-RAY FLUORESCENT ANALYSIS OF SULFATE
SAMPLING TUNNEL PARTICULATE RESIDUE FOR DISTANCE ACCUMULATION CARS
Car
EM-1 2000 mi
EM-2 2000 mi
EM-3 2000 mi
EM-4 2000 mi
EM-2 10000 mi
EM-3 10000 mi
EM-4 10000 mi
EM-1 15000 mi
EM-2 15000 mi
Total Weight
Collected
grams
0.053
0.163
0.051
0.019
0.123
1.265
0.133
0.190
0.016
Weight
X-rayed
mg
1.36
2.16
1.31
1.46
1.65
1.78
1.62
1.66
1.20
Elements, Percent by Weight
Al
0.4
0.2
0.4
0.2
0.2
1.0
0.5
Fe
29.3
24.2
28.1
21.8
29.6
36.0
32.6
31.0
16.8
S
0.2
0.3
0.5
0.2
0.7
0.5
0.3
0.5
0.8
Pb Zn Cr Si
0.2 0.4
0.1 0.1
0.9
0.1
0.2
0.2
0.5
1.3 5.1
Mn
0.2
0.4
— —
___
ro
-------
V. SULFATE REGULATION STUDIES
This section covers the testing done in support of the EPA activities
to develop regulations for sulfate exhaust emissions during the period
from April through August 1975.
A. Background
On January 31, 1975, the EPA published an Issue Paper^5) which pre-
sented an evaluation of the potential public health impact of sulfate
emissions from catalyst equipped cars. The risk-benefit analysis con-
tained in that paper was the basis for the EPA decision to grant a one
year delay in the statutory standards and to recommend to Congress a fur-
ther five-year delay. Then on March 5, 1975, it was announced that the
EPA had begun the activities necessary to develop a sulfate emission stan-
dard with the necessary driving cycle, test procedures and etc. The stan-
dard would be applicable beginning with the 1979 model year. The Department
of Emissions Research at SwRI was selected as one of four laboratories to
participate in the test procedure development. The other participating lab-
oratories were Exxon Research; EPA, Research Triangle Park; and EPA, Ann Arbor,
B. Purpose
This phase of the project had two principal purposes. One was to
compare alternate preconditioning procedures and test sequences. The
second purpose was to investigate the test-to-test variability of sul-
fates for the proposed driving cycle compared to other driving cycles on
the cars provided. As testing progressed, two additional objectives were
added. One was to investigate the effects of the evaporative emission
canister, the second to investigate driver-to-driver differences.
C. Cars Tested
For the SwRI portion of this procedural development study, two 1975
AMC Hornet Sportabouts were obtained by EPA from American Motors Corporation.
These cars were designed to meet the Federal emissions standard, and to be
sold outside California. AMC catalyst cars with V-8 engines are one of
the few car models for 49-state use equipped with air injection to the
catalyst. The two cars were identical except for color and could be con-
sidered "matched cars" for emissions testing purposes. The AMC Engineering
Department designation for the two cars was D50-34 and D50-36. At SwRI,
these two cars were designated EM-5 and EM-6, respectively. Table 27 is
a description of the cars. Figure 62 shows general views of the cars and
test equipment.
Upon receipt of the cars, a 1975 FTP was run on each car for compa-
rison with AMC tests conducted prior to shipment to SwRI. The comparison
of these two sets of tests is shown in Table 28.
D. Fuel Used
The base fuel used for all tests under this phase of the project ex-
cept Sequence E of Part II was an unleaded gasoline obtained by EPA in a
125
-------
TABLE 27. DESCRIPTION OF VEHICLES TESTED
FOR PROCEDURAL DEVELOPMENT STUDIES
SwRI NO.
EM-5
Manufacturer
Model
Model Year
Inertia Weight Class
Engine Size
Catalyst
Air Injection
Vehicle Identification No.
Manufacturer Engine Design
Idle rpm
Timing
Curb Weight
Odometer Miles When Received
AMC
Hornet Sportabout
1975
3500 Ibs
304 CID V-8
160 in 3 pelletized
yes
ASA 087H209929
D50-34
700
5° BTDC
3401 (Ibs)
2995
EM-6
AMC
Hornet Sportabout
1975
3500 Ibs
304 CID V-8
160 in 3 pelletized
yes
ASA 087H214562
D50-36
700
5° BTDC
3406 (Ibs)
3152
TABLE 28. COMPARISON OF AMC AND SwRI LIGHT DUTY
FTP EMISSIONS FROM TWO 1975 HORNET SPORTABOUTS
HC
CO
NOV
Emissions, grams/km
Car D60-34
SwRI
0.27
2.77
1.19
AMC
0.28
2.39
1.61
Car D50-36
SwRI
0.24
2.13
1.29
AMC
0.26
1.96
1.78
126
-------
FIGURE 62. GENERAL VIEWS OF CARS AND TEST EQUIPMENT
127
-------
large batch, by Dr. R. Bradow of EPA-ORD, Research Triangle Park, North
Carolina. An analysis of that fuel is presented in Appendix F. By the
time this phase of the project had begun, additional data had become
available on national average gasoline sulfur content. This information
showed the average fuel sulfur content to be approximately 0.03 percent
rather than the 0.04 percent that had been used in previous phases of the
project. Thiophenehad been added to the base fuel to bring its sulfur level
up to 0.03 percent. This fuel was identified within SwRI as EM-236-F.
The fuel used during the tests of car EM-3 under Sequence E of Part II
of this phase was the same fuel the car was using for distance accumulaion.
This fuel was an unleaded gasoline with a sulfur level of 0.04 percent. The
fuel is described in Section IV of this report and in Appendix F.
E. Test Schedule and Procedures
The test schedule was divided into two parts. The first part was
designed to investigate differences in sulfate emissions from the SET-7
due to test order and to investigate test-to-test variability of sulfate
emissions. The test schedule for both cars for Part I is shown in Table 29.
Note that two different types of road distance accumulations are specified,
the AMA durability cycle and the Ann Arbor Road Route.
The route used by SwRI for the AMA durability cycle is described in
Appendix H. The route used for the Ann Arbor Road Route, named the San
Antonio Sulfate Preconditioning Route, is described in Appendix I. Item 1
of the Part I schedule, 3000 miles of AMA durability running was performed
by AMC prior to shipment of the cars to SwRI. Catalyst temperatures were
recorded on a multipoint temperature recorder during all tests. Catalyst
temperature on each car was taken during one of the Ann Arbor Road Route
preconditioning runs. The catalyst temperature and vehicle speed were
manually recorded every 30 seconds over the road course. At the end of
each test sequence (i.e., after the FET in Part 2A), the catalyst con-
version efficiency was checked on the dynamometer at 30 mph and at 50 mph
by sampling the exhaust before the catalyst for 2 minutes then after the
catalyst for 2 minutes at each speed, it was realized that stable condi-
tions were notreached during this time. The purpose of this sample was
to ensure that the catalyst was performing consistently while putting a
minimum amount of extra miles on the vehicle.
After completion of the Part I testing, the EPA held a meeting on
July 15, 1975 in Ann Arbor, Michigan. In attendance were all four labor-
atories working on sulfate testing in support of the sulfate regulation
studies. As a result of this meeting, the original test schedule for the
Part II testing was changed. The testing requested of SwRI was outlined
in an EPA memo from J. H. Somers to J. p. DeKany, dated July 18, 1975.
This schedule was further modified by a telephone conversation on July 30,
1975 with Mr. Dick Lawrence, contract Project Officer. The resulting Part
II test sequence is shown in Table 30.
In Part II of this phase, a third car, the 1975 California Plymouth
Fury (car EM-3) used in the study of distance accumulation on sulfates,
-------
2. Sequence A.
4. Sequence B.
5.
6.
Sequence C.
7. Sequence D.
8. Sequence E.
TABLE 29. SULFATE TEST SCHEDULE, PART I
Run AMA to 3,000 miles
(regular AMA, 11 laps, 70 mph maximum speed)
Ann Arbor Road Route - 1 hour
1 LA-4 (hot start)
• 4 hot start sulfate emission tests (SET)
Ann Arbor Road Route - 1 hour
1 LA-4 (hot start)
Overnight soak
• Federal Test Procedure (FTP)
• Fuel Economy Test (FET)
Repeat A
Repeat A again
Run 300 miles of modified AMA*
Ann Arbor Road Route - 1 hour
1 LA-4 (hot start)
Overnight soak
. FTP
• SET - 2 times
. FET
Repeat B
Repeat B again
Run 300 miles of modified AMA
Ann Arbor Road Route - 1 hour
1 LA-4 (hot start)
Overnight soak
. FTP
. FET
• SET - 2 times
Repeat C
Repeat C again
• Run SET x times until stable sulfate emission
value is obtained
•Run a series of 12 SET-7 tests, 6 with fuel
evaporative emissions canister connected,
6 with canister disconnected on car EM-5 only
* 55 mph top speed, no WOT accels
• Sulfate and S02 emissions taken
129
-------
TABLE 30. PART II TEST SCHEDULE
Sequence A:
Sequence B:
Sequence C:
Sequence D:
Sequence E:
(Car EM-5, 1975 49 State Hornet)
12 Replicate SET-7 Tests with One Driver
(Car EM-5, 1975 49 State Hornet)
5 Constant Speed 35 mph Tests (1 hour, each test)
2 SET-7
(Car EM-5, 1975 49 State Hornet)
5 Constant Speed 50 mph Tests (20 minutes, each test)
2 SET-7
(Car EM-5, 1975 49 State Hornet)
12 SET-9 Tests with One Driver
(Car EM-3, 1975 California Plymouth Gran Fury)
30 SET-7 Tests With Three Drivers
130
-------
was included in the test series to investigate driver-to-driver differ-
ences. The car is described in Section IV of this project. Also in
Part II, a "noise free" version of the SET-7 test, designated as SET-9,
was evaluated.
F. Test Results
1. Part I Results
As part of the test, catalyst temperatures on each of the two cars
was measured on the San Antonio sulfate preconditioning route. The temp-
erature and vehicle speed, as a function of time, is shown in Figures 63
and 64. These temperatures can be compared with the temperatures during
the various dynamometer test cycles.
The purpose of this part of the test program was to investigate dif-
ferences in sulfate emissions due to preconditioning and the order of
testing in the test sequence. Tables 31 and 32 list the mean emission
levels for each test sequence in Part I by test cycle. For Sequence D
which was 20 repetitive SET-7 cycles and Sequence E on EM-5 which was also
repetitive SET-7 test, the standard deviation and coefficient of variation
are also listed. A complete listing of the results for each test is con-
tained in Appendix I. As an aid to comparing the various tests, the sul-
fate emissions for each test are plotted in Figure 65.
It should also be noted that the FTP tests in Sequence A were per-
formed in a slightly different manner than the FTP tests of Sequence B
and C. For Sequence A, two 23 minute LA-4 cycles were run, one with a
cold start and one with a hot start, one bag sample and one sulfate filter
were taken during each 23 minute period. The results of the two cycle were
then averaged, weighting the cold cycle 43 percent and the hot cycle 57 per-
cent. For Sequence B and C, a regular "3 bag" FTP was run, taking only one
sulfate filter and one SO2 sample for the entire FTP. This means that while
the emissions of HC, CO, and NOX are weighted for the cold and hot start
portions of the test, the sulfate and SO2 emissions are not weighted.
From the examination of the tables, it appears that the order of the
SET-7 test in the test sequence has an effect on the sulfate emissions;
but little, if any, effect on the HC, CO, and NOX. When the two SET-7
tests followed an FTP test, the average sulfates from the first SET-7 were
approximately 50 percent higher than those from the first SET-7 following
an HFET. However, on the average, the second of the two SET-7 tests fol-
lowing an FTP had approximately 25 percent lower sulfate emissions than
those from the second SET-7 following an HFET.
While the FTP was always first in the test order, there was a dif-
ference in the gaseous and sulfate emissions between Sequence A and Se-
quences B and C. At least part of this difference is probably due to the
differences in test procedure explained earlier. The two procedures are
mathematically equivalent for the gaseous emissions, but not for the sul-
fate emissions. The sulfate emissions from the HFET are also higher for
Sequence A than for Sequences B and C.
131
-------
U)
to
400
16
20
24
28 32
Time, minutes
36
40
44
48
52
56
60
FIGURE 63. CATALYST TEMPERATURE OVER SAN ANTONIO VERSION OF ANN ARBOR ROAD COURSE FOR AMC HORNET NO. D50-34
-------
200
20
24 28 32
Time, minutes
36
40
44
48
52
56
FIGURE 64. CATALYST TEMPERATURE OVER SAN ANTONIO VERSION OF ANN ARBOR ROAD COURSE FOR AMC HORNET NO. D50-36
-------
TABLE 31. SUMMARY OF EMISSIONS FROM CAR EM-5 ON PART I TEST SEQUENCES
Average Emissions
ui
Cycle
SET -7
SET -7
SET -7
SET-7
SET -7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
FTP
FTP
FTP
HFET
HFET
HFET
Sequence
A
B
C
D
D
E
E
A*
B
C
A
B
C
Test
No.
1
2
3
4
2
3
3
4
1 to 20
1 to 20
1 to 20
4 to 20
4 to 20
4 to 20
2 to 5
2 to 5
2 to 5
7 to 12
7 to 12
7 to 12
5
1
1
6
4
2
Replicates
3
3
3
3
3
3
3
3
20
20
20
17
17
17
4
4
4
6
6
6
3
3
3
3
3
3
Statistic
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Std. Dev.
Coef. Var.
Mean
Std. Dev.
Coef. Var.
Mean
Std. Dev.
Coef. Var.
Mean
Std. Dev.
Coef. Var.
Mean
Mean
Mean
Mean
Mean
Mean
HC
0.07
0.07
0.07
0.07
0.08
0.06
0.07
0.05
0.06
0.01
8.3%
0.06
^0.01
8.2%
0.06
0.00
0. 00%
0.06
0. 01
8. 32%
0. 27
0.42
0.43
0.06
0.06
0.05
g/km
CO
0.19
0.11
0. 15
0. 10
0.08
0.07
0. 11
0.09
0. 10
0.09
88. 9%
0. 10
0. 10
100. 0%
0.06
0.02
43. 3%
0.06
0.04
55. 3%
2.46
4.58
4.33
0.09
0.05
0.07
mg/km
NOX
1.20
1.30
1.23
1.28
1.65
1.68
1.44
1.44
1. 50
0. 54
36.4%
1. 36
0. 10
7.3%
1. 80
0. 14
7.6%
1.66
0. 22
13. 5%
1. 13
1.86
2.04
1. 32
1.62
1.44
S02
48
-
-
-
-
-
42
41
36.25
10. 33
28. 5%
38. 35
9.70
25.30
45. 50
11.96
26.3%
33.43
12.42
37. 2%
33
-
25
34
-
25
H2S04
19.84
25. 36
37.06
47. 21
20. 50
17. 73
14.47
23.81
35. 70
9.46
26.6%
37. 86
7. 17
18. 9%
40. 2
6.47
16. 1%
42. 37
5.55
13. 1%
10. 16
4.90
4.91
61. 14
27.68
31. 18
and SO2 emissions are -weighted averages based on one sample for cold LA-4 and one sample for
hot LA-4.
-------
TABLE 32. SUMMARY OF EMISSIONS FROM CAR EM-6 ON PART I TEST SEQUENCES
Average Emissions
Cycle Sequence
SET -7
SET -7
SET -7
SET -7
SET -7
SET -7
SET -7
SET-7
SET -7
SET-7
SET-7
SET-7
SET-7
SET-7
FTP
FTP
FTP
HFET
HFET
HFET
A
B
C
D
D
A*
B
C
A
B
C
Test
No.
1
2
3
4
2
3
3
4
1 to 20
1 to 20
1 to 20
4 to 20
4 to 20
4 to 20
5
1
1
6
4
2
Replicates Statistic
3
3
3
3
3
3
3
3
20
20
20
17
17
17
3
3
3
3
3
3
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Mean
Std. Dev.
Coef. Var.
Mean
Std. Dev.
Coef. Var.
Mean
Mean
Mean
Mean
Mean
Mean
HC
0.07
0.07
0.07
0.07
0.06
0.06
0.05
0.07
0.06
<0.01
6.2%
0.06
•to. 01
7.9%
0.26
0.41
0.44
0.06
0.05
0.04
g/km
CO
0.025
0. 31
0. 11
0.20
0.02
0.08
0.03
0.02
0. 14
0.13
90.4%
0. 13
0. 13
95. 9%
1.99
3. 51
3. 34
0.02
0.02
0.02
mg/km
NOX
1.35
1. 35
1.40
1.42
1.48
1.42
1.41
1.58
1.34
0.07
5.5%
1.35
0.07
5.4%
1.27
2. 11
2.09
1.48
1.37
1.86
S02
38
32
36
_
_
34
35
43
14. 54
33.7%
42
14. 54
34. 8%
-
28
19
-
36
H2S04
26.48
30.41
36.07
49. 17
36.86
29.41
22. 17
36.77
33.45
10.28
30.74
35.97
7.56
21.0%
13.03
13. 10
9.66
72.00
40.02
42.98
*H_SO . and SO, emissions are weighted averages based on one sample for cold LA-4 and one sample for
hot LA-4.
-------
90
SO
70
C
*- c SO
I
£ 40
3
§ 30
20
10
EM-5
EM-6
Sequence A
Sequence B
JL
Sequence C
Sequence D
FIGURE 65. SULFATE EMISSIONS FROM PART I OF PROCEDURAL DEVELOPMENT STUDY
-------
The sulfate emissions thus reach higher levels for all test cycles
during Sequence A than any other sequence. Sequence A had a different
long term preconditioning (regular AMA durability cycle instead of modi-
fied AMA durability cycle) than Sequences B and C. It is possible, there-
fore, that the differences are due to preconditioning. Yet, the regular
AMA durability cycle has a section of wide open throttle (WOT) accelerations
which the modified durability cycle does not. This would appear to indicate
that the regular AMA durability would purge more stored sulfur from the
catalyst, giving lower sulfate emissions on subsequent tests. However, the
dynamics of sulfate production by the catalyst and the effects of sulfur
storage are still not fully understood. At this time, all that can be said
is that there is a possibility that preconditioning contributed to the dif-
ferences in sulfate emissions seen between Sequence A and Sequences B and C.
It should also be mentioned that the results from other laboratories did not
always follow the same trends seen here.
An examination of Sequence D data indicates that from a cold start,
about three SET-7 tests are required to reach relatively stable sulfate
emission levels. Note that when the first three SET-7 tests in Sequence
D are not used, the coefficient of variation is 18.9 percent compared with
26.6 percent for all tests in Sequence D.
Test Sequence E was run to determine the effect of the fuel evapo-
rative emission canister on sulfate emissions. It was thought that per-
haps in some modes the canister could release fuel vapors into the carbu-
retor and possibly have an adverse effect on sulfate emissions. The
average sulfate emissions from tests with the canister connected to the
engine were compared with the average sulfate emissions with the canister
disconnected. The average sulfate emissions are essentially the same for
the two sets of tests being 40.2 and 42.37 for the connected and discon-
nected tests, respectively. The coefficients of variation are 16.1 for
the tests with the canister connected and 13.1 for tests with the canister
disconnected. Thus, it appears that the fuel evaporative emissions canister
has no effect on repetitive SET-7 sulfate emissions.
2. Part II Results
The purpose of the testing under Part II of this phase was to inves-
tigate test-to-test repeatability. The repeatability of the SET-7 test
was compared to that obtained at 35 mph cruise, 50 mph and an alternate
sulfate test cycle SET-9. The sulfate emission differences of tests with
different drivers were also investigated. It was requested that the test
results from this part of the test program be expressed in grams (or milli-
grams) per mile so that the results could easily be compared with other
laboratories working on this project. Therefore, the data in this section
will be in those units rather than in all metric units as is done for the
other sections of this report.
Table 33 lists the mean, standard deviation and coefficient of varia-
tion of the exhaust emissions for test Sequences A, B, C, and D. For
the two SET-7 tests at the end of Sequences B and C, only the mean and
the range are shown. Appendix I contains the results for each individual
137
-------
CJ
00
TABLE 33. STATISTICAL SUMMARY OF EMISSIONS FROM
TESTS ON PART H, TEST SEQUENCE A, B, C, AND D
S02,
mg/mile
60.12
10.28
17.1
59.61
11.04
18.5
Test
Test
Sequence Cycle Variable
A
A
B
i
r
c
D
SET -7 Mean
Std. Dev.
Coef.Var,%
SET -7 Mean
Std. Dev.
Coef . Var, %
35 mph Mean
Std. Dev.
Coef. Var, %
35 mph Mean
Std. Dev.
Coef. Var, %
SET -7 Mean
Range
50 mph Mean
Std. Dev.
Coef. Var, %
50 mph Mean
Std. Dev
Coef. Var, %
SET -7 Mean
Range
SET -9 Mean
Std. Dev.
Coef. Var, %
SET -9 Mean
Std. Dev.
Coef. Var, %
HC,
CO,
NOX
g/mile g/mile g/mi
0.10
0.02
15.7
0.09
0.02
20.0
0.06
0.03
58.2
0.07
0.02
28.6
0.08
0.00
0.06
0.01
16.7
0.06
0.01
23.5
0.11
0.20
0.11
0.05
45.8
0.10
0.02
21.1
0.06
0.03
53.9
0.06
0.04
64.3
0.04
0.03
82.2
0.03
0.03
100.0
0.04
0.06
0.02
0.03
104.6
0.02
0.02
115.5
0.11
0.09
0.09
0.11
119.7
0.07
0.04
63.0
2.18
0.11
5.1
2.19
0.12
5.3
2.37
0.08
3.2
2.36
0.08
3.5
2.78
0.25
1.97
0.15
7.6
1.99
0.16
8.0
2.54
0.09
2.30
0.10
4.2
2.31
0.08
3.6
40
13
32
44
11
26
146.31
48.95
44
24
8
30
6
2
33.
4.
13.
33.
5.
15.
65.
,42
,46
3
39
15
4
68
11.51
46.76
12.95
27.8
50.88
5.85
11.5
H2SO4» AvB- Cat- No- of
mg/mile Temp., °F Tests
56.73
9.29
16.4
61.35
2.45
4.0
28.48
8.65
30.4
32.02
4.01
12.5
122.93
67.26
62.06
2.98
4.8
62.91
2.64
4.2
72.71
1.49
68.29
7.19
10.5
70.93
3.82
5.4
912
3.0
0.3
912
2.8
0.3
751
8.4
1.1
749
8.8
1.2
922
1
966
5.4
0.6
965
5.7
0.6
906
3.0
907
5.3
0.6
905
2.5
0.3
12
(tests 1-12)
(tests 4-12)
5
(tests 1-5)
4
(tests 2-5)
2
5
(tests 1-5)
4
(tests 2-5)
2
12
(tests 1-12)
(tests 4-12)
-------
test. The table contains the statistical summary for each sequence based
on all tests in the sequence and also based only on the tests considered
to represent a stabilized condition.
The sulfate results from Sequence A of Part II show better repeat-
ability than seen in the Part I tests. The reasons for this are not
known. However, two items may contribute to the improved repeatability.
The first item is that only one driver was used for all 12 tests; the
second is that the spectrophotometer areas indicating the sulfate con-
centrations were determined using an automatic computer integrating sys-
tem starting with Sequence A of Part II instead of manual integration with
a polar planimeter. It should be noted that the catalyst bed temperatures
from Part II, Sequence A show better repeatability than in the Part I tests.
The sulfate emissions coefficient of variation from the stabilized
SET-7 tests of Sequence A can be compared with the sulfate emission coef-
ficient of variation for the other test types. When this is done, it ap-
pears that the SET-7 test cycle repeatability is as good as, or better
than, the other test cycles. In fact, the sulfate coefficient of variation
for all test cycles compares favorably with the coefficient of variation
from the gaseous emissions of the same test cycle. When the SET-7 tests
are compared to the SET-9 tests, the average sulfate emissions from the
SET-9 tests are found to be approximately 16 percent higher than the sul-
fates from the SET-7 tests. The coefficient of variation for the two
types of tests are not significantly different, being 4.0 for the SET-7
test and 5.4 for the SET-9 tests. From these test series it would appear
that the SET-9 does not offer any real improvement in test-to-test repeat-
ability over the SET-7.
The differences in sulfate emissions between the two SET-7 tests
following the 35 mph sequence and the two SET-7 sets following the 50 mph
tests are worthy of vote. If the 35 mph test sequence is examined on a
test by test basis using Table 1-11 in Appendix I, it can be seen that the
35 mph test started out in a storage mode and apparently finally reached
equilibrium at the fifth test, after four hours of running. The first
SET-7, which had the highest sulfate emissions seen during the entire project
(157 mg/mi), apparently was releasing a portion of the sulfur stored during
the previous five hours of running at 35 mph. This conclusion is supported
by the fact that the second SET-7 test of this sequence has a considerably
lower sulfate emission rate. The SET-7 tests following the 50 mph tests,
which apparently were operating close to equilibrium for all tests, showed
little difference in sulfate emissions between the two tests. In addition,
the level of sulfates was lower than the SET-7 tests following the 35 mph
sequence and more in line with the sulfate levels from the stabilized SET-7
tests of sequence A. These tests again support the conclusion, reached
in the discussion of the Part I results, that differences in SET-7 sulfate
emissions can occur because of differences in prior operation of the car.
To help in comparing the various repetitive tests, including those from
Part I the average sulfate emissions and standard deviation for each test
sequence are shown in Figure 66.
139
-------
100
0)
r-H
-H
e
o
w
CM
CO
n)
co
(D
4J
(0
M-l
.H
3
80
60
40
20
0
f
EM-5
EM-6
Std. Dev.
Sequence
Test Type
D
SET
7
E
SET
7
E*
SET
7
1 I
A
SET
7
B
35
mph
C
50
mph
D
SET
9
PART I
PART II
* Fuel evap cannister disconnected
FIGURE 66. SULFATE EMISSIONS FROM REPETITIVE TESTS OF VARIOUS TEST CYCLES
-------
In order to ascertain if part of the variation seen in SET-7
sulfate emissions in Part I were due to driver effects, test Sequence E
was run using car EM-3. This test sequence consisted of 30 SET-7 tests
using three different drivers. A statistical summary of these tests is
shown in Table 34. The results of each individual test are given in Table
1-14. The tests were run on two different days, 15 tests on each day. In
keeping with the finding from Part I, the first three tests on each day
were considered warm-up tests and not used in the analysis. Remember that
car EM-3 with 0.04 percent sulfur fuel was used for this test sequence,
while EM-5 with 0.03 percent sulfur fuel was used for Sequences A, B, C,
and D of Part II. The tests of the 1975 California Plymouth give an average
sulfate emission level of 26.7 nag/mile (exclusive of the first three tests
on each day of testing) at the 0.0415 percent fuel sulfur level. If this
average level is normalized to 0.03 percent fuel sulfur, the sulfate emis-
sion level would be 19.3 mg/mile.
Examining the table, it can be seen that there is a considerable
difference in the average sulfate emissions between the two test days. The
reason for this difference is not known. The coefficients of variation for
the data groupings are in the 20 to 30 percent range. This is more like
the coefficient of variation seen in Part I Sequence D for car EM-5. There
is a difference in the average sulfate emissions for each driver, whether
each day is considered separately or all the data is taken together. To
determine if the differences were statistically significant, an analysis
of variance (ANOVA) was run for each test day separately and both days to-
gether with driver as the independent variable. The results of the ANOVA
are also shown in Table 34. When the test days are considered separately,
the driver was a significant variable at the 0.10 level, but not at 0.025
for each day. When the two days are considered together, the driver was
not a significant variable below the 0.10 level. Considering the dif-
ference in average sulfate emissions for the two days, perhaps more emphasis
should be placed on the results from the individual days. In that case,
it appears that driver difference may explain some, but not all, of the
test-to-test variation seen in the sulfate emissions.
141
-------
TABLE 34. STATISTICAL SUMMARY OF SULFATE EMISSION
FROM REPETITIVE SET-7 TESTS (CALIF. PLYMOUTH)
Part II, Sequence E
Average No.
H2SO4 of
mg/mile Tests
Tests 4 to 15
Tests 4 to 15
Tests 4 to 15
Driver A Tests
Driver B* Tests
Driver C Tests
Driver A Tests
Driver B* Tests
Driver C* Tests
Driver A Tests
Driver B* Tests
Driver C* Tests
8/1/75
8/5/75
8/1 and 8/5
8/1/75
8/1/75
8/1/75
8/5/75
8/5/75
8/5/75
8/1 and 8/5
8/1 and 8/5
8/1 and 8/5
20.58
32.24
26.66
18.38
18.59
24.32
31.16
24.53
39.37
24.77
22.15
31.80
11
12
Z3
5
2
4
5
3
4
10
5
8
Std. Coefficie
Dev. of Variat
mg/ mile Percent
3.96
8.65
8.95
3.97
1.31
6.78
4.93
8.25
8.53
4.77
9.77
19.2
26.8
33.6
21. b
5.4
21.7
20.1
21.0
34.4
21.5
30.7
Results of ANOVA
Groups *
F
Drivers on 8/1/75
Drivers on 8/5/75
Drivers on 8/1 & 8/5/76
statistic
5. 15
4.00
2.50
Significance
0.05<^p<0.
0. 10
-------
VI, BASELINE TESTING
As part of the EPA sulfate baseline study, SwRI measured sulfate
emissions on eight cars. While administratively this work was done under
Task 2 of Task Order 68-03-2196, the test results are reported here, as
specified in the task order.
A. Background
To gain information on the sulfate emission levels on a broad spectrum
of cars, the EPA initiated a sulfate baseline study in the late summer of
1975. This program involved the testing of 59 vehicles for sulfuric acid
and gaseous emissions (HC, CO, NOX). A variety of catalyst and noncatalyst
cars were tested. These cars included both current production cars and cars
designed to meet advanced emissions standards. Five different laboratories
participated in this program.
B. Purpose
There were two main purposes of this study. The first was to obtain
sulfate emission factors on a wide group of different in-use and prototype
vehicles. These emission factors can then be used to evaluate sulfate
emissions from individual emission control systems and vehicles as well as
being used for input to air quality models assessing the impact of automotive
sulfate emissions. The second purpose of the study was to determine the
effect on sulfate emission from vehicles meeting increasingly stringent emis-
sion standards for HC, CO and NOX.
C. Cars Tested
As its part of the baseline study, the Department of Emission Research
at SwRI tested eight cars. Two of the cars were 1975 production models
without catalysts. One was a 1975 production model with catalyst and air
injection, designed to meet 1975 Federal emission standards. Two were 1975
California production models with catalysts and air injection. One was a
1975 production model diesel powered car. The remaining two were proto-
type fuel injected vehicles with three-way catalysts. A complete descrip-
tion of the cars is given in Table 35.
Cars 1-3 and 1-4 were obtained from local rental sources. Car IlA-l
was one of the cars used in the procedural development phase of this pro-
ject and was supplied by the manufacturer. Cars IIB-1 and IIB-6 were two
of the distance accumulation cars leased new for the distance accumulation
study. Car III-7 was supplied by EPA. Car IV-4 and IV-17 were in reality
one car with two different exhaust catalyst systems. The car was a pro-
totype loaned to EPA by the manufacturer.
D. Fuel Used
The fuel that had been planned for use on the baseline gasoline powered
cars was part of the batch of Phillips Petroleum unleaded gasoline obtained
tn a large batch by Dr. R. Bradow of EPA-RTP. An analysis of this fuel is
143
-------
TABLE 35. SULFATE BASELINE CARS
TESTED AT SOUTHWEST RESEARCH INSTITUTE
EPA
Number
1-3
1-4
IIA-1
IIB-1
IIB-6
III-7
IV-4
IV-17
Year
1975
1975
1975
1975
1975
1975
197X
197X
Make
Ford
Dodge
Hornet
Chevrolet
Plymouth
Mercedes
Ford
Ford
Model
Granada
Coronet
Sportabout
impala^
Gran Furyd
240D(2)
Pinto
Pinto
Engine
CID
351W
318
304
350
> 360
147
140
140
Distance
Accumulated
km<3>
9,886
16,605
8,473
24,135
16,090
2,824
1,900
1,900
Catalyst
No
No
Yes w/air
Yes w/air
Yes w/air
No
3-way Degussa
+ Oxidation
w/air
3-way
Engelhard
TWC-9
California model
(2)Diesel powered
(3)on catalyst cars, distance accumulated refers to
distance accumulated on catalyst
144
-------
contained in Appendix F. Thiophene was added to the fuel to raise the
fuel sulfur level to 0.03 percent. This doped fuel was identified within
SwRI as EM-236-F. This fuel was used for the tests of cars 1-3, 1-4, IIA-1,
and IV-4.
Recall that cars IIB-1 and IIB-6 were part of the distance accumulation
project. Since the cars were still in the process of accumulating distance,
it was felt that the fuel used for the baseline tests should be the same as
used in the distance accumulation project. This fuel, identified as EM-212-P
had a nominal sulfur level of 0.04 percent.
The diesel fuel used for car III-7 was a commercially-available Gulf 2D
diesel fuel. This fuel was chosen rather than a diesel fuel blended to meet
the EPA specifications for emissions test fuel. The emission test fuels are
higher in sulfur and aromatics than normal diesel fuels. The diesel fuel
used was numbered EM-246-F.
Car IV-17 started its preconditioning on the Phillips fuel, EM-236-F,
however, engine operation problems were encountered during the preconditioning
of car IV-17. With the assistance of representatives from Ford Motor Company,
the problem was traced to stuck fuel injectors.
The car ran approximately 750 miles on the Phillips fuel before en-
countering operational problems. New injectors were installed and after 60
miles of operation and an overnight soak, the new injectors were also stuck.
It seems unlikely that a fuel that the car had run on for 800 miles would
cause new injectors to stick after a single overnight soak. More likely,
something in either one barrel of the fuel or in the vehicle fuel tank was
the cause.
To eliminate either cause, the vehicle fuel tank was drained, removed
from the vehicle and thoroughly cleaned. Water and some biological growth
were found in the drained fuel and in the fuel drum from which the vehicle
had been fueled. It was likely that this growth was what fouled the in-
jectors. The vehicle was refueled with the Gulf Oil Company Gulf Crest un-
leaded fuel used throughout the mileage accumulation part of this project,
except that the sulfur level was adjusted to 0.03 percent. This fuel was
identified as EM-243-F.
E. Test Sequence and Procedure
The test sequence for all eight cars is shown in Table 36. As shown
in the table, the noncatalyst cars received the normal FTP preconditioning.
In this case, the preconditioning consisted of 1 LA-4 driving schedule,
followed by step 1 of the test procedure, an overnight soak. The catalyst
cars with air injection were all operated for 1609 km on the modified AMA
durability route shown in Appendix H prior to an overnight soak. The pro-
totype car with the three-way catalyst was operated for 805 km on this
route prior to an overnight soak with each exhaust configuration. The test
procedures were the same as those used in the other phases of this project
and outlined in Section II of this report.
145
-------
TABLE 36. SULFATE BASELINE TEST SEQUENCE
Preconditioning
Car Procedure
1-3, 1-4, III-7 Normal FTP preconditioning
II-AI, II-BI, II-B6 1000 Miles Modified AMA
IV-4, IV-17 500 Miles Modified AMA
Test Procedure
Step Operation
1 12-20 hour soak
2 1975 FTP (1 sulfate filter, 1 SO2 sample)
3 Idle (5 minutes)
4 SET-7
5 Idle
6 SET-7
7 Idle
8 HWFET
9 Idle
10 SET-7
11 Idle
12 SET-7
Repeat Steps 1 to 12 without any other preconditioning.
Emissions of HC, CO, NOX, CO2, H2S04 and SO2 are to be taken during
all test modes except idle.
F. Test Results
A summary of the sulfate and SO2 test results is given in Table 37.
A listing of the complete test results for each test is contained in
Appendix J. To aid in the comparison of the H2SO4 emissions, Figure 67
contains histograms of the sulfate emissions for each car.
The sulfate emissions from the two noncatalyst cars agree with
sulfate emissions seen on other noncatalyst cars tested at SwRI and at
other laboratories. Cars IIA-1, IIB-1 and IIB-6 all had been tested rather
extensively and their baseline test results are as expected from past tests
Recall that cars IIB-1, IIB-6 were tested using a fuel with 0.04 percent
sulfur. While it is not known if sulfate emissions vary directly with fuel
sulfur content, if it is assumed that they do, the results from cars IIB-1
and IIB-6 can be adjusted to 0.03 percent sulfur fuel. When this is done,
the average SET-7 test sulfate emissions are 6.82 mg/km for car IIB-1 and
23.43 mg/km for car IIB-6. The reasons for the differences in these two
146
-------
TABLE 37. SUMMARY OF SULFATE AND S02 EMISSIONS FROM BASELINE TESTS AT SwRI
EPA Car Number
Make
Model
Model Year
Engine CXD
Catalyst
Test Dates
Percent S in Fuel
FTP
mg/km
H2S04
SO2
Percent of Fuel S
H2S04
S02
Total Recovery
SET-7 (8 tests per, car)
mg/km
H2S04
so2
Percent of fuel S
H2S04
so2
Total Recovery
HWFET
mg/km
H2S04
SO2
Percent of fuel S
H2S04
S02
Total Recovery
1-3
Ford
Granada
1975
35 1W
None
10/23,11/6/75
0.030
1-4
Dodge
Coronet
1975
318
None
10/28-29/75
0.030
IIA-1
Hornet
Sportabout
1975
304
Pelleted
10/7-8/75
0.030
IIB-1
Chevrolet
Impala
1975
350
Pelleted
11/6-7/75
0.0415
IIB-6
Plymouth
Gran Fury
1975
360
Mono.
10/2-3/75
0.0415
III-7
Mercedes
240D
1975
147
None
11/18-19/75
0.23
IV-4
Ford
Pinto
19 7X
140
3 -way
Degussa
10/6-7/75
0.0300
IV- 17
Ford
Pinto
197X
140
3 -way
TWC-9
10/28-29/75
0.030
0.88
66
0.70
81.53
82.23
1.05
73
0.73
76.10
76.83
8.67
38
8.38
57.81
66.19
3.12
109
1.41
74.07
75.48
5.50
88
2.40
58.33
60.73
11.06
338
2.05
96.32
98.36
24.46
34
27.99
61.26
89.25
0.53
53
0.58
90.82
91.40
0.36
55.5
0.41
94.84
95.25
1.68
54.25
1.64
80.12
81.75
16.24
50
21.38
96.57
115.60
9.43
80
6.16
79.42
85.57
32.41
69
21-. 59
69.19
93.57
10.84
303
2.41
102.83
105.24
50.95
34
78.67
79.46
156.26
0.11
52
0.16
121.55
121.71
0.45
65
0.56
120.55
121.11
2.17
50
2.47
87.55
90.02
38.01
36
55.84
81.78
137.62
10.09
58
7.18
62.01
69.19
58.56
62
45.84
73.85
119.68
9.50
326
2.29
120.31
122.60
51.74
35
84.81
87.06
171.87
0.15
50
0.25
129.50
129.75
-------
00
70
60
50
E
J*
x.
& 40
0* 30
CN
BC
20
10
'TEST
~
-
-
Test *
Car
70
60
50
E
$ 4°
^ 30
0
w
CN
33 20
10
™._Q
r
1
2
3
4
5
6
CYCLE TEST
FTP
7
SET-7 8
SET-7 9
HFET 10
SET-7 11
SET-7 12
2 3 "* 5 6 7 8 9 10 11
j 1 i i i
«b^
12 1 2 3 "t 5 6 7
1-3
^^H
•M
—
IHMI
n
^^
^•i
CYCLE
FTP
SET-7
SET-7
HFET
SET-7
SET-7
|— f~\ — | — |
8 9 10 11 12
1-4
rTTTTTl
M\
rr
I i
—
"H
1 2 3 i* 5
6
11 JTTTfkfflf
789 10 11 12 123 U56 78 9 10 11 12
IIA-1 IIB-1
^^
— -
—
—i
—
^
^j | || i ii i i i ii
Test 1 23". 5 6789 10 11 12 1 23«»5678 9 10 11 12
Car IIB-6 III-7
123U5 67 89 10 11 12 1231* 567891011 12
IV-4 IV-17
FIGURE 67. SULFATE EMISSIONS FOR BASELINE TEST SEQUENCE FROM EIGHT BASELINE CARS
-------
cars with similar emissions systems are fully discussed in Section IV of
this report.
The test results from car IV-4 are of interest since this car is a 197X
Ford Pinto equipped with an experimental fuel injection system together with
a Degussa three-way catalyst followed by an air injected oxidation catalyst.
This system would appear to offer the possibility of high sulfate emissions.
Examination of the data contained in Table J-6 shows this to be the case,
with an average of 51 rag/km for the SET-7 tests. The total recovery indi-
cates that a great deal of storage must take place at some operating con-
ditions. The stored sulfur appears to have been given up during the SET-7
and PET tests, since the total recovery (which starts at almost 200 percent)
decreased toward 100 percent with each successive SET-7 test.
It is interesting to compare the test results from car IV-4 and car
IV-17 since these are both the same car but with different catalyst systems.
Car IV-17 was equipped with an Engelhard TWC-9 three-way catalyst and no
air injection. A comparison of both systems in Table 37 shows significantly
lower sulfate emissions levels for the car with the TWC-9 catalyst; for
example, 0.11 mg/km H2S04 for the TWC-9 catalyst versus 50.95 mg/km H2SO4
for the Degussa catalyst car for an average SET-7. It has been shown in a
tightly controlled fuel-air ratio near stocihometric produces almost no sul-
fates.'16) it is reasonable to conclude, therefore, that the high sulfate
emissions from car IV-4 are probably due to the air injected-oxidation
catalyst downstream of the three-way catalyst.
The diesel car was a special case. The diesel car tested converted
approximately the same percentage of fuel sulfur to sulfates as did the non
catalyst cars and non air-injected catalyst cars. However, because of the
high level of sulfur in the diesel fuel (average of 0.23 versus 0.03 weight
percent for gasoline used in most of the baseline) the sulfate emissions in
mg/km were similar to the air-injected catalyst cars.
No attempt has been made to rank order the sulfate emissions of these
cars or to otherwise statistically analyze the test results. Since this
was only a small part of the total EPA baseline, it should be analyzed in
the context of the results from all the baseline cars.
One general conclusion seems to be warranted however. It appears that
noncatalyst cars produce the least sulfates and that air-injected catalyst
cars, the most sulfates. The diesel seems to fall at the lower end of the
air-injected catalyst range. The three-way catalyst alone appears to be
capable to attaining sulfate emission levels as low as noncatalyst cars.
149
-------
LIST OF REFERENCES
1. Moran, J. B., Manary, O. J., Fay, R. H. and Baldwin, M. J.,
"Development of Particulate Emission Control Techniques for
Spark-Ignition Engines." EPA-OAP Publications APTD-0949
(NTIS PB 207312) July, 1971.
2. Gentel, J. E., Manary, O.J. and Valenta, J. C.,"Characterization
of Particulates and other Nonregulated Emissions From Mobile
Sources and the Effect of Exhaust Emissions Control Devices on
These Emissions." EPA OAWP Publication APTD-1567, March, 1973.
3. Pierson, W. R., Hammerle, R. H. and Kummer, J. T., "Sulfuric
Acid Aerosol Emissions from Catalyst-Equipped Engines." SAE
Paper 740287 presented at SAE Automotive Engineering Congress,
Detroit, February, 1974.
4. EPA Contract 68-03-0497 "An Assessment of Sulfate Emission Control
Technology." Exxon Research and Engineering Company, contractor.
5. Bradow, R. L. , Carpenter, D. A., et al."Sulfate Emissions from
Catalyst and Non-Catalyst Equipped Automobiles." SAE Paper
740528, October, 1974.
6. EPA Contract 68-02-1275 "Protocol to Characterize Gaseous Emissions
as a Function of Fuel and Additives Composition - Prototype Vehicles."
Southwest Research Institute, contractor.
7. Bradow, R. L. and Moran, J. B., "Sulfate Emissions from Catalyst
Cars: A Review." SAE Paper 750090, February, 1975.
8. Dietzmann, Harry. E., "Protocol to Characterize Gaseous Emissions
as a Function of Fuel and Additives Composition." Final report EPA-
600/2-75-048, September, 1975
9. Begeman, C. R., Jackson, M. W. and Nebel, G. J., "Sulfate Emissions
from Catalyst-Equipped Automobiles." SAE Paper 741060, October, 1974.
10. Somers, J. H., Garbe, R., Fett, C. E. and Baines, T. M., "Automotive
Sulfate Emissions, A Baseline Study." To be presented at the
American Chemical Society Meeting, San Francisco, California, August,
1976.
11. EPA Contract 68-02-1777 "Characterization of Diesel Gaseous and Par-
ticulate Emissions." Southwest Research Institute, contractor.
12. Beltyer, M. , Campion, R. J., Harlan, J. and Hochhauser, A. M.,
"The Conversion of SO2 Over Automotive Oxidation Catalyst." SAE
Paper 750095, February, 1975.
13. Hammerle, R. H. and Mikkor, M., "Some Phenomena Which Control Sulfuric
Acid Emission from Automotive Catalysts." SAE Paper 750097, February,
1975.
151
-------
LIST OF REFERENCES (cont'd)
14. Federal Register Vol. 38, Number 124, Thursday, June 28, 1973,
Paragraph 85.075-28.
15. Moran, J. B., "Issue Paper: Estimated Public Health Impact as a
Result of Equipping Light-Duty Motor Vehicles with Oxidation
Catalysts .""EPA, January 31, 1975.
16. Cohn, J. G~ , Mannion, W. A., Thomson, C. E. and Hansel, J. G.,
"Effect of Three Way Conversion Catalyst Operation on the Chemical
State of Automotive Sulfur Emissions." SAE Paper 750096, February,
1975.
152
-------
APPENDIX A
SPEED VERSUS TIME LISTING OF SET-7
DRIVING CYCLE
-------
EPA SULFATE 7 DRIVING CYCLE
PAGE 1 OF 7
CYCLE DIST
AVG SPEED
13.51 MI
34.78 MPH
SEC MPH
SEC
MPH
SEC
MPH
SEC MPH
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
IB
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.60
4.50
7.20
9.70
11.70
13.30
14.30
14.90
15.00
15.70
16.20
15.40
14.70
14.70
15.00
15.00
14.90
13.90
11.60
10.00
10.00
10.00
10.00
10.70
12.20
13.50
14.50
14.80
15.00
15.20
15.50
15.00
15.00
15.20
15.10
15.80
17.00
18.60
20.20
21.60
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
dl
b2
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
23.10
24.50
26.00
27.60
28.80
29.60
31.50
32.50
32.50
31.20
29.50
29.10
29.40
30.80
30.80
30.80
30.70
30.70
30.70
29.70
28.80
27.20
25.00
22.50
20.50
19.30
19.30
19.50
20.70
21.30
20.60
20.10
20.00
20.30
20.10
20.00
20.40
21.10
22.20
23.40
24.50
25,50
26.60
27.70
28.70
29.50
30.80
30.60
30.40
29.90
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
29.10
28.70
29.60
30.30
30.70
30.00
29.40
27.80
25.60
25.00
25.00
24.80
23.50
23.00
23.00
23.60
24.00
25.00
26.30
27.30
28.30
29.30
29,90
30.40
31.90
32,40
32.40
32.00
31.60
31.00
29.60
28.90
27.80
26.30
24.40
22.10
19.70
17.40
15.80
15.00
15.00
15.00
15.10
16.10
17.40
18.60
19.70
20.00
20.50
20.00
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
20.00
19.80
20.00
19.60
18.10
15.70
12.60
10.30
10.00
9.50
9.70
10.00
10.00
10.00
10.00
10.50
11.80
13.60
15.20
16.80
18.40
19.60
20.00
20.20
20.00
19,80
20.00
19.50
18.20
16.20
13.50
10.90
10.00
10.00
9.70
10.00
10.30
10.30
10.00
10.10
10.60
11.60
12.90
14.00
15.10
16.20
17.30
18.40
19.30
19.90
A-2
-------
EPA SULFATE 7 DRIVING CYCLE
PAGE 2 OF 7
SEC MPH SEC MPH SEC MPH SEC MPH
201 20.00 251 56.00 301 46.00 351 51.10
202 20.00 252 56.50 302 46.90 352 50.20
203 20.00 253 56.50 303 48.00 353 49.80
204 20.40 254 56.30 304 49.00 354 49.50
205 21.40 255 56.00 305 49.90 355 49.50
206 22.70 256 55.50 306 50.90 356 49.40
207 24.60 257 55.20 307 51.90 357 49.60
208 26.50 258 55.00 308 52.90 358 49.80
209 28.20 259 54.80 309 53.80 359 50.00
210 29.80 260 54.50 310 54.50 360 50.00
211 31.50 261 54.20 311 54.90 361 50.20
212 33.20 262 53.90 312 55.20 362 50.40
213 34.90 263 54.00 313 55.00 363 50.30
214 36.70 264 54.50 314 54.70 364 50.00
215 38.20 265 54.50 315 54.30 J65 49.70
216 39.30 266 52.80 316 53.50 366 49.00
217 40.00 267 50.40 317 53.00 367 47.80
218 40.70 268 50.00 318 52.70 368 46.20
219 41.00 269 49.60 319 53.30 369 44.00
220 41.00 270 49.70 320 53.70 370 41.00
221 41.00 271 50.00 321 53.70 371 38.00
222 41.00 272 50.50 322 53.70 372 34.70
223 40.00 273 50.30 323 54.50 373 31.40
224 39.50 274 50.00 324 55.00 374 28.10
225 39.30 275 49.30 325 55.00 375 24.80
226 39.60 276 47.80 326 55.20 376 21.80
227 39.90 277 45.30 327 55.40 377 20.50
228 40.00 278 42.30 328 55.50 378 20.00
229 40.40 279 40.20 329 55.60 379 20.00
SJ ll.ll 280 40^ 330 55.60 380 20.00
231 42.20 281 39.80 331 55.50 381 9.70
232 43.60 282 39.70 332 55.40 382 18.50
233 44.90 283 40.00 333 55.30 383 6.30
,, _,, '>*,. /.« t>A ^14 RR.30 384 U.cU
— •"*•* T~T • ^ v fc- -—• •**• ,»w_— r" f" "1 rt
234 46.20 284 40,20 334 55.30
235 47:45 285 40.50 335 55.30 385 0.60
236 48.60 286 42.40 J36 55.60 386 0.00
237 49.80 287 44.20 337 55.90 387 10.00
238 51.00 288 45.00 338 56.10 388 9.90
239 52 30 289 45.50 339 56.10 389 9.60
-° »:* 2 2:2! ll\ IS:!! S? !:3
— 'V .»*J • T I/ fc.*w - — -<« •- ^ 1 /i
241 54.30 291 45.40 -341 56.10
242 54 QO 292 45.00 342 55.90 392 6.TO
243 55 30 293 45.00 343 55.60 393 5.60
244 55*50 294 44.80 344 55.30 394 5.00
245 55*SO 295 44.00 345 55.10 395 4.80
246 55^0 296 43.80 346 54.90 396 4.30
247 55^0 297 43.50 347 54.70 397 4.00
248 55.00 298 44.10 348 54.10 398 4.50
249 55.00 299 44.60 349 53.30 399 5.00
250 55.00 300 45.30 350 52.20 400 5.00
A-3
-------
EPA SULFATE 7 DRIVING CYCLE
PAGE 3 OF 7
SEC
MPH
SEC
MPH
SEC MPH
SEC
MPH
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
444
445
446
447
448
449
450
5.00
5.00
5.40
7.20
9.00
9.80
9.70
9. SO
9.20
9.30
9.50
9.90
10.20
10.40
10.70
12.10
13.50
14.70
15.00
15.00
15.20
15.00
14.70
15.00
15.00
15.10
16.20
17,60
18.90
19.90
20.00
20.00
20.00
20.00
19.80
18.80
16.80
13.80
10.50
7.20
4.50
1.80
0.0
0.0
0.0
0,0
0.0
0.20
2.20
5.00
451
452
453
454
455
456
457
458
459
460
461
462
463
464
465
466
467
468
469
470
471
472
473
474
475
476
477
478
479
480
481
482
483
484
485
486
487
488
489
490
491
492
493
494
495
496
497
498
499
500
7.80
10,20
12.10
13.50
14.50
15.20
15.00
14.80
14.80
14.80
14.80
15.00
15.10
15.20
15.30
15.30
16.70
18.60
20.70
22.60
24,30
24.50
24.80
25.00
25.40
26.00
26.20
26.10
25.50
25.20
25.00
24.30
22.60
19.60
16.40
13.10
10.20
9.70
9.40
9.00
8.80
8.50
8.10
8.40
8.80
9.10
9.00
8.90
8.90
9,50
501
502
503
504
505
506
507
508
509
510
511
512
513
514
515
516
517
S18
519
520
521
522
523
524
525
526
527
528
529
530
531
532
533
534
535
536
537
538
539
540
541
542
543
544
545
546
547
548
549
550
9,40
9.00
7.10
5.20
5,00
5.00
5.00
5.00
5,00
5.00
5.00
5.00
5.00
4.40
3.00
1.00
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.50
3.30
6.30
9,40
12.70
16.00
19.30
22.60
25.90
29.00
32.00
34.50
35.50
35.30
35.30
35.30
35.30
35.20
35.10
35.00
35.00
34.80
33.90
551
552
553
554
555
556
557
558
559
560
561
562
563
564
565
566
567
568
569
570
571
572
573
574
575
576
577
578
579
580
581
582
583
584
585
586
587
588
589
590
591
592
593
594
595
596
597
598
599
600
32.30
29.80
26.80
23.50
20.20
17.00
14.00
11.00
9.80
9.60
9.50
9.50
9.50
9.50
9.60
9.90
10.40
11.40
12.50
13.50
14.50
15.20
15.60
15.80
15.50
15.50
15.30
15.50
15.00
14.30
11.30
8.00
5.00
b.OO
5.00
5.00
5.00
5.10
6.10
7.40
8.60
9.70
10.00
10.20
10.10
9.90
9.80
9.80
9.90
9.90
A-4
-------
t-PA SULFATE 7 DRIVING CYCLE
PAGE 4 OF 7
SEC
MPH
601
602
603
604
605
606
607
608
609
610
611
612
613
614
615
616
617
618
619
620
621
622
623
624
625
626
627
628
629
630
631
632
633
634
635
636
637
638
639
640
641
642
643
644
645
646
647
648
649
650
9.30
8.00
6.30
5.00
5.00
5.20
5.40
5.10
5.00
5.90
8.10
10.20
12.30
14.30
15.30
16.00
16.60
16.50
16.00
16.10
lb.80
15.20
14.90
15.10
15.10
14.90
14.50
13.60
12.30
10.80
10.00
10.10
10.60
10.90
10.80
9.90
9.20
9.70
10.00
10.40
11.30
12.70
14.00
15.20
16.50
17.80
19.00
19.80
20.20
20.10
SEC
MPH
651
652
653
654
655
b56
657
658
659
660
661
662
663
664
665
666
667
668
669
670
671
672
673
674
675
b76
677
678
679
680
b81
682
683
684
685
686
687
b88
689
690
691
692
693
694
695
696
697
698
699
700
20.00
19.80
19.70
19.70
19.90
19.90
20.00
20.20
20.00
20.80
22.10
24.00
26.40
28.70
30.80
32.90
35.00
37.10
39.30
41.50
43.20
44.40
45.00
45.30
45.60
45.80
45.70
45.10
44.50
44.00
43.90
44.10
44.60
45.00
45.10
45.00
44.90
44.30
43.30
41.90
40.50
39.80
39.70
40.00
40.00
40.00
40.00
40.00
40.10
40.30
SEC
MPH
SEC
MPH
701
702
703
704
705
706
707
708
709
710
711
712
713
714
715
716
717
718
719
720
721
722
723
724
725
726
727
728
729
730
731
732
733
734
735
736
737
738
739
740
741
742
743
744
745
746
747
748
749
750
41.00
42.40
43.80
44.90
45.10
45.40
46.10
46.70
47.10
47.10
47.00
46.30
45.60
45.20
44.90
45.00
45.10
45.40
45.80
46.80
48.10
49.20
50.30
51.50
52.60
53.70
54.60
55.00
55.40
55.80
55.90
56.50
57.00
57.00
57.00
56.70
55.80
54.90
54.20
53.80
53.30
52.80
52.70
53.00
54.00
55.00
55.80
55.90
55.90
56.00
751
752
753
754
755
756
757
758
759
760
761
762
763
764
765
766
767
768
769
770
771
772
773
774
775
776
777
778
779
780
781
782
783
784
785
786
787
788
789
790
791
792
793
794
795
796
797
798
799
800
56.00
56.00
56.00
55.50
55.00
55.00
55.00
55.00
54.70
54.80
55,00
55.00
54.90
54.50
53.70
52.60
51.30
50.30
49.70
49.50
49.20
48.90
48.70
48.50
48.70
48.80
48.90
50.00
50.10
50.30
50.30
50.00
50.00
50.20
50.10
50.20
50.60
51.20
51.90
52.50
53.10
53.80
54.40
54.80
55.00
55.50
55.70
56.00
56.30
56.50
A-5
-------
EPA SULFATE 7 DRIVING CYCLE
PAGE 5 OF 7
SEC MPH SEC MPH SEC MPH SEC MPH
801 56.20 851 45.20 901 19.70 951 18.70
802 56.00 852 45.00 902 19.40 952 20.60
803 55.50 853 45.00 903 19.70 953 22.30
804 55.00 854 45.00 904 19.90 954 24.00
805 55.00 855 45.00 905 20.00 955 25.70
806 55.00 656 45.00 906 20.10 956 27.60
807 54.50 657 45.00 907 20.90 957 29.00
808 54.70 658 45.00 908 21.90 958 29.90
809 55.00 859 45.00 909 22.90 959 30.20
810 55.50 660 45.00 910 23.90 960 30.50
811 56.00 661 44.90 911 24.80 961 30.80
812 56.50 662 44.50 912 25.30 962 30.60
813 56.00 863 43.60 913 25.60 963 30.80
814 55.50 864 42.30 914 25.40 964 30.60
815 55.00 865 40.90 915 25.30 965 30.40
816 55.00 866 40.00 916 25.20 966 30.20
817 55.00 867 40.00 917 25.00 967 30.10
818 55.00 868 39.70 918 25.00 968 30.20
819 55.00 869 39.40 919 25.00 969 30.30
820 55.00 870 39.30 920 24.80 970 31.20
821 55.00 871 39.00 921 23.90 971 32.30
822 55.00 872 39.50 922 22.30 972 33.20
823 55.00 873 39.70 923 20.50 973 34.30
824 54.70 874 40.00 924 20.00 974 34.90
825 54.00 875 39.50 925 20.00 975 35.20
826 52.90 876 37.70 926 20.00 976 35.50
827 51.50 877 35,30 927 20.00 977 35.20
828 50.30 878 35.00 928 20.00 978 35.10
829 50.00 879 35.00 929 19.70 979 35.00
830 49.70 880 35.00 930 19.50 980 35,00
831 50.00 881 35.00 931 19.30 981 34.80
832 51.30 882 35.00 932 19.10 982 34.20
833 51.70 883 35.00 933 19.30 983 33.00
834 52.00 884 35.00 934 19.50 984 31.50
835 52.00 885 35.00 935 19.70 985 30.20
836 51.70 886 34.80 936 19.90 986 30.00
837 51.40 887 34.60 937 19.10 987 29.80
838 51.20 888 33.00 938 17.50 988 29.60
839 51.00 889 30.00 939 15.60 989 29.80
840 50.70 890 27.50 940 15.00 990 29.60
841 50.30 891 25.00 941 15.00 991 29.80
842 50.00 892 25.00 942 14.70 992 29.60
843 50.20 893 25.30 943 14.30 993 29.40
844 50.50 894 25.50 944 14.00 994 29.80
845 50.30 895 25.20 945 14.20 995 30.30
846 50.10 896 24.90 946 14.50 996 30.90
847 50.00 697 24.40 947 14.70 997 31.80
848 49.70 898 23.10 948 15.00 998 32.90
849 49.20 899 21.30 949 15.60 999 33.90
850 47.30 900 20.00 950 16.90 1000 34.90
A-6
-------
EPA SULFATE 7 DRIVING CYCLE
PAGE 6 OF 7
SEC
MPH
SEC
MPH
SEC MPH
SEC MPH
1001
1002
1003
1004
1005
1006
1007
1008
1009
1010
1011
1012
1013
1014
1015
1016
1017
1018
1019
1020
1021
1022
1023
1024
1025
1026
1027
1028
1029
1030
1031
1032
1033
1034
1035
1036
1037
1038
1039
1040
1041
1042
1043
1044
1045
1046
1047
1048
1049
1050
35.90
36.90
37.90
38.80
39.50
40.50
41.00
41.40
41.60
41.30
41.00
40.70
40.50
40.40
40.30
40.20
41.90
43.70
45.00
45.SO
46.00
46.40
46.30
46.10
45.90
45.70
45.50
45.30
45.10
45.00
44.90
44.40
43.60
42.40
40.80
38.80
36.90
35.50
35.00
35.00
35.00
35.00
35.00
35.00
3b.lO
36.30
37.70
39.10
40.00
40.50
1051
1052
1053
1054
1055
1056
1057
1058
1059
1060
1061
1062
1063
1064
1065
1066
1067
1068
1069
1070
1071
1072
1073
1074
1075
1076
1077
1078
1079
1080
1081
1082
1083
1064
1085
1086
1087
1088
1089
1090
1091
1092
1093
1094
1095
1096
1097
1098
1099
1100
40.70
40.80
40.90
40.70
40.50
40.70
40.80
40.60
40.80
40.80
40.90
42.50
44.00
45.00
45.00
45.50
46.00
46.30
46.60
46.30
46.00
45.70
45.40
45.10
44.90
44.70
44.50
44.30
44.50
44.60
44.80
45.00
45.00
45.10
45.80
47.00
48.40
49.60
50.90
52.10
53.40
54,40
55.00
55.50
56.00
56.30
56.50
56.30
56.00
55.30
1101
1102
1103
1104
1105
1106
1107
1108
1109
1110
1111
1112
1113
1114
1115
1116
1117
1118
1119
1120
1121
1122
1123
1124
1125
1126
1127
1128
1129
1130
1131
1132
1133
1134
1135
1136
1137
1138
1139
1140
1141
1142
1143
1144
1145
1146
1147
1148
1149
1150
55.50
55.30
55.10
54.90
54.70
54.50
54.30
54.10
53.90
53.70
53.50
53.40
53.30
53.20
53.30
53.40
53.60
53.80
54.00
54.20
54.30
54.30
54.40
54.60
54.80
54.90
55.00
54.80
54.10
52.60
50.80
50.20
49.90
50.10
50.00
50.10
50.20
50.30
50.10
50.00
50.00
50.00
49.90
49.70
49.90
50.00
50.30
50.90
51.60
52.30
1151
1152
1153
1154
1155
1156
1157
1158
1159
1160
1161
1162
1163
1164
1165
1166
1167
1168
1169
1170
1171
1172
1173
1174
1175
1176
1177
1178
1179
1180
1181
1182
1183
1184
1185
1186
1187
1188
1189
1190
1191
1192
1193
1194
1195
1196
1197
1198
1199
1200
52.90
S3. 60
54.30
54.80
55.20
55.50
55.70
55.90
56.00
56.10
55.90
55.80
55.60
55.40
55.20
55.10
55.20
55.30
55.20
55.10
55.10
55.00
55.00
55.00
54.90
54.70
54.50
54.60
54.60
54.70
54.80
54.90
54.80
54.70
54.60
54.70
54.70
54.80
54./0
54.60
54.70
55.00
55.00
55.00
55.00
54.90
54.50
53.80
52.70
51.40
A-7
-------
EPA SULFATE 7 DRIVING CYCLE
PAGE 7 OF 7
SEC
MPH
SEC
MPH
SEC
MPH
SEC
MPH
1201
1202
1203
1204
1205
1206
1207
1208
1209
1210
1211
1212
1213
1214
1215
1216
1217
1216
1219
1220
1221
1222
1223
1224
1225
1226
1227
1226
1229
1230
1231
1232
1233
1234
1235
1236
1237
1238
1239
1240
1241
1242
1243
1244
1245
1246
1247
1248
1249
1250
50.40
49.60
49.00
48.30
48.00
47.90
46.00
48.30
48.30
48.30
48.30
48.70
50.10
50.30
50.40
50.40
50.10
49.90
50.00
50.00
50.00
50.20
50.50
50.90
51.00
50.70
50.90
50.80
51.60
52.30
53.00
53.70
54.40
54.90
55.10
55.40
56.10
56.30
56.30
56.10
56.20
56.30
56.00
56.00
55.70
55.20
55.00
55.00
55.10
55.20
1251
1252
12??
1254
1255
1256
1257
1258
1259
1260
1261
1262
1263
1264
1265
1266
1267
1268
1269
1270
1271
1272
1273
1274
1275
1276
1277
1278
1279
1280
1281
1282
1283
1284
1285
1286
1287
1288
1289
1290
1291
1292
1293
1294
1295
1296
1297
1298
1299
1300
55.00
54.80
54.50
54.00
53.70
53.80
53.70
53.90
54.30
54.70
55.00
55.00
54.70
54.50
54,80
54.90
55.00
55.10
55.10
55.70
56.30
56.60
56.80
56.50
56.10
55.70
55.60
55.60
55.60
55.30
55.00
54.90
54.60
54.10
53.30
52.30
51.20
50.40
50.00
49.70
49.50
49.00
48.30
47.80
48.00
48,20
48.20
<+8.30
48.70
49.40
1301
1302
1303
1304
1305
1306
1307
1308
1309
1310
1311
1312
1313
1314
1315
1316
1317
1318
1319
1320
1321
1322
1323
1324
1325
1326
1327
1328
1329
1330
1331
1332
1333
1334
1335
1336
1337
1338
1339
1340
1341
1342
1343
1344
1345
1346
1347
1346
1349
1350
49.20
49.00
49.20
49.10
49.10
49.10
49.60
49.90
50.30
51.10
51.90
52.70
53.60
54.40
54.90
55.10
55.30
55.70
56.00
56.20
56.00
55.50
55.70
55.70
55.70
55.70
55.50
55.70
55.90
56.20
56.60
56.70
56.30
56.00
56.00
55.80
55.70
55.50
55.30
55.00
55.20
55.30
55.20
55.20
55.00
54.80
54.70
54.50
54.00
53.60
1351
1352
1353
1354
1355
1356
1357
1358
1359
1360
1361
1362
1363
1364
1365
1366
1367
1366
1369
1370
1371
1372
1373
1374
1375
1376
1377
1378
1379
1380
1381
1382
1383
1384
1385
1386
1387
1388
1389
1390
1391
1392
1393
1394
1395
1396
1397
1398
53.90
54.30
54.50
54.40
54.40
54.40
54.20
54.00
53.60
53.10
53.50
53.40
53.40
53.40
53.00
51.00
48.00
45.00
42.00
39.00
36.00
32.80
29.50
26.20
22.90
19.60
16.60
14.00
12.00
11.00
10.00
10.00
10.00
8.80
6.70
4.60
2.50
1.50
0.90
0.0
o.o
0.0
0.0
0.0
0.0
0.0
0.0
o.o
A-8
-------
APPENDIX B
BCA-SULFATE PROCEDURE
AND INTERFERENCE CHECKS
-------
DETERMINATION OF SOLUBLE SUL.FATES: BARIUM CHLORANILATE METHOD
(Adapted from a procedure supplied to SwRI by EPA, ORD developed
by Dr. L. Teajeda, EPA, RTF, March, '74.)*
1. Principle and Applicability
1. 1 This method is for the determination of watersoluble sulfates
from diluted automobile exhausts collected on Fluoropore filters.
This method is quite general and may be used for trace sulfate
analysis of any sample from which sulfates can be leached out
with water or aqueous alcoholic solutions. There are interfer-
ences from some anions and methods for minimizing or elimi-
nating these are still being worked out. The method as written
is applicable to sulfate analysis of exhaust emissions from cars
run on non-leaded gasoline.
1. 2 Auto exhaust is mixed with air in a dilution tunnel and sampled
through isokinetic probes. SO3 reacts with available moisture in
the exhaust to form H2SO^ aerosols and is trapped on Fluoropore**
filters with 0. 50 micron pore size. The sulfate is extracted from
the filter with 60/40 isopropyl alcohol/water solution (i. e. 60 ml
isopropyl alcohol (IPA) + 40 ml water). The extract is fed by a high
pressure liquid (chromatographic) pump through a column of cation
exchange resin to remove cationic interferences and then through a
column of solid barium chloranilate where BaSO4 precipitates out.
An equivalent amount of reddish colored acid chloranilate ion is re-
leased ' and is measured colorimetrically at 310 nm3' . To use
this method for aqueous sulfate solutions, four parts by volume of
the solution are mixed with six parts of IPA before feeding through
the columns. Manual method or a dynamic sampling system can be
used.
2. Range and Sensitivity
Working concentration range and sensitivity depend on sample size.
A sensitivity better than 0. 5 i^g SO^ per ml in 60% IPA and working
range of 0-25M.g/ml were obtained using a 0. 5 ml external sampling
loop injection system in conjunction with a du Pont liquid chromato-
graph UV detector. Sensitivity may be further increased by increasing
the alcohol content of the solvent, as this would further decrease the
solubility of BaSO^ and barium chloranilate. This, however, requires
a much tighter control of the water/IPA ratio in the sample and in the
mobile phase. To minimize spurious results arising from water im-
balance, it is recommended that both the extracting solvent and the
mobile phase for analytical runs be taken from the same stock solution.
Sample size as large as 1. 5 ml has been successfully used.
* The reader is advised to obtain the most recent version of the EPA BCA
method from EPA, Ann Arbor, Michigan.
**Registered trade mark. Obtainable from Millipore Corp. , Bedford, Mass.
B-2
-------
3. Interferences
Cations interfere negatively by reacting with the acid chloranilate to
form insoluble salts. These, however, are conveniently removed by
passing the sample through a cation exchange resin in the hydrogen form.
Some anions such as Cl~. Br", F~. PO^ interfere positively l>y
precipitating out as barium salts with subsequent release of acid
chloranilate ions. Some buffer systems ~ are reported to mini-
mize anion interference. These systems are being investigated
for possible incorporation in the present procedure. Alternative
clean-up methods are also under consideration. Fortunately, for
non-leaded exhaust samples collected on filters, ionic interference is
minimal. Interference from aromatic compounds is minimized by
using a 300 nm cut-off filter in the optical path of the detector system
or by using a spectrophotometer with narrow (i. e. 2. Onm) slit width.
4. Stability _
4. 1 Sulfuric acid standards containing 10 and 100/tg SO4 /ml in 60%
IPA are stable for at least one month when stored in tightly capped
volumetric flask which has been cleaned with 1:1 nitric acid and
copiously rinsed with deionized water. Alternative storage con-
tainers are capped polyethylene reagent bottles.
4. 2 For samples known to contain cations, it is advisable to remove
these cations by external treatment with cation exhange resin prior
to injection into the sampling loop.
4. 3 As the barium chloranilate column is depleted each time sulfate
samples are fed through, it is good practice to run sulfuric acid
standards before and after the sample.
4.4 Exposure of alcoholic samples, standards, and solvents to the
atmosphere should be minimized, since IPA solution picks up
atmospheric water on standing.
5. Apparatus
A schematic of the principal components of the set-up is shown in
Figure B- 1.
5. 1 Hardware
a. Reservoir (LR) for the solvent (60% IPA).
b. High pressure (HPS) capable for delivery liquid at flow
rates of up to 3 ml/min at pressures as high as 1000 psi.
B-3
-------
c. Flow or pressure controller (FC).
d. High pressure switching valve (SV) equipped with inter-
changeable external loop (L).
e. Ultraviolet detector (D) equipped with appropriate filters
to isolate a narrow band of radiation centered at 310nm.
f. Recorder to monitor detector response.
g. Cation exchange resin column (CX) - standard 1/4" O. D. x
10" stainless steel column packed with analytical grade
Dowex 50W-X2 cation exchange resin in hydrogen form.
h. Barium chloranilate column (BC) - standard 1/4" O. D. x
5" stainless steel column packed with barium chloranilate.
5. 2 Principle of Operation
Solvent (60% IPA) in reservoir (LR) is continuously fed through
cation exchange (CX) and barium chloranilate columns at flow
rates of about 3 ml/min. by a high pressure source (HPS). Back-
ground absorbance is continuously measured by a UV detector (D)
at 310 nm and visually monitored on a strip chart recorder. A
switching valve (SV) is used for filling the external sampling loop
(L) with samples injecting the sample into the columns. Samples
may be introduced into the sampling loop by syringe injection.
At CX cations are removed and at BC, color reaction takes place.
The BaSC>4 precipitate is retained in the column while the acid
chloranilate is carried by the solvent through the detector system
for colorimetric measurement.
For manual operation SV may be retained or replaced by a simi-
lar switching valve equipped with an extended handle for manual
switching.
6. Reagents
6. 1 Isopropyl alcohol (IPA) spectroquality grade or equivalent.
Volatile solvent, safety class IB.
6. 2 60% IPA. Add four parts water to six parts IPA by volume.
Store in tightly capped bottle. About three liters are needed
for a 12 hour operation.
6. 3 Barium chloranilate, suitable for sulfate analysis.
6.4 Dowex 50W-X2 cation exchange resin, hydrogen form, 100-200
mesh.
6. 5 Hydrochloric acid (4N). Add 30 ml concentrated hydrochloric
acid to 60 ml deionized water. (Danger, strong acid)
6. 6 Standard sulfuric acid (IN). Dilute to the mark 2. 8 ml of con-
centrated sulfuric acid with deionized distilled water in a liter
volumetric flask which has been washed in 1:1 nitric acid and
copiously rainsed with deionized distilled water. Standardized
against accurately weighed sodium carbonate to get exact nor-
mality. 0. IN H2SO4 is equivalent to 4800yw,g/SO4=/ml. (Danger,
strong acid.)
B-4
-------
6.7 Standard sulfate solution (1000/
-------
7. 2 Priming System for Analytical Run
Connect the cation exchange and barium chloranilate columns with
1/4" union packed with glass wool as shown in Figure 1. Fill sol-
vent reservoir (LR) with 60% IPA, activate liquid pump, detector,
recorder, switching valve, sampler, and peristalic pump. Allow
to cycle normally to clean out all components. For this initial
operation, dip the sampling probe in at least 100 ml of 60% IPA.
Set liquid flow rate at about 3 ml/min. Let run for at least 30
minutes. Deactivate switching valve, sampler, and peristaltic
pump. Leave other components in operating mode. When back-
ground is stable at attenuation of .01 absorbance units full scale,
system is ready for analysis.
7. 3 Preparation of Calibration Standards
Either sulfuric acid or sodium sulfate standards may be used.
Add 200 ml of 0. 1 N H2SO aqueous stock solution to 300 ml
100% IPA in 500 ml volumetric flask. (Note: There is a volume
decrease of about 2. 7% when these proportions of water and IPA
are mixed.) Dilute to the mark with 60% IPA. This is equivalent
to 1, 920 g SO4=/ml in 60% IPA. Prepare from this alcoholic
stock solution calibration standards in the range of 0. 5-25 g
SO4=/ml by dilution of appropriate aliquots with 60% IPA.
7.4 Extraction of Soluble Sulfates from Fluoropore Filters Place
filter in one oz. polyethylene bottle, add 10 ml 60% IPA and
cap tightly. Shake until filter collapses and is completely im-
mersed in liquid. Let stand overnight.
7. 5 Analysis
Set Instrument in operating mode, remove sampling probe from
holder, and dip in 100 ml 60% IPA. Let it run at flow rate of 3
until stable background is obtained, then remount sampling probe to
holder. In the meantime, fill sample cuvettes with sample extract
and blank solutions (60% IPA) and place on turntable. Sampling
pattern is blank, blank, samplg, blank, blank at the rate of about
six minutes per sample or blank. Blanks are used to wash out
system between samples and minimize sample overlap. One blank
between samples is adequate for dilute samples. (See also 5. 2.)
A series of standards (see 7. 3) is run, preferably before sample
runs and calibration curve, area vs. concentration, is plotted. A
control standard may also be placed after every ten samples as a
quality check on the stability of the system.
8. Calculations
Calculate the concentration of sulfate.aSyixg 804 /ml using the calibration
curve. Total soluble sulfates SO 4 _ in filter is then given by:
SO4= j. = (/xg SO4=/m) x Vo x d
where: Vo = total volume of original sample extract
d = dilution factor
B-6
-------
Example: Suppose 10 ml 60% IPA was used to oxt rai-t !lu> soluhlo
sulfates in the filter and that 2 ml of this was diluted further to o nil
with 60% IPA to bring detector response within calibration range.
Suppose that the concentration of the diluted sample was found to be
5 ug/ml. Then, _ 6
S04 F= (5/tg/ml) x 10 mix* = I
B-7
-------
References
1. R. J. Bertolacini and J. E. Barney II, "Colorimetric Determi-
nation of Sulfate with Barium Chloranilate, " Anal. Chem. 29,
281 (1957).
2. Ibid, "Ultraviolet Spectrophomometric Determination of Sulfate,
Chloride and Fluoride with Chloranilic Acid," Anal. Chem. 30,
202 (1958).
3. H. N. S. Schafer, "An Improved Spectrophotometric Method for
The Determination of Sulfate with Barium Chloranilate as Applied
to Coal Ash and Related Material s," Anal. Chem. 39, 1719 (1967).
4. S. C. Barton and H. G. McAdie, "An Automated Instrument for
Monitoring Ambient t^SO Aerosol" in Proceedings of the Third
International Clean Air Congress, Dusseldorf, Federal Republic
of Germany, 1973, VDl-Verlag GmbH, 1973, P. C25.
5. M. E. Gales, Jr. , W. H. Kaylor and J. E. Longbotton, "Deter-
mination of Sulfate by Automatic Colorimetric Analysis, " Analyst
93, 97 (1968).
B-8
-------
D
RECORDER
HPS
W
LR
n
BCA
y
TO WASTE
CX
TO WASTE
FIGURE B-l. FLOW SCHEMATIC FOR AUTOMATED SULFATE INSTRUMENT
-------
1/4" UNION
»
H-
o
1/4" TO 1/161' REDUCER
GLASS WOOL PLUG
FIGURE B-2. CONFIGURATION FOR LOADING COLUMN
-------
RESULTS OF STUDIES OF INTERFERENCES
IN BCA SULFATE PROCEDURE
PERFORMED AT SwRI DURING NOVEMBER, 1974
Although a cation exchange column is included as part of the
sampling system, concern has been expressed for the analysis of
sulfate on engines operating on leaded fuel. The Dowex SOW X-2 cation
exchange column has been included to eliminate, or at least reduce, any
lead that might be collected on the filters for sulfate analysis. Since
the efficiency of the cation exchange column may not remove all of the
lead ions it was decided to conduct a series of experiments to determine
how much interference from lead might be expected. These experiments
were conducted with an ion exchange column, which had been used for
about one month on lead free samples.
A working sulfate standard of 23. 93/*g SO^/ml was used to make
comparisons with the various lead blends. Lead nitrate blends were pre-
pared in 60 percent IPA in concentrations of 25. 0, 12. 5, and 5. 0/*-g
Pb++/ml. These solutions were analyzed in the same manner as an ex-
tracted sample and the corresponding peak was calculated as response as
yU-g SO^/ml with Pb++ concentrations ranging from 25 to 5/t.g Pb /ml. It
was apparent that not all of the lead is being removed by the ion exchange
column.
Since lead is generally added to the fuel in the form of a motor mix
containing ethylene dichloride and ethylene dibromide as scavengers, it
was decided to determine if these will produce erroneous results. The
first experiment involved the preparation of three concentrations of chlo-
ride in 60 percent IPA. Sodium chloride was used in the preparation of
the 24. 3, 12. 1 and 4. 8/Jg Cl'/ml. Again, these blends were analyzed
just as a normal sulfate sample and the corresponding peak calculated as
response as/*g/SO=/ml. These results are found in Table 1 and/*g Cl/ml
as a function of response as/*g SO^/ml is shown in Figure 1. The response
as^g SO!/ml varied from 7. 1 to 2. 1 with a range in^ng Cl"/ml of 24. 3 to
5. 0. In comparison with the experiment in lead interference, it was found
that the chloride ions produced some 4-6 time greater interference than
the lead ions alone.
A similar experiment involving the interference of bromide ions was
conducted. Sodium bromide was added to 60 percent IPA in concentrations
31. 1,15. 5 and 6. 2 g Br'/mL These blends were also analyzed according
to the standard barium chloranilate procedure. The range of response as
u.g SO7/ml was from 5. 1 to 1. 9 for the concentrations of Br'tested.
B-ll
-------
Of the three interference species evaluated, it appears that with the
normal barium chloranilate procedure, lead has the least interference and
chloride the greatest. _ A nominal IByi/tg Pb++/ml concentration produced a
response as one/tg SO^/ml. A bromide concentration of 3-6 /*g Br~/ml
provide an equivalent response to one ,ug SO^/ml. The chloride ion con-
centration required to give a response as t*.g SO^/ml ranged from 2-3 g Cl"/tnl.
B-12
-------
TABLE B-l. EFFECT OF LEAD CHLORIDE AND BROMIDE IONS
ON SULFATE RESULTS USING THE BARIUM CHLORANILATE
LIQUID CHROMATOGRAPH PROCEDURE
Response as Response Ratio
Sample Description jj.g SO^/ml jtg Pb^/mlJ jig SO^-f/ml
23. 93 /*g SO~/ml 23. 93
25.0 p.% Pb++/ml 1.71 14.6
12.5 /ig Pb++/ml 0.66 18.9
5.0 we Pb++/ml 0.33 15,1
24. 3 jug Cl'/ml 7.06 3.4
12. 1 ytg Cl'/ml 4. 23 2. 9
4. 8 itg Cl'/ml 2. 12 2. 3
31.1 ^g Br"/ml 5.07 6.1
* 15. 5 /ig Br~/ml 4.04 3.8
6. 2 ug Br-/ml 1. 92 3.2
* These are reasonable levels of Cl and Br that might be expected from
leaded fuel tests.
B-13
-------
da
i—
^
O 5
en ->
to 4
«3
CD
CO
C
o 3
a°
to
CO
0
0
O Chloride
^ Bromide
Lead
10
15 20
Interference/ml
FIGURE B-3. THE EFFECT OF LEAD, CHLORIDE AND BROMIDE
INTERFERENCES IN THE BARIUM CHLORANILATE PROCEDURE
-------
APPENDIX C
SUMMARY OF PULSED FLUORESCENCE
ANALYZER INTERFERENCE CHECKS AND
EXHAUST RECOVERY TESTS
-------
MODEL 40 PULSED FLUORESCENT SO2 ANALYZER INTERFERENCES
The use of the TECO-Model 40 pulsed fluorescent SOz analyzer in
the presence of other exhaust gas components could cause potential
interference problems. The intended use of this instrument will be
in sampling CVS exhaust on a continuous basis. Since the exhaust
will be essentially an air-based sample, the experiments described
are orientated toward this particular application.
CO and CO2 Interferences
Initial CO and COz interference checks were conducted using
a single bottle cart containing eight golden standards named by EPA
Ann Arbor. This group of bottles contained multi-component blends
as well as single component mixtures. All eight bottles contained
nitrogen as a balance gas. The first set of data was obtained using
standard regulators with neophrene diaphragms and teflon tubing. The
results of these tests are found in Table C-l. Response as SO2 ranged
TABLE C-l. MULTICOMPONENT BLENDS OF CO AND CO2/N2
RESPONSE AS SO2 IN MODEL 40 PULSED FLUORESCENT
ANALYZER (NORMAL NEOPHRENE DIAPHRAGM REGULATOR)
Concentration. %* Response as
Test CO CO2 ppm SO2
1 9.58 5.70 15.5
2 - 14.16 10.3
3 - 12.36 16.0
4 - 11.22 16.5
5 5.39 10.46 17.5
6 2.79 13.18 17.0
7 1.39 - 16.5
8 0.48 15.23 17.5
#balance gas N2
from 10. 3 to 17. 5 ppm with no apparent correlation for response as ppm
SO2 and interference concentration. The CO concentrations varied from
0.48 to 9. 58 percent, while the CO2 values ranged from 5.7 to 15.23 per-
cent.
Since it was obvious that something other than a straightforward
single compound interference was involved, additional experiments to de-
termine the extent of other variables that might lead to apparent inter-
ferences were conducted. The first such variable checked was the effect
C-2
-------
of regulator diaphragm type on the response as ppm SC^. Since other
data was previously run and substantial data available for neophrene
regulator diaphragms, it was decided to investigate the response of
several of the previously tested bottles using metal diaphragm regulators
like those used for hydrocarbon span gases. The results of this experi-
ment are found in Table C-2. Although it is difficult to make any defi-
nite conclusions, it was observed that the response as ppm SO 2 for these
same three CO/CC^ bottles was 2. 5 to 3.0 ppm less for the metal dia-
phragm.
TABLE C-2. MULTICOMPONENT BLENDS OF CO AND
RESPONSE AS SO2 IN MODEL 40 PULSED FLUORESCENT
ANALYZER (METAL DIAPHRAGM REGULATOR)
Concentration, %* Response as
Test CO CO2 ppm
1 9.58 5.70 13.0
2 5.39 10.46 14.5
3 0.48 15.23 15.0
*balance gas N2
The next item checked was CO£ in balance zero air. A clean
Tedlar bag was prepared with a double end shut off quick connect and
filled with zero air. The bag sample was then analyzed in the Model
40 SO2 instrument and no response was observed. The bag was then
doped with some pure CO2 to give a CO2 concentration of about 13 per-
cent. The bag was then run in the SO2 instrument and still no response
was observed. As a result of this experiment, it was obvious that CO2
alone could not be considered to be an interference compound; however,
in conjunction with other species could present interference problems.
At this point, two facts were apparent; first, CO2/N blends gave 10-16
ppm SO2 response and secondly, CO2/Air blends gave no response.
To determine the extent of the CO2/N£ interference, additional
experiments were conducted. The availability of a range of O2/N2
blends was used to narrow down this problem. The bottles were N2
zero gas, 5 percent O2/95 percent NZ, 10 percent O£/90 percent N2,
15 percent O2/85 percent N2, and 20 percent Oz/^2- Several fresh
bags were prepared and each blend was analyzed for response as ppm
SO2. Then each bag was doped with pure CO2 to a level of about 10 per-
cent. These bags were then run and the results of these tests are found
in Table C-3.
It was apparent that by running the oxygen -nitrogen blends with-
out any CO2, certain effects could be observed. As the amount of oxygen
in the sample decreased (and the nitrogen concentration increased), a
C-3
-------
positive response as ppm SO2 was observed, even though no other compounds
were known to be present. When the blends of about 12 percent CC>2
in various C>2/N2 ratios were analyzed, it was found that the CC>2 and
O2 acted much the same in that the sum of the CO2 and QZ concentra-
tions had the same quenching effect as the Oz concentrations alone.
TABLE C-3. MULTICOMPONENT BLENDS OF CO2/O2/N2
RESPONSE AS SO2 IN MODEL 40 PULSED FLUORESCENT ANALYZER
Concentration, %* Response as
Test C02 02 N2 ppm SO?
1 - 0 100 10+
2 5 95 o.5
3 - 10 90 0.2
4 15 85 o.l
5 20 80 o.O
6 10% 0 90 10+
7 10% 4.5 85.5 0.5
8 10% 9.0 80.0 0.2
9 10% 13.5 76.5 o.l
10 10% 18 72 00
11 100% - 2.0
Initial conclusions regarding CO and COz interferences indicate
that these two exhaust species do not interfere as positive SO2 response
provided there is a sufficient quenching effect provided by oxygen in the
sample. Problems could be present if direct exhaust samples are ob-
tained and oxygen levels are low. Preliminary experiments indicate
that oxygen levels above 5 percent have less than 0. 5 ppm response as
S02. In cases where a CVS air diluted sample is obtained, no inter-
ferences due to CO or CO2 were observed.
NOX Interferences
Five bottles of NOX/N2 were used to conduct initial NOX interfer-
ence experiments. These were also golden standards named by EPA
Ann Arbor. Although these bottles were named as NOX, they were actually
NO in N2 cylinders as verified by chemiluminescent analysis. The con-
centrations were selected to be typical ranges that might be expected in
1975 FTP testing. The results of this test are found in Table C-4. NOX
concentrations ranged from 42 to 220 ppm and the apparent interferences
as ppm S02 varied from 17. 0-36. 0. This was the only gas tested which
appeared to produce an increased response with increasing component
concentration. It should be noted that N2 zero gas produced some 10+
ppm response as SO2.
C-4
-------
TABLE C-4. MULTICOMPONENT BLENDS OF NOX/O2/N2
RESPONSE AS SOz IN MODEL 40 PULSED FLUORESCENT ANALYZER
Concent ration Response as
Test NOX> ppm O2, % N2, % ppra SO2
1 42 - 100 17.0
2 78 - 100 24.3
3 95.5 - 100 27.0
4 133.5 - 100 32.0
5 220 - 100 36.0
6 140 21 79 0,1
7 400 21 79 0
8 550 20 80 0.25
9 710 22 78 0.
10 1125 20 80 negative
11 1400 19 81 negative
12 1750 20 80 negative
There was a definite trend observed regarding NOX concentration
as a function of response as ppm SO2, as shown in Figure C-l. Previous
experiments involving CO and CO2 interference checks indicated that
the presence of nitrogen and the lack of oxygen could lead to apparent
interferences. With this in mind, several blends of NO/N2 were diluted
with oxygen to obtain a nominal 20% 03. The conversion of NO to NO2
was immediately apparent due to the color change of the NO-*NO2 reaction.
Although the previous NOX check involved NO/N2 blends, this experiment
actually was NO2/Air and comparison is somewhat difficult. The con-
centration of NOX ranged from 140-1400 in the bag samples analyzed. The
O2 and N2 concentrations were relatively the same for purposes of this
experiment. At any rate, the low concentrations (140-700) of NO2/Air
produced only slight response as ppm SO2- At higher concentrations of
NO2, a negative response was observed for several gases,
It is difficult to make any absolute conclusions based on the data
presented in Table C-4. Although NO/N2 blends do give a positive response
as ppm SO2, it is impossible to determine the extent of NO/Air interferences
due to the NO-*NO2 oxidation in air. Bag samples obtained from a CVS
are significantly air rich and have O2 concentrations above 15 percent under
most conditions. Since the CVS bag samples contain relatively low concen-
trations of NOX diluted in air, it is not felt that any significant NOX inter-
ferences will be experienced.
C-5
-------
O
w
a
0,
(0
«J
V
0)
c!
O
(X
CO
40 r
35
30
25
20
15
10
0
lr
"db rfej
NOX Concentration, ppm
Figure C-l. The Effect of NOX Concentration (balance N2)
on Response as ppm SC>2
C-6
-------
HC Interferences to Model 40 Pulsed Fluorescent SO2 Analyzer
Several experiments were conducted using typical hydrocarbon
blends in N£ and air. The initial tests were conducted using propane
in N2 and propane in air. The results of these tests are found in Table
C-5. Thegolden standard span gases were originally thought to be air
TABLE C-5. PROPANE SPAN GAS RESPONSE AS SO2
IN TECO MODEL 40 PULSED FLUORESCENT ANALYZER
Concentration, Balance Response as
ppmC Gas PPm SO2
25 Air"" O
34 N2 14.0
168 Air 0.0
301 Air 0.0
1024 Air 0.0
based gases, but during the tests it was found that the 34 ppm C bottle
was actually a balance N2 gas. This accounted for the fact that all of
the other propane in air gases gave no response, whereas the 34 ppmC
/N2 8as gave an apparent response of 14 ppm SO2. Hydrocarbon con-
centrations, varying from 25 to 1024 ppm C balance air, were found to
produce no response as ppm SO2.
It is suspected that the balance N2 was responsible for the apparent
interference in the 34 ppm C bottle. Once it was verified that typical air
based HC span gases produced no interferences, it was decided to check
the Model 40 pulsed fluorescent SO2 instrument response to aromatic hydro-
carbons. Two aromatic hydrocarbons typically found in automotive exhaust
were selected for this experiment. These were benzene and toluene. The
availability of several gases containing various ratios of O2 and N2 were
selected for these tests. Baseline readings were obtained on each of these
gases and these results are presented in Table C-6. A bag sample of
each of these gases was obtained and a predetermined amount of benzene
and toluene were added to each bag. Nominal benzene concentration was
120 ppm C and toluene concentration was about 140 ppm C.
The results of these experiments are illustrated in Figure C-2. In
comparing the response as ppm SO2 to the base O2/N2 blends to those same
blends with added benzene and toluene it is apparent that some sort of inter-
ference due to aromatic compounds is present. It almost appears that the
interference found in this test is an exponential function. Initial conclusions
from this interference check indicate that samples containing less than 5
percent O2 can have significant interference. These evaluations were con-
ducted on the 0-10 ppm scale and the maximum interference that might be
expected during CVS operation would be 0.2 ppm or 2 percent of full scale.
C-7
-------
10.0
0.0
0
A
C>2 + N2 only
120 ppraC benzene
140 ppmC toluene
10
15
20
Percent Oxygen - Balance Nitrogen
Figure C-2. The Effect of Benzene and Toluene in
Various O2/N2 Blends as pprr SO2 in
Model 40 Pulsed Fluorescent Analyzer
C-8
-------
TABLE C-6. MULTICOMPONENT BLENDS OF BENZENE,
TOLUENE/02, NZ RESPONSE AS SOz
IN MODEL 40 PULSED FLUORESCENT ANALYZER
Concentration, ppm C Concentration, % Response as
Test Benzene Toluene O2 N% ppm 50%
1 - 0 100 10+
2 - 5 95 0.5
3 - 10 90 0.2
4 - 15 85 0.1
5 - - 20 80 0.0
6 140 160 0 100 10+
7 140 160 5 95 0.8
8 140 160 10 90 0.4
9 140 160 15 85 0.2
10 140 160 20 80 0.15
General Comments of Model 40 Pulsed Fluorescent SO? Analyzer
Upon completion of the aforementioned experiments, several
contacts were made with other individuals who had working experience
with the instrument or was involved with Thermo Electron Corporation.
The first contact was Glenn Reschke at General Motors. He had conducted
numerous experiments with this model instrument, many of the same
nature of the SwRI evaluations. Although his particular application was
for use in undiluted automotive exhaust sampling, his conclusions regarding
the various component interferences were essentially identical to those
presented herein.
Further verification of individual component interferences conclu-
sions was obtained from Dennis Helms of Teco. He re-iterated the items
presented in this report and those indicated by Glenn Reschke. Recom-
mendations for specific application to CVS type exhaust sampling have been
previously incorporated into the exhaust sampling system.
It may be considered a concensus of opinion that sampling from any
air-rich CVS system and using air balance SO2 span gases and air zero
gases minimize on potential interferences. Should direct exhaust sampling
with relatively low oxygen concentrations (less than 5 percent), additional
interference checks might be warranted.
C-9
-------
SUMMARY OF PULSED FLUORESCENCE ANALYZER EXPERIMENTS
The SO£ levels from the tests using the PF analyzer are shown in
Tables C-7, C-8 and C-9 for 30 mph; 60 mph, and the '75 CVS test re-
spectively. As can be seen from these tables, the PF analyzer greatly
overstates the amount of SO2 in the exhaust. It was felt that some effort
had to be expended to try and determine the cause of this problem. Since
tests run with the PF analyzer on another project using the same fuel, but
with a 0. 1 percent sulfur level (twice as high as the sulfur level on this
project) had shown sulfur recovery of approximately 115 percent, it was
reasoned that perhaps sulfur level had an effect on recovery. Stated in
a different manner, there may be a constant positive interference, which
of course becomes less significant as the SO2 concentration in the exhaust
increases. To check this hypothesis, a series of 30 mph steady state
tests were run with 4 different sulfur levels in the same base fuel. The
results of these tests are shown in Table C-10 and graphically in Figure C-3.
It appears that there is indeed a constant interference that causes the re-
covery to increase far above 100 percent as the sulfur level in the fuel
decreases. As a. further check, one test was conducted with straight iso-
octane as the fuel with thiophene added to give 0. 051 percent sulfur. The
results of the test run with this fuel at the 30 mph steady state condition
are shown below.
Pet. S
in fuel
.051
Test Exhaust SO2
Date by PF, grams
11/21/74 1.23
Exhaust S
grams
0.616
Fuel S
grams Recover
0. 752 82%
Fuel
Iso-octane
It appears that recovery is a function of fuel composition also.
During the first week of December, 1974, the PF analyzer manu-
facturer, Thermo Electron Corporation (TECO), was contacted to solicit
any comments and ideas they might have concerning the SO, recovery
problem. Mr. Arvin Smith of TECO was in San Antonio on December 4,
1974 and visited the Emissions Research Department at SwRI to discuss
the problem. It was his feeling that the high SO 2 readings from the ana-
lyzer were caused by light scattering from small particulates or aerosols
not removed in the filtering system or even from glass fiber particles
from the Gelman Spectro-Glass Fiber filters used as the primary filter in
the sampling system.
To test this theory, a series of tests were run on December 5 and
6 with various sample filtering schemes. The results of these tests are
shown in Table C-ll. Two different fuels (iso-octane and regular grade
gasoline) were used, each with two sulfur levels (0. 02 percent and 0. 1
percent). From the table it can be seen that while the 0. 5 micron and 10
C-10
-------
millimicron '.filters give an acceptable sulfur recovery with 0. 1 percent
sulfur in the regular grade gasoline used as the base fuel so far in this
project, these filters do not give an acceptable sulfur recovery with 0. 02
percent sulfur in the base fuel. Interpolating to the 0. 04 percent sulfur level
used in this project, it appears that the recovery would not be acceptable.
Thus it was concluded that finer filters would not solve the sulfur recovery
problem experienced with the PF analyzer at the fuel sulfur levels used
in this project.
It was felt that enough time had been spent attempting to obtain
an acceptable sulfur balance with the PF analyzer and that an alternate
method would have to be used to determine SC>2 levels in the exhaust
gases for this project.
C-ll
-------
TABLE C-7. EXHAUST SO2 EMISSIONS FROM A 1972 PLYMOUTH
AT 30 MILES PER HOUR USING A PULSED FLUORESCENT ANALYZER
(.051 Percent Sulfur in Fuel)
Pulsed Fluorescent Analyzer
Sulfur in Fuel P. F.
Run SO2 Emissions SO2 Exhaust, Sulfur, Analyzer,
Test Date Duration grams grams /km grams grams Recovery
90 min
90 min
90 min
12.59
14.80
13.74
0. 174
0.204
0. 190
6. 12
7.41
7. 16
3. 33
2.89
3.29
183%
256%
218%
TABLE C-8. EXHAUST SO2 EMISSIONS FROM A 1972 PLYMOUTH
AT 60 MILES PER HOUR USING A PULSED FLUORESCENT ANALYZER
(. 051 Percent Sulfur in Fuel)
Pulsed Fluorescent Analyzer
Test Date
11/8/74
11/8/74
11/18/74
11/21/74
Run
Duration
70 min
60 min
60 min
60 min
SO2 Emissions
grams
26.84
17.81
22.75
16.72
S02
grams /km
0.238
0. 184
0.236
0. 173
Sulfur in
Exhaust,
grams
13.43
8.91
11.39
8.37
Fuel
Sulfur,
grams
5.69
4.59
5. 10
5. 12
P. F.
Analyzer
Recovery
236%
194%
223%
163%
TABLE C-9. EXHAUST SO2 EMISSIONS FROM A 1972 PLYMOUTH RUN ON
THE 1975 CVS PROCEDURE USING A PULSED FLUORESCENT ANALYZER
(. 051 Percent Sulfur in Fuel)
Pulsed Fluorescent Analyzer
Test Date
JO/22/74
11/7/74
11/19/74
11/20/74
SO2 Emissions
SO
'2
grams
4.34
5.59
6.05
4.94
Sulfur in Fuel P. F.
Exhaust, Sulfur, Analyzer
grams/km grams
0.25 2.17
0.34 2.79
0.37 3.03
0.30 2.47
grams Recovery^
1.66 131%
1.59 177%
1.63 186%
1.53 161%
C-12
-------
TABLE C-10. SULFUR RECOVERY IN EXHAUST BY PULSED
FLUORESCENT ANALYZER FROM 30 MILE PER HOUR STEADY STATE TESTS
Test Date
11/25/74
11/25/74
10/22/74
ll/'7/74
11/18/74
11/26/74
11/26/74
11/25/74
11/26/74
11/27/74
Percent Sulfur
in Fuel
0. 019
0.019
0. 051
0. 051
0. 051
0. 051
0. 051
0.10
0. 10
0. 20
Percent Sulfur Recovery
Using PF Analyzer
483%
614%
183%
256%
218%
259%
287%
134%
186%
143%
Fuel Type
Unleaded
Unleaded
Leaded
Leaded
Leaded
Unleaded
Leaded
Unleaded
Unleaded
Unleaded
C-13
-------
TABLE C-ll. SULFUR DIOXIDE EMISSIONS FROM 197Z PLYMOUTH
USING VARIOUS SAMPLE FILTERS AT 30 mph STEADY STATE CONDITIONS
Fuel sulfur
Fuel level, %
Iso-octane
Iso-octane
Iso-octane
Iso-octane
Iso-octane
Base
Base
Base
Base
Base
Base
0.02
0.02
0.10
0.10
0.10
0.02
0.02
0.02
0.10
0.10
0.10
Filter*
A
B
A
B
C
A
B
C
A
B
C
P.F.**
so2,
g/km
0.20
0.18
0.84
0.77
1.14
0.62
0.59
0.90
1.08
1.10
1.91
Exhaust
sulfur, g
0.16
0.14
0.68
0.62
0.92
0.50
0.48
0.72
0.87
0.89
1.54
Fuel
sulfur, g
0.19
0.19
0.92
0.92
0.92
0.17
0.17
0.17
0.89
0.89
0.89
Percent
recover
"
84
74
74
67
100
294
282
424
98
100
173
* Filter code: A - 0. 5 micron Fluoropore
B - 10 millimicron Millipore
C - Gellman Spectro Glass Fiber
##P. F. SO2 is from dilute continuous sample.
Note: Base fuel is an unleaded regular grade gasoline.
C-14
-------
'— j*-^*-^^--*.*1^ vj JX • W^-Ji*X"kJ -
^ --
-------
APPENDIX D
SwRI SO2-BCA PROCEDURE
AND VALIDATION TESTS
-------
THE MEASUREMENT OF SULFUR DIOXIDE
USING THE BARIUM CHLORANILATE METHOD
(SO2-BCA)
February 1975
Harry E. Dietzmann
Southwest Research Institute
San Antonio, Texas
D-3
-------
I. BACKGROUND
The measurement of sulfur dioxide (802) in dilute automotive
exhaust has been a difficult task. Although there are several continuous
recording SC^ instruments commercially available, they have not dem-
onstrated the degree of accuracy necessary at the SO2 levels observed
in dilute automotive exhaust. A number of other wet chemical procedures
are also available but are considered either excessively time consuming
or lacking in sensitivity. With this in mind, an idea was conceived by
EPA Research Triangle Park to use some basic concepts in the Federal
Register and to adapt these concepts for measuring SO? in dilute automo-
tive exhaust.
This procedure uses midget impingers with 3 percent hydrogen
peroxide to oxidize the SO2 to sulfate. The samples are then evaporated,
treated, extracted and analyzed according to the barium chloranilate
method for sulfate analysis. The main advantages of this procedure are
the sensitivity and the simplicity of analysis.
II. APPARATUS
This procedure incorporates two midget impingers in series with
a 0. 5ji filter in the sample line. Other items in the sample train include
drierite tube, wet test meter, sample pump and flowmeter. A flow sche-
matic is presented in Figure 1 to illustrate the relative positions of the
various individual components. The sample probe is glass and the filter
is a 0. 5^i SS filter press-fit into the teflon union connecting the glass
sample probe and the first bubbler. By use of appropriate valving, a
dual system could be assembled if consecutive samples were desired
such as in the cold start 505 and the stabilized portion of the 1975 FTP.
A. Midget impingers - capable of handling 25 ml of absorbing reagent.
B. Sample pump - must have sample flow capacity of at least 2 1/m.
C. Drierite column - filled with mixture of indicating and non-indicating
drierite.
D. Wet test meter - capable of accurately measuring sample flow
rates at least in the range of 2 1/min.
E. Flow meter - capable of monitoring flow rates in the range of
2 1/min.
D-4
-------
F. Sample probe - glass should be of minimum length.
G. Filter - O.Su stainless steel filter disc press-fit into teflon union.
H. Barium Chloranilate Sulfate Analysis System' '.
III. REAGENTS
A. 30 percent stabilized hydrogen peroxide (H2O2) ACS reagent grade.
Store in refrigerator.
B. 3 percent hydrogen peroxide solution, dilute 30 percent 10:1 to
obtain the required 3 percent H2O2. Use only distilled water
as the dilutent. Prepare the day of use,
C. Ammonium hydroxide, 1M. Use ACS reagent grade diluted to
obtain the desired 1M solution.
D. Red litmus paper.
E. Isopropyl alcohol, spectroquality identical to that used in the sul-
fate analysis.
F. 60 percent IPA - 40 percent H2O, same solvent that is used in
the barium chloranilate method for sulfate analysis.
G. Distilled water, used in preparation of absorbing reagent (3
percent H2O2) and extraction solvent (60 percent IPA).
H. Ammonium sulfate, ACS grade, used in the perparation of ammo-
nium sulfate standards.
I. Miscellaneous analytical and chemical support items, routinely
used in the Barium Chloranilate Procedure.
IV. PREPARATION OF SULFATE STANDARDS (USING (NH4)2SO^)
A. Comments
Weigh out exactly 2. 750 g of ACS reagent grade (NH4)2SO4 into a
pre-weighed clean dry beaker. Dissolve the (NH4)2SO4 in 60 percent IPA
and dilute to a total of 1000 ml in a Class A volumetric flask. The resulting
1 ' Designates that which is attached.
D-5
-------
sulfate concentration is then 2000ug SC>4/ml. This solution is called
the dilute primary standard and is to be used to prepare working cali-
bration standards.
B. Calculations
2. 750 g (NH4)2S04 = 2. 750 g (NH4)2SO4 x 96 awu SO^
132 awu (NH4)2SO4
2. 750 g (NH4)2S04 = 2. 000 g SO4 =
2.000 g S04/l = 2.000 g SO4/1 x II x 1 O
1000 ml 1 g
2.000gSOj/l = 2. OOP x 106jag = ZOOOyg/ml
10-5 ml
C. Preparation of Working Standards
Volume of Dilute Volumetric Sulfate Concentration
Sample Primary Standard* Flask, ml»« jug SO;;/ ml
1
2
3
4
5
10
15
5
5
1
1000
2000
1000
2000
1000
20.0
15.0
10.0
5.0
2.0
* Measured using Class A volumetric pipet.
#* Measured using Class A volumetric flask.
After each set of standards are prepared, run to establish the validity
and linearity of the new working standards.
All glassware should be thoroughly cleaned and no visible glass-
ware spots should be tolerated. Once the working standards are prepared,
they should be transferred to clearly marked glass reagent bottles for
storage.
V. PROCEDURE
A. Sample Acquisition
The exhaust sample to be analyzed is bubbled through the two
midget impingers in series. Prior to sampling, it is important to leak
D-6
-------
check the sampling system to insure nc leaks are present. Once the ab-
sence of leaks is verified, pipet 25 ml of freshly prepared 3 percent
hydrogen peroxide into each of the bubblers. All ground glass fittings
should have stopcock grease to insure leak tight connections. Prior to
testing, the drierite column is freshly prepared and the wet test meter
is read. Once the test has started, the flow is adjusted to 1.5 1/min.
Sampling times will vary depending on the concentration of the SO? in the
exhaust sample; however, the extracted sample can be diluted if necessary.
Tests have shown that sufficient sample can be obtained from 10
minutes at 2 to 3 ppm SO2 levels, bubbling at a rate of 1. 5 1/min. It
might be possible to use somewhat higher sample flow rates if necessary,
but high recoveries have been observed at 1. 5 1/min. Generally, sampling
for periods of more than 20 minui.es will require dilution at the 2 to 3 ppm
SO2 level. It should be pointed out that this will vary somewhat depending
on the range capability of the individual BCA system.
B. Extraction Procedure
1. After the bubbling is complete, quantitatively transfer the ab-
sorbing reagent to a 100 ml beaker. Rinse the impinger tip and bubbler
thoroughly several times with 3 percent t^O, Add these rinsings to the
original absorbing reagent in the 100 ml beaker. This will bring the total
volume to about 30 ml. The final volume at this point is not critical
since the absorbing reagent will be evaporated to dryness.
2. Place the 100 ml beaker on a steam bath and begin evaporating.
Once the volume has evaporated to about 10 ml, make the solution slightly
basic to litmus with 1M ammonium hydroxide. Use a stirring rod tip to
touch the sample to a strip of red litmus paper. Usually 2 to 4 drops
will be sufficient. Complete the evaporation to dryness to insure that
no ammonium hydroxide remains in the beaker. Several experiments in
determining recovery rates have indicated that any ammonium hydroxide
remaining will create an interference.
3. Once the beaker is thoroughly dry, remove from the steam
bath and allo'v to cool. The entire evaporation procedure requires
about 4 to 5 hours per beaker. The ammonium sulfate appears as a
white deposit on the bottom and sides of the beaker. Use a rubber police-
man on a glass stirring rod with about 2 ml of 60 percent IPA to gently
break loose the deposit and put into solution. This step is repeated
several times using about 2 ml of 60 percent IPA each time. After each
time, add the rinsing to a 10 ml volumetric flask. After a minimum of
three extraction-rinsings, dilute to the mark with additional 60 percent
IPA. After the sample has been properly prepared, it is then considered
ready for analysis in the barium chloranilate system.
D-7
-------
C. Analysis
After the sample has been bubbled, evaporated, treated and ex-
tracted, it is analyzed using the barium chloranilate procedure. Since
these samples are essentially ammonium sulfatc in 60 percent 1PA, the
working standards are also ammonium sulfate in 60 percent IPA. A copy
of the barium chloranilate procedure is found in Appendix B. Standards
are run before and after each sample and blanks are run between all
samples and standards. A typical trace of a standard, blank, sample
sequence is shown in Figure 2.
D. Calculations
The equation used to calculate the ppm SO2 in an exhaust sample
using the SO2-BCA procedure is listed below:
ppm SO2 sample =(6.67 x cone SO4 ~ std, jug)x (area SO 4 sample, in )x DF
(area 504^ std, in^)x Cdensity,^4g/l)x sample volume, 1
The derivation of this equation is presented as an attachment and is ap-
plicable to this specific procedure.
Although calculations use peak areas, it would be possible to use
peak heights under certain conditions:
(Example 1) - Assume an exhaust sample was bubbled through two
bubblers in series and a total of 12. 75 liters was sampled. The gas en-
tering the dry gas meter was 0°C at a barometric pressure of 29. 92" Hg.
A SO4~ standard of 19.2ug/ml gave a response of 1.56 in2. When diluted
5:1 for the first bubbler and left at full strength for the second, the un-
known sample gave a response of 2. 05 in2 for the first bubbler and 0.42 in2
for the second bubbler.
ppm SO2 = 6. 67 x 19. 2 x 2. 05 x 5 = 22. 5 ppm
(bubbler 1) 1.56x2.927x12.75
ppm SO2 = 6.67 x 19.2 x 0.42 x 1 =0.9 ppm
(bubbler 2) 1.56x2.927x12.75
Total Sample ppm SO2 = 22. 5 ppm + 0.9 ppm =23.4 ppm
(Example 2) - Assume an exhaust sample was bubbled through two
.bubblers in series and a total of 1.436 ft^ was sampled. The gas entering
the dry gas meter was 30* C at a barometric pressure of 29.31" Hg. An
504 standard of 9.6ug SO^/ml gave a response of 0. 78 in2. When diluted
10:1 for the first bubbler and leaving the second at full strength, the un-
known sample gave a response of 3. 25 in for the first bubbler and 0. 21 in
D-8
-------
for the second bubbler. (Note that there are two differences in the ex-
amples, this example has the sample volume in ft^ rather than liters
and the sampling conditions are not at STP. ) The first calculation will
be to obtain the density of SG>2 at 30° C and 29.31" Hg.
density SO, at 0° C and 29. 92" Hg = 2.927 g
11
1 liter at 0° C and 29. 92" Hg = 1.133 liters at 30° C and 29. 31" Hg
11 = 11 x 273 +30°K x 29.92" Hg = 1.133 1
273°K 29.31"Hg
density SO2 at 30°C and 29. 31" lig = 2.927 g = 2. 583 g/1
1.133 1
ppm SO 2 = 0. 2356 x9.6x3.25xlO = 25.4 ppm
(bubbler 1) 0.78x2.583x1.436
ppm SO2 = 0. 2356 x 9.6 x 1.95 x 1 =1.5 ppm
(bubbler 2) 0.78x2.583x1.436
Total Sample ppm SO,, =25. 4 +1.5 =26. 9 ppm
D-9
-------
SOUTHWEST RESEARCH INSTITUTE
DATA SHEET
SUBJECT DER/VATtOU OF
SHEET NO.-J OF V-SHEETS:
PROJECT
DATE
BY
£ 1 rjFRow Djiterry
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-------
SOUTHWEST RESEARCH INSTITUTE
DATA SHEET
SUBJECT DEftWATlQM OF Sl)ApUF\ED
SO? - BCf\ ETQOATIONl
SHEET NO..
PROJECT -
DATE
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Note: All tubing in sample train up to the impingers is glass or teflon.
teflon union w/SS
frit insert
glass probe
d
t
H-•
IS)
pump
wet test
meter
dilution tunnel
midget impingers
thermocouple
flowmeter
FIGURED-;. SO2-BCA FLOW SCHEMATIC
-------
• 'llillllLlIb^l'. '1JT": rV "^ '"' LlTilllfn^'';'^''H;'''••''f; '!"•'
~ '
. "i T"
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S; T7P1CAL BCA STANDARD AMD SAMPLE TRACE
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ffepfititfi^
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-------
RESULTS OF VALIDATION TESTS OF THE SO2-BCA METHOD
RUN AT SwRI
Extensive experiments were conducted to validate the sampling
and extraction procedures. The experiments were conducted in both
areas of the procedure, the sample acquisition and the sample analysis.
Experiments involving the sample acquisition phase of the pro-
cedure proved to be the most troublesome. Items investigated during
this phase of experiments involved sampling flow rates, bubbler ef-
ficiencies, sample system positioning, reagent selection, and absorbing
reagent temperature. The tests were conducted basically with 3g Pb/gal
and 0.051 percent sulfur fuel. Through a series of experiments involving
the sampling parameters, the recommended sampling procedure in this
Appendix was formulated.
Several tests involving sample extraction and analysis were also
conducted. Calibration standards were prepared in absorbing reagent,
and the extraction procedure parameters were investigated. Between
97 and 100 percent recovery was obtained on known sulfate levels once
the extraction procedure variables were determined. Variables investi-
gated included the degree of evaporation (dryness or semi-dry), amount
of ammonium hydroxide added, and the removal of the (NH4),SO4 deposit
from the extraction beaker.
Most tests involving sulfur balances on the 1972 Plymouth were
conducted using steady state conditions. Comparisons were made be-
tween on-line continuous sampling and bag samples analyzed once the
test were complete. Several LA-4 tests were also performed (single
bag 23-minute sample) where bag samples were also analyzed. A sat-
isfactory recovery level could not be obtained from the bag samples.
Several tests on a low level sulfur fuel were conducted and recoveries
averaged 96 percent for three 30 mph and two 60 mph steady states.
The development testing resulted in a procedure that gives a sat-
isfactory sulfur balance. Tables D-l, D-2 and D-3 summarize the test-
ing done on 30 and 60 mph steady state and '75 light duty FTP testing
respectively.
The average sulfur recovery for the steady state tests is approxi-
mately 106 percent with a range of approximately ±20, with most tests with-
in ±10 percentage points of the average. The 1975 LD FTP has a somewhat
lower average sulfur recovery of 92 percent, but a range of only 22 percentage
points. These sulfur recovery levels are orders of magnitude better than
the TECO PF analyzer and an improvement over what others have seen
using titration or gravimetric analysis of hydrogen peroxide SO2 collection
systems.
D-14
-------
TABLE D-l. SUMMARY OF SO2 EMISSIONS FROM 30 MPH STEADY STATE TESTS
OF A 1972 PLYMOUTH USING THE SwRI SOz-BCA METHOD
Continuous Dilute Sampling With Glass Probe, 30 Min. Sample)
Ul
Run
Time, Fuel
Fuel Used, Grams S Exhaust SO2, Exhaust S, Recovery,
Date
1/9/75
1/9/75
1/9/75
1/10/75
1/10/75
1/10/75
1/24/75
1/24/75
1/24/75
* EM -22
Speed
30
30
30
30
30
30
30
30
30
,5-F is 11
Min
102
102
102
94
94
94
90
90
90
nlftaded
Type
EM-225-F
EM-225-F
EM-225-F
EM-225-F
EM-225-F
EM-225-F
EM-225-F
EM-225-F
EM-225-F
rftcmlar arade
grams*
6641
6641
6641
6056
6056
6056
5922
5922
5922
trasoline wit
in Fuel
3.39
3.39
3.39
3. 08
3.08
3.08
3.02
3.02
3.02
h . 051 nercc
grams
7.00
6.71
7.48
7.46
7.46
7.46
6. 21
5. 16
5.40
;nt sulfur
grams
3.50
3.36
3.74
3.73
3.73
3.73
3. 11
2.58
2.70
Avg.
Max
Min
Std. Dev.
CV = 13%
%
103
99
111
121
121
121
103
85
89
106
121
85
14
208-FC is leaded regular grade gasoline with .051 percent sulfur
-------
TABLE D-2. SUMMARY OF SOz EMISSIONS FROM 60 MPH STEADY STATE TESTS
OF A 1972 PLYMOUTH USING THE SwRI SO2-BCA METHOD
Continuous Dilute Sampling With Glass Probe, 30 Min. Sample)
Run
Time, Fuel
Fuel Used, Grams S Exhaust SO2, Exhaust S, Recovery,
Date
1/13/75
1/13/75
1/13/75
t> 1/13/75
i
^ 1/21/75
1/21/75
1/21/75
1/23/75
1/23/75
1/23/75
* EM-22E
Speed
60
60
60
60
60
60
60
60
60
60
i-F is un'
Min
84
84
84
84
60
60
60
60
60
60
Leaded :
Type
208-FC
208-FC
208-FC
208-FC
EM-225-F
EM-225-F
EM-225-F
EM-225-F
EM-225-F
EM-225-F
recmlar erade s
grams*
10215
10215
10215
10215
7507
7507
7507
7203
7203
7203
jasoline with
in Fuel
5. 21
5. 21
5.21
5.21
3.82
3.82
3.82
3.67
3.67
3.67
. 051 nerce
grams
11.94
13. 08
10.79
11. 50
6.80
8.51
8. 74
6.86
7.20
8. 26
nt sulfur
grams
5.97
6.54
5.40
5.75
3.40
4.26
4.37
3.43
3. 60
4. 13
%
115
126
104
110
89
112
114
93
98
113
Avg. 107
Max. 126
Min. 89
Std. Dev 11
CV = 11%
CT tJ G7 J.
208-FC is leaded regular grade gasoline with .051 percent sulfur
-------
TABLE D-3. SUMMARY OF 1975 LD FTP TESTS
OF A 1972 PLYMOUTH USING THE SwRI SO2-BCA METHOD
Continuous Dilute Sampling With Glass Probe
Date
Type
Fuel
1/14/75 208-FD
1/21/75 225-F
1/23/75 225-F
1/24/75 225-F
Fuel Used,
grams*
2703
2717
2853
2694
Fuel S,
grams
Exhaust
SOz,
grains
Exhaust
S,
grams
1.38
1.39
1.46
1.37
2.77
2.71
2.31
2.45
1.39
1.36
1. 16
1.23
Recovery,
101
98
79
_9_0
Avg. 92
Max 101
Min 79
Std Dev. 10
UlrU J-Xti V • A V
* EM-225-F is unleaded regular grade gasoline with .051 percent sulfur
208-FD is leaded regular grade gasoline with . 051 percent sulfur
D-17
-------
APPENDIX E
METHOD-8 DETERMINATION OF SULFURIC ACID MIST
AND SULFUR DIOXIDE EMISSIONS FROM
STATIONARY SOURCES
-------
METHOD 8—DERBMXNATXON OT SU1TUSIC ACID
MIST AND SDlnnt DIOXIDE EMISSIONS rtUOf
STATIONARY SOUaCTS
1. Principle and applicability.
1.1 Principle. A gas sample u extracted
from a sampling point In the stack and the
acid mist including sulfur trioxide is sepa-
rated from sulfur dioxide. Both fractions are
measured separately by the barlum-thorln
UtraUon method,
1.2 Applicability. This method is applica-
ble to determination of sulfurlo acid mist
(Including sulfur trloxlde) and sulfur diox-
ide from stationary sources only when spe-
cified by the test procedures for determining
STACK
compliance with the New Source Perform-
ance Standards.
2. Apparatus.
2,1 sampling. See Figure 8-1. Many of
the design specifications of this sampling
train are described In APTD-OS81.
3.1.1 Nozzle—Stainless steel (316) with
sharp, tapered leading edge.
2.1.2 Probe—Pyrex' glass with a heating
system to prevent visible condensation dur-
ing sampling.
3.1.3 .Pltot tube—Type 8. or equivalent.
attached to probe to monitor stack gas
velocity.
2.1.4 Filter holder—Pyarex > glass.
2.1.5 Implngera—Four as shown In Figure
8-1. The first and third are of the Greenburg-
Smlth design with standard tip. The second
and fourth are of the Oreenburg-Smlth de-
sigh, modified by replacing the standard tip
with a %-lnch ID glass tube extending to
one-half inch from the bottom of the 1m-
plnger flask. Similar collection systems,
which have been approved by the Adminis-
trator, may be used.
2.1.6 Metering system—Vacuum gauge,
leak-free pump, thermometers capable of
measuring temperature to within 5* P., dry
gas meter with 2% accuracy, and- related
equipment, or equivalent, as required to
maintain an IcoUaetlc sampling rate and
to determine sample volume.
2.1.7 Barometer—To measure atmospheric
pressure to ±0.1 Inch Hg.
1 Trade name.
.CHECK
VALVE
•.::•: '• VUf':":!!: r-if
iilS , & iaf M
.VACUUM
LINE
VACUUM
GAUGE
JH-TIGHT
PUMP
DOT TEST METER
Figure 6>1. Sulfurlc add mist sampling Iraln.
2.3.2
2.3.3
2.3.4
2.3.S
2189.1
2.2 Sample recovery.
3.3.1 Wash bottles — Two.
2.2.2 Graduated cylinders— 250 ml., BOO
ml.
2.2.3 Glass sample storage containers.
2.2.4 Graduated cylinder — 250 ml.
2.3 Analysis.
2.3.1 Pipette— 25 ml., 100 ml.
Burette— 60 ml.
Erlenmeyer flask — 290 ml.
Graduated cylinder — 100 ml.
Trip balance— 300 g. capacity, to
measure to ±0.03 g.
2.3.6 Dropping bottle — to add indicator
solution.
3. Reagents.
3.1 Sampling.
3.1.1 Filters— Glass fiber. MSA type 1106
BB, or equivalent, of a suitable size to At
In the filter holder.
3.1.3 Silica gel— Indicating type, 6-10
mesh, dried at 175* C. (350* F.) for 2 hours.
3.1.3 Water— Delonlzed, distilled.
3.1.4 Isopropanol, 80%— Mix 800 ml. of
Isopropanol with 200 ml. of delonlzed, dis-
tilled water.
3.1.6 Hydrogen peroxide, 3%— Dilute 100
ml. of 30% hydrogen peroxide to 1 liter with
delonlzed. distilled water.
3.1.6 Crushed ice.
3.2 Sample recovery.
3.2.1 Water— Delonized. distilled.
3.2.2 Isopropanol, 80%.
3.3 Analysis.
, 3.3.1 Water— Delonlzed, dlstUled.
3.3.2 Isopropanol.
34.3 Thorln Indicator — l-(o-arsonophen-
ylazo)-2-naphthol-3, 6-dlsulfonlc acid, dl-
' sodium salt (or equivalent). Dissolve 0.20 g.
In 100 ml. distilled water.
3.3.4 Barium perchlorate (0.01AO — Dis-
solve 1.05 g. of barium perchlorate |Ba
. (CO,), 3 H.O| In 200 ml. distilled water ana
dilute to 1 liter with Isopropanol. Standardize
with suit uric acid.
3.3.5 Sulturic acid standard (0.01JV) —
Purchase or standardize to ± 0.0002 JV against
0.01 AT NaOH which has previously been
standardized against primary standard po-
tassium acid phthalate.
4. Procedure.
4.1 Sampling.
4.1.1 After selecting the sampling site and
•the minimum number of sampling points,
determine the stack pressure, temperature.
moisture, and range of velocity head.
4.1.2 Preparation of ' collection train.
Place 100 ml. of 80% Isopropanol In the first
imploger. 100 ml. or 3% hydrogen peroxide in
both the second- and third Implngers, and
•bout 200 g. of silica gel In the fourth 1m-
pinger. Retain a portion of the reagents for
use- as blank solutions. Assemble the train
without the probe as shown in Figure 8-1
with the filter between the first and second
Implngers. Leak check the sampling train
at the sampling site by plugging the inlet to
the first implnger and pulling a 15-inch Hg
vacuum. A leakage rate not In excess of 0.02
clja, at a vacuum of IS Inches He Is ac-
ceptable. Attach the probe and turn on tlie
probe heating system. Adjust the probe
heater setting during sampling to prevent
any visible condensation. Place crushed ice
•round the implngers. Add more ice durlnff
the run to keep the temperature of the S^c3
leaving the last Implnger at 70* F. or. less,
4.1.3 Train operation. For eacii run, re-
cord the data required on the example sheet
shown in Figure 8-4. Take readings at each
sampling point at least every A minutes and
when significant changes in stack conditions
necessitate additional adjustments in flow
rate. To begin sampling, position the nozzle
at the first traverse point with the tip point-
Ing directly Into the gas stream. Start the
pump and immediately adjust the flow to
isoklnetlc conditions. Maintain isokinetic
sampling throughout the sampllnc period.
Nomograph* are available which aid in the
FEDERAL REGISTER, VOL 36, NO. 247—THURSDAY, DECEMBER 21, 1971
E-2
-------
W
rapid adjustment of the sampling rate with-
out other computations. APTD-O578 detail
the procedure for using these nomographs.
At tlia conclusion of each run, turn off thr
pump ami record the filial readings. Remove
the probe from the stack and disconnect it
'ram the train. Drain the tea bath and purge
'•ha remaining part of the train by drawing
clean ambient air through the system for 15
minutes.
/ °R \ ^
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4.3 Sample recovery.
4.3.1 Transfer the Isopropanol from, the
first Implnger to a 250 ml. graduated cylinder.
Rinse the probe, first Implnger, and all con-
necting glassware before the filter with 80%
Isopropanol. Add the rinse solution to the
cylinder. Dilute to 250 ml. with 80% Isopro-
panol. Add the filter to the solution, mix.
and transfer to a suitable storage container.
Transfer the solution from the second and
third Implngers to a 600 ml. graduated cyl-
inder. Rinse all glassware between the filter
and silica gel Implnger with delonlzed, dla-
ttlled water and add this rinse water to the
cylinder. Dilute to a volume of BOO ml. with
delonlzed, distilled water. Transfer the solu-
tion to a suitable storage container.
4.3 Analysis.
4.3.1 Shake the container holding iso-
propanol and the filter. If the filter breaks
up, allow the fragments to settle for a few
minutes befoie removing a sample. Pipette
a 100 ml. aliquot of sample Into a 250 ml.
Erlenmeyer flask and add a to 4 drops of
thorln Indicator. Titrate the sample with
barium perchlorate to a pink end point. Make
sure to record volumes. Repeat the tltra-
tlon with a second aliquot of sample. Shake
the container holding the contents of the
second and third Implngers. Pipette a 25 ml.
aliquot of sample into a 250 ml. Erlenmeyer
flask. Add 100 ml. of isopropanol and 2 to 4
drops of thorln Indicator. Titrate the sample
with barium perchlorate to a pink end point.
Repeat the tltratlon with a second aliquot of
sample. Titrate the blanks In the same
manner as the samples.
5. Calibration.
5.1 Use standard methods and equipment
which'have been approved by the Adminis-
trator to calibrate the orifice meter, pltot
tube, dry gas meter, and probe heater.
5.2 Standardize the barium perchlorate
with 35 ml. of standard sulfuric acid con-
taining 100 ml. of Isopropanol.
6. Calculations.
6.1 Dry gas volume. Correct the sample
volume measured by the dry gas meter to
standard conditions (10* F., 29.92 Inches Hg)
by using Equation 8-1.
Volume of gas samp'.e through the
dry gas meter (sundard condi-
tions) . cu. It.
V,.— Volume of gas sample through the
dry gas meter (meter condi-
tions) , cu. ft.
T ,. = Absolute temperature at standard
conditions, 630* R.
L.OSX1
o4= Concentration of nillurlo acid
at standard conditions, dry
basis, ibycvu It. .
1.08X10-*= Conversion factor Including the
number ol grams per gram
equivalent of sulfuric acid
(49 g./g.-eq.), 453.6 g./lb.. and
1.000 miyi., lb.-iyg.-ml.
V,=Volume of barium perchlorate
tltrant used for the sample.
mL
Vt,=Volume of barium perchlorate
tltrant used lor the blank, ml.
Cgo,=
where:
CM>,— Concentration of sulfur dlralde
at standard conditions, dry
ba«la, Ib./cu. ft.
7.05 X10-»=> Conversion factor Including the
number of grama per gram
equivalent of sulfur dioxide
(32 gyg.-eq.) 453.6 g./lb, and
1,000 ml./l.. lb.-l./g.-ml.
Vt—Volume of barium perchlorate
tltrant .used for the sample,
mL
V,k—Volume of barium perehlorate
tltrant used for the blank, mL
H—Normality of barium p^rchlorate
.tltrant, g.-eq./l.
V..,,—Total solution volume of sulfur
dioxide (second and third Im-
plngers) , ml.
V.—Volume of sample aliquot ti-
trated, ml.
equation S-l
T = Average dry fjas meter temperatura,
'R.
P^,,—Barometric pressure at the orifice
meter. Inches Hg.
AH=Pressure drop across the orifice
meter, inches H,O.
13.6—Specific gravity of mercury.
P,,4—Absolute pressure at standard con-
ditions, 29.02 Inches Hg.
6.2 Sulfuric acid concentration.
equation 8-2
N —Normality of barium perchlorate
tltrant, g.-eq./l.
V..,,= Total solution volume of sul-
furic acid (first implnger and
filter), ml.
V,= Volume of sample aliquot ti-
trated, ml.
V»..ti=» Volume of gas sample through
the dry gas meter (standard
conditions), cu. ft., see Equa-
tion 8-1.
6.3 Sulfur dioxide concentration.
Va,tl| equation 8-3
Vn,u= Volume of gas sample through
the dry gas meter (standard
conditions), cu, ft., see Equa-
tion 8-1.
7. References.
Atmospheric Emissions from Sulfuric Acid
Manufacturing Processes, U.S. DHEW, PH6.
Division of Air Pollution, Public Health Serr-
Ica Publication No. 999-AP-13. Cincinnati,
Ohio, 1965.
Corbett, D. P., The Determination of SO,
and SO, In Flue Gases, Journal of the Insti-
tute of Fuel, 24:237-243,1981.
Martin, Robert M.. Construction Details of
Isoidnetic Source Sampling Equipment, En-
vironmental Protection Agency, Atr Pollution
Control Office Publication No. APTD-0581.
Patton, W. P., and J. A. Brink, Jr., Now
Equipment and Techniques for Sampling
Chemical Process Oases, J. Air Pollution Con-
trol Assoc. 11, 162 (1963).
I
in
O
70
m
O
I
g
FEDERAL REGISTER, VOL. 36, NO. 247—THUtSDAY, DECEMBER 23, 1971
-------
APPENDIX F
ANALYSIS OF FUELS USED
-------
TABLE F-l. LIST OF FUELS USED
Date in
Service5
12/30/75
2/25/75
5/7/76
SwRI
Designation
EM-205F
EM-208FD
EM-225F
EM-2I2F
Type
Fuel
Base
Stock
9/15/75 EM-243F
EM-250F
EM-254F
EM-258F
EM-246F
unleaded gas
Sulfur
0.013
leaded gas EM-205F 0.051
unleaded gas EM-205F 0.051
unleaded gas Gulf Crest 0.042
unleaded gas Gulf Crest 0.042
unleaded gas Gulf Crest 0.041
unleaded gas Gulf Crest 0.041
unleaded gas Gulf Crest 0.041
diesel - 2 Gulf 2D 0.25
SwRI Additives
to Base Stock
None
Project Phase
Using Fuel
base stock
motor mix, thiophene characterization
thiophene
thiophene
EM-233F unleaded gas Gulf Crest 0.033 thiophene
EM-236F unleaded gas EM-205F 0.031 thiophene
thiophene
thiophene
thiophene
thiophene
Ditertiary
butyl disulfide
distance accumulation
characterization
procedure development
baseline
baseline (IV-17)
procedure development
baseline
distance accumulation
distance accumulation
distance accumulation
distance accumulation
distance accumulation
characterization
and baseline
*Applies to distance cars only
-------
TABLE F-2. ANALYSIS OF PHILLIPS
UNLEADED GASOLINE, EM-205-F
F>MIL.I_IV=>S
PHILTEX PLANT
ITROLEUIVI COMPANY
PHILLIPS. TEXAS
UNLEADED GASOJjriE BLFMD
CONTRACT NUMBER; 68-02-1122
T-817
DATE OF SHIPMENT
CUSTOMER ORDER NO
INV OR HEON NO. ,
Specification
Research Octane Nurcber
Met or Octane U
fteid Vapor Pressure, psia
Distillation, AST1I D-86, F
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)
1
0.00004
0.0
0.1
8.*0
8.3
5.4
was inhibited with 5 lbs/1000 bbls of Dupont 22 oxidation inhibitor.
(1) Pails Specification, Waiver obtained from customer.
(2) Benzene and Toluene were determined by infrared analysis
techniques.
100^
API Gravity 0 60 F
EU Analysis
Aromatic s >
Olefins JS
Paraffins %
AS1M Gum, r^/100 ml
Stability, hrs
Sulfxir, ppm
Phosphorous, ppm
**ad, g/gallon
W.ene W umber, raeq/liter
?uel Composition, LV %
Benzene
Toluene
n-Bxitane
I sop en t an e
n-pentane
Min.
91.5
82
8
9.8
—
.
320
^
24
7
62
Nonobservable
24+
ZT
—
-
^.
.
.
.
_
Max^.
93.5
85
10
10.2
140
250
350
380
28
10
69
-
100
30
0.01
1
4
15
12
12
e
direct calibration
E. J. Horning \f
Quality Control Superintendent
F-3
-------
TABLE F-3. ANALYSIS OF GULF CREST
UNLEADED REGULAR GASOLINE, EM-212-F
(Prior to Addition of Thiophene)
Property
Distillation (Deg.F*)
(curve attached)
Test Method
ASTM D-216
Results
R.V. P.
V/L calculated
ASTM D-323
ASTM D-439
Gravity
Lead
Sulfur
F. I. A.
Phosphorus
Research Octane
Motor Octane
R + M/2
ASTM D-287
ASTM D-3237
ASTM D-1266
ASTM D-1319
ASTM D-3231
ASTM D-2722
ASTM D-2723
I. B. P.
5%
10%
20%
50%
70%
90%
95%
E. P.
% Recovered
% Residue
% Loss
87°
109°
119°
137*
215°
260°
352"
387°
420a
98.00
.80
1.20
8. 1 Corrected
Temp. F° @ V/L = 4 132
Temp. F' @ V/L = 10 136
Temp. F' @ V/L = 20 141
Temp. F° @ V/L= 30 145
Temp. F° @ V/L=45 150
API 60. 6 @ 60*C
Specific 0.7366 corrected
0.005 g/gal
0.015 wt. %
% Aromatic s 31.86
% Olefins 1.18
% Saturates 66. 96
Temp. O'C - 0.0008 g/g*1
92.0
83.8
87.9
F-4
-------
TABLE F-4. ANALYSIS OF GULF CREST
UNLEADED GASOLINE, EM-250-F
RON
MON
RVP
Sp. Gravity
Pb G/gal
S% wt.
P g/gal
F. I. A.
SAT.
on.
Aro.
DIST. .
IBP
10%
20%
50%
70%
95%
EP
Res. %
Loss %
91.6
80.2
11.1 psi
.7316
0.002
0.041
0.0008
%
73.4
5.2
21.3
F
85
111
125
205
261
395
427
98.0
0.9
F-5
-------
TABLE F-5. ANALYSIS OF GULF 2D DIESEL FUEL, EM-176-F
(Used as Base Fuel for EM-246-F)
Property Results
Gravity, APIat60°F 36.4
Sulfur, % wt. 0. 11
Flash Pt. , °F 150
Vis. at 100°F 2.60 cs
(34. 75 SuS)
Cetane No. (Calc) 47.59
FIA
Aromatics 25.6
Olefins 71.7
Saturates 2. 7
Distillation:
IBP, °F 368
10%, °F 424
20%, °F 444
30%, °F 461
40%, °F 479
50%, °F 482
60%, °F 508
70%, °F 525
80%, °F 544
90%, °F 571
95%, °F 598
End Point, °F 623
F-6
-------
TABLE F-6 . X-RAY FLUORESCENCE ANALYSIS FOR SULFUR
OF SEVERAL SwRI FUELS
EXfON RESEARCH AND ENGINEERING COMPANY
^^ "~ " ~ ~ D /"I DT\V K1 t
P.O. BOX 51. LINDEN. N.J. 07036
PRODUCTS RESEARCH DIVISION
R.R. CECIL
Director
Fuels Research Laboratory
April 3, 1975
Gasoline Sulfur
Analysis for SWRI
Ref. No. 7512 1431
Dr. Melvin Ingalls
Southwest Research Institute
8500 Culebra Road
Post Office Drawer 28510
San Antonio, Texas 78284
Dear Dr. Ingalls:
The sulfur analysis results on the gasoline samples you sent
us are as follows:
SWRI Sample
Description
EM-212F
EM-217F
EM-208F
Unlabeled
EM-212F
Wt. %
Sulfur
0.10*
<0.01
0.053
0.094
0.045
The second sample labeled EM-212F was received several weeks
after the other samples and had a sulfur content of 0.045 wt. %. The
analytical method used was x-ray fluorescence.
If I can be of further assistance to you, please contact me.
Yours truly,
M. BELTZER
MB:pc
*Typographical error, should be 0.01 per telecon with
M. Beltzer
F-7
-------
TABLE F-7. X-RAY FLUORESCENCE ANALYSIS FOR SULFUR
OF SwRI FUEL EM-236-F
RESEARCH AND ENGINEERING COMPANY __ .
P.O. BOX 51. LINDEN. N.J. 07036
PRODUCTS RESEARCH DIVISION
R.fi. CECIL
Director
Fuels ResRarct) Laboratory
June 25, 1975
Sulfur Analysis of SWRI Fuels
Ref. No. 7512 1524
Mr. Melvin Ingalls
Southwest Research Institute
8500 Culebra Road
Post Office Drawer 28510
San Antonio, Texas 78284
Dear Mel:
The results of the sulfur analyses of the fuel samples you
sent are as follows:
Sample
Designation
1
2
3
4
5
6
7
8
9
EM
EM
EM
EM
EM
EM
EM
EM
EM
EM 10
EM 11
EM 12
EM 13
EM 14
EM 15
EM 16
EM 17
EM 18
EM 19
EM 20
Fuel Sulfur,
Wt. %
0.030
0.030
0.027
0.030
0.031
0.029
0.031
0.030
0.027
0.032
0.031
0.031
0.025
0.031
0.027
0.030
0.030
0.025
0.032
0.030
Please let me know if we can "be of further help to you.
Yours truly,
M. BELTZER
MB:ph
F-8
-------
TABLE F-8. COMPARISON OF EXXON X-RAY AND
ARMY F&L LAB LAMP SULFUR
Fuel
EM-208F
EM-212F (w/o thiophene)
EM-212 (w/ thiophene)
EM-236 Barrel 1
11 Barrel 2
" Barrel 3
11 Barrel 4
" Barrel 5
11 Barrel 6
" Barrel 7
" Barrel 8
" Barrel 9
" Barrel 10
Exxon
X-Ray
0.053
0.010
0.045
0.030
0.030
0.027
0.030
0.031
0.029
0.031
0.030
0.027
0.032
Army F&L Lab
Lamp Sulfur
0.0528
0. 0440
0.030
0.030
0.031
0.032
0.032
0.031
0.033
0.032
0.029
0.031
F-9
-------
TABLE F-9. ANALYSIS OF SULFUR IN TEST FUELS
BY U. S. ARMY F&L LABORATORY
F&L Lab Fuel
Report No. Designation
Number of
Times Analyzed
Average Percent
Sulfur
3730
3818
3926
4111
4236
4257
4303
1378(5/12/76)
EM-208-F(B)
EM-212-F
EM-236-F (1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
EM-243-F
EM-246-F
EM-250-F
EM-254-F
EM-258-F
3
3
2
2
1
1
1
1
1
1
1
1
3
1
2
2
2
0.0528
0.0440
0.030
0.030
0.031
0.032
0.032
0.031
0.033
0.032
0.029
0.031
0.042
0.246
0.041
0. 041
0.041
F-10
-------
APPENDIX G
RESULTS FROM INDIVIDUAL TESTS OF
SULFATE CHARACTERIZATION CARS
-------
TABLE G-l. EXHAUST EMISSIONS FROM A 1972 PLYMOUTH FURY
WITH A 360 CID ENGINE (NO CATALYST)
(LEADED FUEL, 0.051 PERCENT SULFUR)
Exhaust Emissions , <;
Test
Date
10/22/74
11/7/74
11/19/74
11/20/74
1/14/74
2/18/74
Average
10/22/74
11/7/74
11/18/74
11/19/74
2/17/75
2/18/75
Average
11/8/74
11/8/74
11/18/74
11/21/74
1/13/75
1/13/75
Average
Test
Type
'75 FTP
'75 FTP
'75 FTP
•75 FTP
• 75 FTP
'75 FTP
'75 FTP
48 kph
48 kph
48 kph
48 k£h
48 kph
48 kph
48 kph
96 kph
96 kph
96 kph
96 kph
96 kph
96 kph
96 kph
Test
Duration
90 min.
90 min.
90 min.
90 min.
90 min.
90 min.
90 min.
60 min.
60 min.
60 min.
60 min.
84 min.
84 min.
HC
2.91
3.04
3.20
2.42
2.89
S=.34
Cv=12%
1.59
1.35
1.59
1.80
1.52
1.24
1.51
S=.2Q
Cv=13%
1.07
0.99
1.33
0.92
1.08
S=.18
Cv=17%
CO
54.42
54.37
60.45
50.91
55.04
3.96
7%
25.5
23.5
37.8
27.3
32.6
28.2
29.15
5,22
18%
7.1
5.4
9.8
4.7
6.75
2.27
34%
NOX
3.68
3.19
3.07
2.80
3.19
.37
12%
0.35
0.20
0.51
0.66
0.50
0.44
0.17
39.4%
2.62
3.14
4.60
4.15
3.63
.91
25%
[/km mg/km Percent Percent
BCA BCA Fuel S Fuel S Total
SO? H2SO4 as SO2 as H2SO4 Recovery
On £ ___ QA 1 __—
01 A — — — QA 1 _ —
01 A — — — QQ t: __ _
, 09 — y /*o - - -
»08 ob. £. —
— -. Q-l Q
ft
OAQ _.._ T n~7 n -. — _
Ono -.—— T m "7 — _ —
• Uo — J.UJ* / — — *~ —
-------
TABLE G-2. EXHAUST EMISSIONS FROM A 1972 PLYMOUTH FURY
WITH A 360 CID ENGINE (NO CATALYST)
(UNLEADED FUEL, 0.51 PERCENT SULFUR)
Exhaust Emissions/ g/km
U)
Test
Date
1/28/75
1/29/75
Average
1/27/75
1/28/75
Average
1/29/75
1/29/75
Average
Test
Type
'75 FTP
•75 FTp
'75 FTP
48 kph
48 kph
48 kph
96 kph
96 kph
96 kph
Test
Duration
90 min.
90 min.
90 min.
60 min.
60 min.
60 min.
HC
2.73
2.52
2.63
0.96
1.45
1.21
0.89
1.07
0.98
CO
52.59
50.00
51.30
33.7
30.3
32.0
6.3
8.4
7.4
NOV
3.76
3.14
3.45
0.38
0.38
0.38
3.64
3.67
3.66
BCA
SO?
1.71
1.46
1.59
0.08
0.08
0.08
0.08
0.08
0.08
mg/km
BCA
H2SO4
2.30
1.86
2.08
0.11
0.13
0.12
2.70
1.00
1.85
Percent
Fuel S
as SO?
97.1
102.5
99.8
87.1
90.9
89.0-
88.7
87.3
88.0
Percent
Fuel S
as H2SO4
0.8
0.9
0.9
0.1
0.1
0.1
2.1
0.7
1.4
Total
Recovery
97.8
103.5
100.8
87.3
91.0
89.1
90.8
88.0
89.4
-------
TABLE G-3.
EXHAUST EMISSIONS FROM A 1974 HONDA CVCC CIVIC
WITH A ISOOcc ENGINE
(Unleaded Fuel, 0. 041 Percent Sulfur)
2/11/75
2/12/75
2/10/75
2/19/75
£ 2/10/75
3/12/75
Run
Test Duration
Type (Min.)
.75 FTP
'75 FTP
Avg. '75 FTP
48 kph 90
48 kph 90
Avg. 48 kph
96 kph 60
96 kph 30
Avg. 96 kph
Exhaust Emissions g/km
HC
0.83
0.59
0.71
0.09
0. 05
0.07
0.04
0.00
0.02
CO
2.41
2.45
2.43
1.07
1.08
1.08
0.89
0.23
0.56
NOX
0.60
0.50
0.55
0.44
0.29
0.37
1.45
1.34
1.40
BCA
so2
0, 05
0.05
0.05
0.03
0.04
0.04
0.05
0.04
0.04
mg/fcm
BCA
H2S04
0. 5
0.3
0.4
0.2
0. 2
0.2
0.6
1. 1
0.9
Percent
Fuel S
as SO2
77.7
85.7
81.7
92. 3
133.6
113.0
127.2
83.5
105.4
Percent
Fuel S
as H2SO4
0.6
0.4
0.5
0.5
0. 5
0.5
1.0 •
1.7
1. 3
Percent
Fuel S
Recovered
78.3
86. 1
82.2
92.8
134. 1
113. 5
128.2
85.2
106.7
-------
TABLE G-4.
EXHAUST EMISSIONS FROM A 1975 FORD GRANADA
WITH A 351 CID ENGINE (NO CATALYST)
(Unleaded Fuel, 0.041 Percent Sulfur)
9
i
Ul
Test
Date
3/7/75
3/10/75
3/6/75
3/7/75
3/6/75
3/7/75
Run
Exhaust
Emissions, g/km
Test Duration
Type
175 FTP
'75 FTP
(Min. )
Average '75 FTP
48 kph
48 kph
Average 48 kph
96 kph
96 kph
Average 96 kph
30
30
30
30
HC
1.05
0.97
1.01
0.26
0.19
0.22
0. 16
0. 18
0. 17
CO
5.68
5.86
5.77
1.21
1.09
1. 15
1.75
1.83
1.79
NOX
2.02
2. 11
2.07
0.54
0.44
0.49
1.85
1.38
1.62
'BCA
S02
0. 10
0. 11
0. 10
0.05
0.06
0.06
0.06
0.06
0.06
mg/km
BCA
H2SO4
0.5
0.4
0.5
0.2
0. 1
0. 1
0.3
0.2
0.2
Percent
Fuel S
as SO?
91.0
89.0
90.0
83.6
81.5
82.6
89.4
108. 2
98,8
Percent
Fuel S
as H2SO4
0.3
0.2
0.3
0. 1
0. 1
0. 1
0.3
0.2
0. 2
Percent
Fuel S
Recoveret
91.3
89. 2
90.3
83.7
81.6
82.7
89.7
108.4
99.0
-------
NOTE:
For Characterization Tests of:
1975 Federal Plymouth Gran Fury
1975 Federal Chevrolet Impala
1975 California Plymouth Gran Fury
1975 California Chevrolet Impala
See the 3200 km tests of cars EM-1, 2, 3 and 4 in Appendix H.
G-6
-------
TABLE G-5. EXHAUST EMISSIONS FROM A 1975 MERCEDES 240D
(Diesel fuel, 0. 23% Sulfur)
Date
H/18/75
H/19/75
1/20/75
Average
H/18/75
H/19/75
H/20/75
Average
H/18/75
Jl/l9/75
H/20/75
Average
H/18/75
H/19/75
Jl/20/75
Average
H/18/75
H/19/75
Jl/20/75
Average
E/km
Test Type
FTP
FTP
FTP
SET-7
SET-7
SET-7
SET-7
SET-7
SET-7
FET
FET
FET
SET-7
SET-7
SET-7
'18/75 SET 7
jj'19/75 SET-7
1/20/75 SET-7
Average
U/19/75 48
'-1' 20/75 48
Average
1l/l9/75 48
'I '20/75 48
Average
J!'1 9/75 96
j /20/75 96
Average
Ij/l9/75 96
'20/75 96
Verage
Accel
Accel
kph S/S
kph S/S
Accel
Accel
kph s/S
kph S/S
Duration HC
23 min
23 min
23 min
23 min
23 min
23 min
12 min
12 min
12 min
23 min
23 min
23 min
23 min
23 min
23 min
20 min
20 min
20 min
20 min
10 min
10 min
10 min
10 min
0.23
0.05
0.00
0.09
0. 10
0.04
0.02
0.05
0.05
0.02
0.02
0.03
0.04
0.05
0.05
0.05
0.08
0.06
0.03
0.06
0.05
0.01
0.03
0.03
0.04
0.02
0.03
0.02
0.02
0.02
0.01
0.03
0.02
0.00
0.02
0.01
CO
0.43
0.49
0.48
0.47
0.36
0.38
0.27
0.34
0.34
0.37
0.30
0.34
0.31
0.31
0.24
0.29
0.38
0.33
0.31
0.34
0.33
0.36
0.33
0.34
0. 14
0.04
0.09
0.20
0.09
0. 15
0.38
0.36
0.37
0.40
0.31
0.36
NOX
0.78
0.77
0.78
0.78
0.74
0.90
0.74
0.79
0.71
0.83
0.77
0.77
0.71
0.82
0.68
0.74
0.71
0.82
0.78
0.77
0.78
0.81
0.79
0.79
0.52
0.44
0.48
0.56
0.49
0.53
1.00
0.90
0.95
1. 16
0.99
1.08
S02
0.392
0.283
0.332
0.336
0.363
0.324
0.290
0.326
0.213
0.277
0.279
0.256
0.356
0.296
0.245
0. 299
0.315
0.310
0.344
0.323
0.342
0.277
0.229
0.283
0.367
0.248
0.308
0.176
0. 124
0. 150
0.313
0.236
0.275
0.375
0.361
0.368
mg/km
H2SO4
9.35
12.77
8.27
10. 13
9.75
11.48
8.31
9.85
10.05
11.02
9.91
10.33
9.39
9.61
10.21
9.74
10.22
11.03
9.67
10.31
11.42
11.70
9.89
11.00
3.23
2.12
2.68
3.69
3.00
3.35
21.85
22.63
22.24
13.56
12.96
13.26
H2SO4 SO2 as
as % of % of
Fuel S
1.78
2.32
1.55
1.88
2. 17
2.50
2.06
2. 24
2.29
2.37
2.28
2.31
2.33
2.24
2.86
2.48
2.32
2.44
2.20
2.32
2.56
2.58
2.25
2.46
1.07
0.87
0.97
1.26
1.04
1. 15
4. 53
4.74
4.64
2.95
2.94
2.94
Fuel S
113.91
78.72
95.49
96.04
123.57
108.35
110.28
114.07
74. 22
90.91
98.46
87.86
134.95
105.63
105.31
115.30
109.52
104.72
119.90
111.38
117.56
93.59
79.93
97.03
185.72
155.40
170.56
91.99
65.93
78.96
99.21
75.68
87.45
124. 62
125.25
124.94
Total
Recovery
115.68
81.04
97.05
97.92
125. 74
110.86
112.35
116.32
76.51
93.28
100.74
90. 18
137.28
107.87
108. 18
117.78
1 1 1 . 84
107. 16
122. 11
113.70
120. 12
96. 17
82. 18
99.49
186.79
156.27
171. 53
93. 25
66.97
80. 11
103.75
80.42
92.09
127.56
128. 19
127.88
G-7
-------
TABLE G-6. EXHAUST SULFUR RECOVERY USING METHOD 8
FOR A 1972 PLYMOUTH WITH 360 CID ENGINE
(Leaded Fuel, 0. 051% Sulfur)
Test
Date
10/22/74
11/07/74
11/18/74
2/17/75
2/18/75
Average
Test
Type
48 kph
48 kph
48 kph
48 kph .
48 kph
48 kph
Run
Duration
90 min.
90 min.
90 min.
90 min.
90 min.
Exhau st
SO2
0.07
0.06
0.08
0.05
0.07
0.07
Emissions g/km
H2SO4
none detected
none detected
none detected
none detected
none detected
none detected
Percent
Fuel S
as SO2
80
77
88
53
74
74
Percent Percent
Fuel Fuel
as HoSO^ Recovered
80
77
88
53
74
74
00
11/08/74
11/08/74
11/18/74
11/21/74
Average
96 kph
96 kph
96 kph
96 kph
96 kph
60 min.
60 min.
60 min.
60 min.
none detected
none detected
none detected
none detected
none detected
70
84
78
J72
76
70
84
78
TL
76
-------
TABLE G-7. EXHAUST SULFUR RECOVERY USING METHOD 8
FOR A 1972 PLYMOUTH WITH 360 CID ENGINE
(Unleaded Fuel, 0. 051% Sulfur)
Test
Date
1/27/75
1/28/75
Average
Test
Type
30 mph
30 mph
30 mph
Run
Duration
90 min.
90 min.
Exhaust Emissions g/km
SO7
0.06
0.06
0.06
H7S04
0.0055
0.0043
0.0049
Percent
Fuel S
as SO?
70
75
72 .
Percent
Fuel as
H?SOA
3.9
3.2
3.6
Percent
Fuel
Recovered
74
78
76
1/29/75
1/29/75
Average
60 mph
60 mph
60 mph
60 min.
60 min.
0.07
0.07
0.07
0.0037
0.0033
0.0035
85
75
80
2.8
2.3
2.6
88
77
83
-------
I
H
O
TABLE G-8. EXHAUST SULFUR RECOVERY USING METHOD 8
FOR A 1974 HONDA CIVIC WITH A ISOOcc CVCC ENGINE
{Unleaded Fuel, 0. 041 Percent Sulfur)
Test
Date
2/10/75
2/19/75
Average
2/06/75
2/10/75
Average
Test
Test Duration
Type -Min.
30 mph
30 mph
30 mph
60 mph
60 mph
60 mph
90
90
60
60
SO2
by Method 8
0, 03
0.03
0. 03
0.04
0.04
0.04
H2SO
by Method 8
0.0017
0.0015
0.0016
0.0050
0.0032
0.0041
Percent
Fuel S
as SO2
81. 5
84. 3
83.0
83.7
90.4
87.0
Percent
Fuel S
as H2SO4
3. 3
3.2
3.2
8.5
5.2
6.8
Percent
Fuel S
Recovered
84.8
87. 5
86.2
92.2
95.6
93.9
-------
APPENDIX H
SUPPORTING INFORMATION
FOR DISTANCE ACCUMULATION CARS
-------
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF AIR AND WATER PROGRAMS * OFFICE OF MOBILE SOURCE AIR POLLUTION CONTROL
A/C MO. ,17 December 20, 1973 PAGE 1 OF.JL PAGES
SUBJECT: Alternate Mileage Accumulation Procedure
A. Purpose
The purpose of this Advisory Circular is to provide an alternate mileage
accumulation driving schedule for use on public roads where the Durability Driving
Schedule as specified in Appendix IV of 40 CFR Part 85 exceeds the legal maximum
speed limit.
B( Background
40 CFR 85.074-7, 85.075-7, 85.175-7, and 85.275-7 provide for a modified
Durability Driving Schedule if "approved in advance by the Administrator." The
reduction in maximum speed limits on public roads to meet the current and'
anticipated fuel shortages establishes a need for an Alternative Durability
Driving Schedule operating within the lowered speed limits.
C. Applicability
This circular is effective immediately and is applicable to gasoline-
fueled and Diesel light duty vehicles and light trucks.
D. Procedure
1. Appendix IV of 40 CFR Part 85 describes the basic driving schedule
consisting of 11 laps of a 3.7 mile closed course and prescribes the driving mode
and speed for each lap.
2. To accommodate highway speed limits, an alternate driving schedule has
been devised. In this alternate driving schedule the first nine laps will be driven
in the manner described in Appendix IV of 40 CFR Part 85. The 10th lap is to be drl^
at a constant speed of 50 or 55 miles per hour (raph) (depending on which speed liB>lt
io in effect) after a normal acceleration from the stop following lap number 9 nnd J
proceeding to n normal deceleration to a stop before Inp 11. The llth lap is begun v
a wide-open-throttle acceleration to 50 or 55 mph, as applicable, a fast decelerati°°
to a stop, and three subsequent wide-open-throttle accelerations and fast decelera-
tions at evenly spaced intervals in the 3.7 mile lap.
H-2
-------
ENVIRONMENTAL PROTECTION AGENCY- OAWP/MSAPC "A/C HO.JL. PAGEJ_OF 3
E. Discussion
1. A comparison of the present 70 mph maximum speed durability driving
schedule and the alternate 50 or 55 mph schedules Is shown In Enclosure 1. It also
serves as a guide to those manufacturers who elect to use the alternate 50 or 55 mph
maximum speed schedules In laying out a public road route..
2. The comparison is based on an assumed uniform acceleration rate of 3 mph
Per second (4.4 ft/sec2) and a uniform wide-open-throttle acceleration rate of 5 mph
per second (7.3 ft/sec2). The rates of deceleration are also assumed to be uniform
with normal deceleration being 6 mph per second (8.8 ft/sec2) and a fast rate of
deceleration being 10 mph per second (14.7 ft/sec2).
3. The actual average speed may be somewhat less than the calculated
average speed since no allowance Is made for driver reaction time.
Approval of Mileage Accumulation Procedure.
1. Each application for certification must Include a description of the
toUeage accumulation procedure. The regulations require that the procedure be
aPproved or disapproved, in writing, by'EPA. EPA will approve an alternate
Procedure as generally described In this Advisory Circular for manufacturers
who accumulate mileage on public roads. Mileage accumulated on dynamometers
°r test tracks will continue to be required to be consistent with the driving
schedule specified in Appendix IV of 40 CFR Part 85.
2. As in the past, EPA will also approve procedures which have
substantially the same average speed, distribution of speeds, number of stops
Per mile, and number of accelerations per mile to the various speeds.
Eric 0. Stork
Deputy Assistant Administrator
for Mobile Source Air Pollution Control
H-3
-------
U.S. ENVIRONMENTAL PROTECTION AGENCY- OAWP/MSAPC
A/C NO.21. PAGE>_!_OFj-
ENCLOSURE 1
Driving Mode
Stops
Normal acceleration from stop
Normal acceleration from 20 mph
Wide-open-throttle acceleration
and fast deceleration
Idle tine
Speed-mph
30
35
40
45
50
55
70
Variable (acceleration and
deceleration)
TOTAL
70 mph
•Top Speed
0.96
0.91
1.11
0.05
13.64 sec
Events per mile
55 mph
Top Speed
1.01
0.91
1.11
0.10
13.64 sec
Percent of Total Miles
50 mph
TOP Speed
1.01
0.91
1.11
0.10
13.64 sec
16.4
23.4
21.9
6.8
8.6
8.1
14.8
100.0
16.4
23.4
21.9
6.8
16.5
15.0
100.0
16.4
23.4
21.9
6.8
16.7
14.8
100.0
Average speed, total distance
traveled divided by total
time (Including idle time)
Hours to complete 50,000
miles
30.21 mph
1655
29.70 mph
1683
29.56 nph
1691
H-4
-------
Events Per Mile
Driving Mode
55 mph Top Speed
Stops
Normal Accelerations From Stop
Normal Accelerations From ZOmph
Wide-Open Throttle Accelerations
And Fast Deceleration
Idle Time
SwRI Course
1.02
0.92
1. 11
0.09
AC No. 37
1.01
0. 91
1. 11
0. 10
13.84 Sec.
Light
13.64 Sec.
Institute
road
South Lap: "A" to "H" - 4. 8 km (3. 0 mi)
North Lap: "H" to "A" - 4. 7 km (2. 9 mi)
11 Laps = 52. 3 km (32. 5 mi)
Loop
410 N. W.
Lap
1
2
3
4
5
6
7
8
9
10
11
Speed
km/hr
64
48
64
64
56
48
56
72
56
89
89
mi/hr
40
30
40
40
35
30
35
45
35
55
55
FIGURE H-l.MODIFIED (AUTOMOBILE) DURABILITY DRIVING SCHEDULE
FOR MILEAGE ACCUMULATION ON PUBLIC ROADS
H-5
-------
SOUTHWEST RESEARCH INSTITUTE
8500 CULEBRA ROAD • POST OFFICE DRAWER 28510 • SAN ANTONIO, TEXAS 78284
January 13, 1975
MODIFIED DURABILITY DRIVING SCHEDULE FOR
MILEAGE ACCUMULATION ON PUBLIC ROADS
1. Leave Institute Fleet Laboratory
2. Proceed to CULEBRA ROAD via INSTITUTE ROAD, 20 & 40 m.p.h.
3. Stop at CULEBRA
4. Left turn onto CULEBRA and proceed to "A", 410, at 40 m.p.h.
(Distance from Fleet Laboratory to "A" is 2.3 miles)
5. Stop at "A", idle 15 sec.
6. Start lap prompter at 1.
7. Accelerate from stop, turn left on access road
8. After left turn, accelerate to lap speed and then decelerate
at "B" to 20 m.p.h., as traffic permits.
9. Accelerate to lap speed as you turn onto 410. Continue on 410
to next exit and then decelerate at "C" to 20 m.p.h., as traffic
permits then accelerate to lap speed.
11. Continue on FRONTAGE ROAD until a full stop can be safely made
at area of point "D". Idle for 15 sees.
12. Accelerate from stop to lap speed and pull onto 410 at next ramp.
Continue on 410 to exit ramp.
13. Take exit, then decelerate to 20 m.p.h., at "E".
14. Accelerate to lap speed.
15. Stop at "F" and idle 15 sees.
16. Accelerate to lap speed and continue to "G". Decelerate to
20 m.p.h., at "G" then accelerate to lap speed.
H-6
SAN ANTONIO, HOUSTON, CORPUS CHRIST), TEXAS, AND WASHINGTON, D.C.
-------
17. Stop at traffic light if red, "H" (this can be as long as
33 sees.) If the light is green, proceed and make an additional
stop along the North lap as traffic permits.
18. As you pass "H" stop light, push the "lap" prompter and observe
the "lap speed".
19. Left turn on MARBACH under 410. Stop at light "I". If light is
green, proceed on North lap and make additional stop as traffic
permits.
20. Left turn to 410 access at "I".
21. Proceed up 410 to "J" at lap speed.
22. Decelerate at "J" to 20 m.p.h., and then accelerate to lap speed.
23. Continue to "K" at lap speed.
24. Decelerate at "K" to 20 m.p.h., and then accelerate to lap speed.
25. Take ramp to 410 and proceed up 410 to exit ramp at "L".
26. Decelerate at "L" to 20 m.p.h., then accelerate to lap speed.
27. Proceed to "M", then stop and idle 15 sees.
28. Accelerate to lap speed then decelerate at "N" to 20 m.p.h., and
then accelerate to lap speed.
29. Take ramp to 410 and continue on 410 to CULEBRA exit ramp.
30. Take CULEBRA exit to stop at "A". Idle 15 sees.
31. Push "lap" prompter for next lap and lap speed.
32. This begins the 3rd lap.
33. Continue with South lap - North lap sequence until lap number 9
is complete.
34. Lap number 10 is run at a steady 55 m.p.h., on 410. Get on 410
at first entrance ramp following the stop at the end of lap
number 9 and stay on 410.
35. Lap 10 is completed when you stop at "A" or "H" after pulling
off onto the ramp nearest the stop.
36. After stop at "A" or "H" Lap Number 10 is complete.
H-7
-------
37. Punch lap button for Lap 11.
38. Accelerate then stop at "B".
39. W.O.T. accelerate to lap speed then fast deceleration
to stop at "D".
40. W.O.T. accelerate to lap speed then fast deceleration to stop
at "F".
41. W.O.T. accelerate to lap speed then normal deceleration to stop
at "H".
42. This completes one cycle of the mileage accumulation.
43. The next cycle of the schedule begins at "H".
44. Complete as many steps per shift as time will allow, then
return to Fleet Laboratory.
H-8
-------
TABLE H-l. MAINTENANCE SCHEDULE FOR 1975 PLYMOUTH GRAN FURY
REQUIRED MAINTENANCE SERVICES FOfl EMISSION CONTROL AND PROPER VEHICLE PERFORMANCE
MILEAGE INTERVALS MILEAGE IN THOUSANDS) 5 | 10 |15 | 20 | 25 | 30 | 3S | 40 | « )
I59JNE1DLE SPEED 4 FAST
CHECK & RESET AS NECESSARY AT INITIAL 5,000 MILES
ENGINE OIL
CHANGE EVERY SIX MONTHS
on
I HOSES
S*25yHETOR CHOKE SHAFT
REPLACE AT INITIAL OIL CHANGE AND EVERY 2ND OIL CHANGETHEREAFTER
EVERY SIX MONTHS
a PIVOT PIN
SYSTEM
£**Nj(CA8E INLET AIR CLEANER
!?*J!!i£OLDMEAT CONTROL VALVE
fJLgjgy BELT (IF SO EQUIPPED) __
. TIMING, IDLE SPEED. IDLE MIXTURE
At« FILTEB
£*5flURETOR AIR FILTEB
KCASE VENT VALVE
gggjTiyE CRANKCASE VENT VALVE
^!5?_SJOBM1E CAWS1ER FILTER ELEMENT
_
I*HAUST QAS RECinCULATION SYSTEM
i (LEADED GAS)
gg*S*_PMJGS (WITH CAT. UNLEADED 6AS)
igjjjJJON CABLES. D1ST. CAP > ROTOR
°Jj£!gEJPARK ADVANCE CONTROL VALVE
*H!gMATIC CHOKE
^VE LASH <6 CYLINDER ENGINES)
[OVER TEMP, PROTECTION SYSTEM
to nection ancl service should also be performed
.„ fr°'ect your emissions warranty. 'Long Life
"terns. "Long (_ife Plugs—50,000 miles when
INSPECT EVERY SIX MONTHS
CHECK AND SERVICE AS REQUIRED
EVERY SIX MONTHS
CLEAN EVERY 12 MONTHS OR
APPLY SOLVENT
CHECK CONDITION AND TENSION
CHECK AND ADJUST AS REQUIRED
CHECK OPERATION
CHECK AND REPLACE AS REQUIRED
CHECK OPERATION
CHECK AND ADJUST AS REQUIRED
CHECK AND ADJUST AS REQUIRED
CHECK AND REPLACE AS 3EQUIREC
m,minrt!nn it ohserved ot suspected. Retain receipts lor all vehicle emission
.oTJ! mn« wh'er^e7w?t° leadSd gas and not equipped w«h catalyst emission
used with unleaded gas.
services
control
^COMMENDED MAINTENANCE SERVICES
who rt °-W'"9 Certified Car Care maintenance services are recommended by the engineers
__ "^signed your car to provide the maximum operating elliciency and enjoyment.
ING.
B. A PLSTC. COMPMTS.
, ,
SCK TOK^EAKS, MISSING
R DAMAGED PARTS
INSPECT FLUID LEVEL
REAR AXLE (ALL)
• INSPECT FLUID LEVEL
^ -N (MANUAL) (1)
rRANSMlSSION (AUTOMATIC)
CHANGE OIL
LUBRICANT
B»AKE AND POWER STEERING HOSES
CHANGE FLUID, FILTER
.^AOTUST BANDS
CHECK FOR DETERIORATION &
LEAKS
HOSES
*lf» CONDITIONED CARS
CHECK FOR DETERIORATION OR I
LEAKS ;
CHECK^ELTS, SIGHT GLASS*ND .
OPERATION OF CONTROLS
AND STEERING LINKAGE
INSPECT SEALS
INSPECT SEALS
CHECKPONDITION AND
TENSION
CONTROL ARM BUSHINGS
C°OLINQ SYSTEM
ROTATE,
CHECK COOLANT LEVEL
DRAmffLUSH AND REFILL
AMPS (2 WIRE/SCREW)^
~
TIGHTEN
INSPECT)
BEARINGS
INSPECT (Z) LUBRICATE f3?
AND TIE HOD ENDS
LUBRICATE
NORMAL
ADDITIONAL SERVICES
REQUIRED WITH
TRAILER TOW
(3} vu"1^ Trailers with Manual Transmission equipped vehicles is not iccommendod |2> Whenevei drums or icsors .ire removed U> mspeol i servicn brake syslom
HOte^nevsr 'he hrake drums or disc brake rotors are resurfaced.
driving co'irlilitms sr special erjuipmenl such as high pe/lofmance cr heavy duly options may require special service refomaiendiii.ni'>
WOT*.
e:
H-9
-------
TABLE H-2. MAINTENANCE SCHEDULE FOR 1975 CHEVROLET 1MPALA
COMPLETE VEHICLE MAINTENANCE SCHEDULE
Color Code: Q Lubrication and General Maintenance | Safety Q Emission Control
When To Perform Services
(Months or Miles, Whichever Occurs First)
Item
No.
Services
nWNFR'S SFRVIPF IOP ilUilrxtl lnse" Montt>- Day' And Mi1ea9e I'-*- May/5/6612) In
OWNER S» SERVICE LOG (Miles) Colmn C|osestTo Mi|eagewhen Service Is Performed
7,500
1S.ODO 22,500
30,000
37,500
45,000
Lubrication and General Maintenance
Every 6 Months or 7,500 Miles
At 1st Oil Chg.— Then Every 2nd
See Explanation
Every 12 Months
Every 12 Months or 1 5,000 Miles
Every 30,000 Miles
1
2
3
4
5
6
7
8
9
10
11
12
Every 6 Months or 7,500 Miles
Every 12 Months or 15,000 Miles
13
14
15
16
17
18
19
20
21
22
"Chassis Lubrication
•'Fluid Levels Check
"Engine Oil Change
'Oil Filter Change
Tire Rotation (Steel- Belted Radiaf)
Rear A
-------
TABLE H-3. 1975 49-STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolithic Catalyst, 0. 0415% Sulfur Fuel
Emissions Summary - 0 Kilometres
ffi
Date
4/24/75
4/25/75
Avg.
4/24/75
4/25/75
Avg.
4/24/75
4/25/75
Avg.
4/24/75
4/25/75
Avg.
4/24/75
4/25/75
Avg.
Test type/
direction
'75 FTP
'75 FTP
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
HC
0.36
0.43
0.39
0. 16
0. 11
0. 14
0.03
0.03
0.03
0. 07
0.05
0.06
0.04
0.03
0.04
CO
10.58
8.87
9.73
0.38
0.38
0.01
0.00
0.01
0.83
0.46
0.64
3.09
2.02
2.56
g/km
NOX
1.07
1.08
1.08
0.85
0.72
0.78
0.78
0.59
0.68
1.33
1.36
1.34
0.50
0.38
0.44
S02
0.063
0.075
0.069
0.017
0.033
0.026
0.009
0.006
0.008
0.237
0.237
0.059
0.093
0.076
H2S04
0.00114
0.00081
0.00098
0.00055
0.00054
0.00054
0.00034
0.00029
0.00032
0.01310
0.01310
0.00015
0.00021
0.00018
% Fuel S
as S
in SO2
42.5
50.9
46.7
26.4
49.5
37.8
15.30
10.48
12.89
323.67
323.67
86.05
133.60
109.83
% Fuel S
as S
in H2SO4
0. 53
0.36
0.45
0.55
0.53
0, 54
0.35
0.30
0.32
11.68
11.68
0. 14
0. 19
0. 16
Total
Recovery
43 n
51.3
47.2
26.95
50.0
38. 5
15. 65
10.78
13.22
335.35
335.35
86. 19
133.79
lOQ QQ
-------
TABLE H-4.
1975 49-STATE CHEVROLET IMPALA (SwRI CAR EM-2)
Pelleted Catalyst, 0. 0415% Sulfur Fuel
Emissions Summary - 0 Kilometres
Date
5/30/75
6/2/75
Avg.
5/30/75
6/2/75
Avg.
£ 5/30/75
,L 6/2/75
^ Avg.
5/30/75
6/2/75
Avg.
5/30/75
6/2/75
Avg.
Test type/
direction
• 75 FTP
'75 FTP
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
HC
0.60
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
37
49
04
07
06
04
11
08
09
09
09
01
01
01
CO
15.
10.
13.
0.
1.
0.
1.
5.
3.
0.
0.
0.
0.
1.
0.
e/km
% Fuel S % Fuel S
as S as S Total
NOX SO2 * H2SO4 in SO 2* in H2SO4 Recovery*
94
89
42
52
06
79
37
71
54
73
81
77
17
21
69
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
0.
0.
0.
99
93
96
32
24
28
19
11
15
02
03
03
72
59
66
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
00090
00025
00058
00066
00021
00044
00019
00000
00009
00739
00506
00623
00159
00477
00316
0.
0.
0.
0.
0.
0.
0.
0.
0.
5.
3.
4.
1.
3.
2.
41
13
27
46
16
31
13
00
07
42
81
62
31
73
52
* SO2 not taken
-------
TABLE H-5,
1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR EM-3)
Monolithic Catalyst, 0. 0415% Sulfur Fuel)
Emissions Summary - 0 Kilometres
Date
6/25/75
6/26/75
Avg.
6/25/75
6/26/75
Avg.
6/25/75
6/26/75
6/25/75
6/26/75
Avg.
6/25/75
6/26/75
Avg.
Test type/
direction
'75 FTP
'75 FTP
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
K/km
HC
0.44
0.67
0.56
0.04
0.04
0.04
0.03
0.03
0.03
0.04
0.02
0.03
0.03
0.02
0.02
CO
6.58
7. 77
7. 18
0. 24
0. 17
0.20
0.03
0.06
0.04
1.56
0.05
0.81
1.04
0.09
0.56
NOX
0.65
0.72
0. 68
0.72
0. 70
0. 71
0. 80
1. 15
0. 98
0.45
0. 57
0.51
0.42
0. 50
0.46
SOz
0. 132
0. 162
0. 147
0.024
0.010
0.017
0.014
0.011
0.013
0. 149
0. 119
0. 134
0.021
0.026
0.024
H2S04
0.00113
0.00210
0.00161
0.00013
0.00034
0.00023
0.00612
0.01074
0.00843
0.02875
0.02739
0. 02807
0.01350
0.02670
0.02010
% Fuel S
as S
in SOz
83. 86
103.66
93.76
35.44
14. 76
25. 10
23. 37
17. 13
20.25
175.82
158.65
167. 24
27. 36
32.90
30. 13
% Fuel S
as S
in HzSO4
0.49
0. 91
0.70
0. 12
0.33
0.22
6.64
10. 88
8. 76
22. 22
23. 85
23.04
11. 23
22. 30
16.77
Total
Recovery
84. 07
104. 57
94.32
35. 56
15.09
25. 33
30.01
28.00
29.00
198.04
182. 50
190. 27
38.59
55. 20
46. 90
-------
TABLE H-6.
1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst, 0.0415% Sulfur Fuel)
Emissions Summary - 0 Kilometres
Date
5/27/75
5/29/75
6/19/75
Avg.
5/27/75
5/29/75
6/19/75
Avg.
5/27/75
5/29/75
6/19/75
Avg.
5/27/75
5/29/75
6/19/75
Avg.
5/27/75
5/29/75
6/19/75
Avg.
Test type/
direction
'75 FTP
'75 FTP
'75
Accel to
30
S/S 30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
S/S 60
g/km
HC
0. 29
0.41
0.41
0. 37
0. 13
0.09
0. 13
0. 12
0.04
0.03
0.05
0.04
0.06
0.06
0. 13
0.08
0.02
0.02
0.04
0.03
CO
8.67
10.01
9.40
9.36
0.30
0.30
0.47
0. 36
0.00
0.06
0.00
0.02
2.43
2. 57
1. 22
2.07
0.02
0.01
0.00
0.01
NOX
0.86
0.86
0.84
0.85
0.25
0.26
0. 23
0. 25
0. 21
0. 23
0. 19
0. 21
0. 64
0.65
0.78
0.69
0.64
0.61
0.60
0.62
S02
_
-
0. 120
0. 120
-
-
0.022
0.022
_
-
0.020
0. 020
..
-
0.060
0.060
_
-
0.063
0.063
H2S04
0.00142
0.00116
0.00242
0.00167
0.00327
-
0.00616
0.00472
0.04202
0.02418
0.03555
0. 03555
0.01517
0.00869
0. 02724
0.01703
0.01484
0.01516
0.01710
0.01570
% Fuel S
as S
in SO 2
_
-
75.
75.
-
-
22.
22.
-
-
20.
20.
-
62.
62.
_
-
71.
71.
45
45
08
08
82
82
25
25
71
71
% Fuel S
as S
in H2SO4
0.
0.
1.
0.
2.
r
4.
3.
26,
14.
24.
24.
10.
6.
18.
11.
10.
12.
12.
11,
59
46
01
68
11
08
10
22
42
21
21
84
14
38
79
83
05
65
84
Total
Recovery
_
-
76.46
76.46
_
-
26. 16
26. 16
_
-
45.03
45.03
_
-
80.63
80.63
_
-
84.37
84.37
-------
TABLE H-7. 1975 49-STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolithic Catalyst, 0.0415% Sulfur Fuel)
Emissions Summary - 3200 Kilometres
Date
6/4/75
6/6/75
Avg.
6/4/75
6/6/75
Avg.
6/4/75
6/6/75
Avg.
6/4/75
6/6/75
Avg.
6/4/75
6/6/75
Avg.
Test type/
direction
'75 FTP
'75 FTP
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
g/km
HC
0. 32
0. 32
0. 32
0. 13
0.09
0. 11
0.03
0.03
0.03
0.08
-
0.08
0.02
-
0.02
CO
7.00
7.54
7. 27
0. 54
1. 07
0.81
0.03
0.04
0.04
1.61
-
1.61
1.62
-
1.62
NOX
1. 33
1.49
1.41
0. 94
1. 17
1. 06
0.82
0.84
0.83
1.33
-
1.33
0. 57
-
0.57
SO 2
0. 105
0.052
0.086
0.026
0.028
0.027
0.018
0. 004
0.011
0. 186
_
0.186
0. 122
-
0.122
H2S04
0.00032
0. 00021
0. 00027
0. 00010
0.00014
0.00012
0.00276
0.00203
0.00240
0.00297
_
0.00297
0.00029
_
0.00029
% Fuel S
as S
in SO 2
73.
44.
58.
40.
43.
41.
28.
6.
17.
248.
_
248.
174.
_
174,
00
63
82
39
11
75
41
13
27
74
74
23
,23
% Fuel S
as S
in H2SO4
0.
0.
0.
0.
0.
0.
2.
2.
2.
2.
-
2.
0.
0.
16
12
14
10
14
12
91
20
56
59
59
27
_
27
Total
Recovery
73. 20
44. 75
58. 98
40. 49
43.25
41.87
31. 32
8.33
19.83
251. 33
-
251.33
174. 51
_
174.51
-------
TABLE H-8.
1975 49-STATE CHEVROLET IMPALA {SwRI CAR EM-2)
Pelleted Catalyst, 0.0415% Sulfur Fuel
Emissions Summary - 3200 Kilometres
Date
7/8/75
7/18/75
Avg.
7/8/75
7/18/75
Avg.
ffi 7/8/75
£ 7/18/75
Avg.
7/8/75
7/18/75
Avg.
7/8/75
7/18/75
Avg.
Test type/
direction
t 75 FTp
' 75 FTP
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
R/km
HC
0.46
0.34
0.40
0.09
0.05
0.07
-
0.03
0.03
0.04
0.02
0.03
0.01
0.01
0.01
CO
7.20
11.98
9.59
0.23
1.08
0.66
-
0.06
0.06
0.87
0. 12
0. 50
1. 11
0. 58
0. 85
NOX
1.28
1. 22
1.25
0.30
0.25
0. 28
-
0. 25
0.25
1. 16
0. 98
1.07
0.74
0.76
0.75
SO2
0.056
0.056
0. 073
0. 016
0. 045
_
0,010
0,010
0. 105
0. 132
0. 119
0. 119
0. 177
0. 148
HES04
0.00011
0.00010
0.00011
0.00076
0.00011
0.00044
_
0.00829
0.00829
0.00504
0.00861
0.00428
0.00182
-
0. 00182
% Fuel S
as S
in SO2
45.84
45.84
99.62
21.61
60.62
„
13. 75
13. 75
147.61
173.03
160. 32
157.36
-
157. 36
% Fuel S
as S
in H2S04
0.06
0.05
0.06
0. 62
0. 10
0. 36
_
7. 32
7.32
4.06
7. 39
5.73
1.44
_
1.44
Total
Recovery
45.88
45.88
100. 39
21. 77
61.08
21.05
21.05
151.67
180, 39
166, 03
158.80
_
158. 80
-------
TABLE H-9.
1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR EM-3)
Monolithic Catalyst, 0.0415% Sulfur Fuel)
Emissions Summary - 3200 Kilometres
% Fuel S
Date
7/15/75
7/17/75
Avg.
7/15/75
7/17/75
Avg.
7/15/75
7/17/75
Avg.
7/15/75
7/17/75
Avg.
7/15/75
7/17/75
Avg.
Test type/
direction
'75 FTP
t 75 FTP
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
g/km
HC
0.20
0.32
0.26
0.04
-
0.04
0.02
0.03
0.03
0.04
0.05
0.05
0.02
0.03
0.03
CO
2.90
3. 56
3. 23
0.08
-
0.08
0.00
0.11
0.06
0.44
0.75
0.60
0.02
0.07
0.05
NOX
0.71
0.78
0.75
0.67
-
0.67
0.67
0.56
0.62
0.44
0.42
0.43
0. 39
0.36
0.38
SO2
_
0. 173
0.173
0.042
0.029
0.036
0.019
0.018
0.019
0. 156
0. 146
0. 151
0.023
0.033
0.028
H2S04
0.00616
0. 00616
0.00019
0.00000
0.00010
0.00424
0.00460
0.00442
0.01756
0.02975
0.02366
0:04250
0.04475
0.04365
as S
in SO 2
120.
120
64.
49.
56.
31.
30.
30.
213.
187.
200.
34.
47.
41.
.92
.92
15
62
89
33
04
69
42
19
31
30
81
06
% Fuel S
as
in H;
2.
2.
0.
0.
0.
4.
5.
4.
15.
S
,S04
89
89
20
00
10
46
09
78
,87
25.00
20,
41
41
41
.44
.96
.95
.96
Total
Recovery
123.80
123.80
64. 35
49.62
56.99
35.79
35. 13
35.46
229. 30
212. 19
220.75
76.26
89.76
83.02
-------
TABLE H-10.
1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst, 0.0415% Sulfur Fuel)
Emissions Summary"- 3200 Kilometres
tfl
MH
00
g/km
Date
7/29/75
7/31/75
Avg.
7/29/75
7/31/75
Avg.
7/29/75
7/31/75
Avg.
7/29/75
7/31/75
Avg.
7/27/75
7/31/75
Avg.
Test type
'75 FTP
'75 FTP
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
HC
0.39
0.49
0.44
0. 13
0. 19
0. 16
0.04
0. 10
0.07
0. 16
0.12
0.14
0.03
0.01
0.02
CO
6.69
9.09
7. 89
0.23
0. 18
0.21
0.00
0.07
0.04
1.31
1.85
1.58
0.00
0.04
0.02
NOX
1.07
0.94
1.01
0.20
0. 22
0. 21
0. 17
0.20
0. 19
0.75
0. 68
0. 72
0.69
0. 54
0.62
S02
0.068
0.050
0.059
0.022
0.018
0 . 0 20
0.011
0.011
0.011
0.067
0.044
0.056
0.025
0.018
0. 022
mg/km
H2S04
11. 82
5.96
8.89
16.60
10.00
13. 30
30.36
34. 10
32.23
27.90
27.64
27.77
16. 11
19.62
17.87
% Fuel S
as S
in SO2
50.
37.
MH^HM*
44.
26.
20.
23.
13.
13.
13.
78.
54.
66.
31.
25.
28.
56
72
14
12
75
44
19
71
45
46
07
27
49
93
71
% Fuel S
as S
in H2SO4
5.
2.
4.
12.
7.
10.
24.
26.
25.
21.
22.
21.
13.
18.
15.
68
79
24
68
68
18
42
77
60
40
02
71
02
96
99
Total
Recovery
56.24
40. 50
48. 37
38. 79
28.43
33. 61
37. 61
40.48
39.05
99.86
76.08
87. 97
34.09
44.89
39.49
-------
TABLE H-ll.
1975 49-STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolithic Catalyst, 0.0415% Sulfur Fuel
Emissions Summary - 8050 Kilometres
Date
6/26/75
7/1/75
Avg.
6/26/75
7/1/75
Avg.
6/26/75
7/1/75
Avg.
6/26/75
7 7/1/75
S Avg.
6/26/75
7/1/75
Avg.
6/26/75
7/1/75
Avg.
6/Z6/75
7/1/75
Avg.
6/26/75
7/1/75
Avg.
6/26/75
7/1/75
Avg.
Test type/
direction
'75 FTP
175 FTP
SET-7
SET -7
SET-7
SET-7
FET
FET
FET
FET
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
g/km
HC
0.28
0.31
0.30
0.08
0. 10
0.09
0. 18
0. 12
0. 15
0.08
0. 10
0.09
0.09
0.08
0.09
0.05
0.13
0.09
0.02
0.02
0.02
0.04
0.08
0.06
0.02
0.03
0.03
CO
8.06
8.26
8.16
3.99
6.76
5.38
11.34
7.67
9.51
4.23
5.68
4.96
4.27
4.25
4. 26
0.59
1.53
1.06
0.06
0.02
0.04
0. 28
1.55
0. 92
0. 14
1.96
1.05
NOX
1.44
1.36
1.40
1.26
1.21
1.24
1.00
-
1.00
1.24
1.22
1.23
1.20
1.20
1.20
0.72
0.85
0.79
0.61
1.08
0.85
1.63
2.34
1.96
1.52
0.76
' 1. 14
S02
0. 100
0.078
0.089
0. 130
0. 103
0. 117
0.086
0.084
0.085
0. 049
0.082
0.066
0.054
0.071
0.063
0.024
0.009
0.017
0.002
0.013
0.008
0.090
0. 101
0.101
0.058
0.069
0.064
H2SO4
0.00076
0.00096
0.00086
0.00043
0.00025
0.00034
0.00039
0.00023
0.00031
0.00038
0.00031
0.00035
0.00010
0.00020
0.00015
0.00017
0.00035
0.00026
0.00022
0.00046
0.00034
.
0.00264
0.00264
_
0.00031
0.00031
% Fuel S
as S
in SOz
80.
60.
70.
152.
110.
131.
96.
92.
94.
54
86
70
99
42
71
43
67
55
68.51
106.79
87. 65
74.71
96.71
85.71
40,05
14.31
27. 18
22
22
138
143
143
91
96
96
.34
.34
.70
.53
.53
.84
.47
.47
% Fuel S
as S
in H2SO4
0.39
0.47
0.43
0.33
0.17
0.25
0.29
0. 16
0.23
0. 35
0.26
0.31
0.09
0. 18
0. 14
0. 18
0.04
0. 11
0.26
0.52
0.39
2,45
2.45
0.29
0.29
Total
Recovery
80.
61.
71.
153.
110.
131.
96.
92.
94.
68.
107.
87.
74.
96.
85.
40.
14.
27.
22,
22.
145
145
96
96
94
34
14
32
59
96
71
84
78
85
05
95
80
89
85
23
, 35
,29
.86
.86
.98
.98
.76
.76
H-19
-------
TABLE H-12.
1975 49-STATE CHEVROLET IMPALA (SwRI CAR EM-2)
Pelleted Catalyst, 0. 0415% Sulfur Fuel
Emissions Summary - 8050 Kilometres
Date
8/27/75
8/29/75
Avg.
8/27/75
8/29/75
Avg.
8/27/75
8/29/75
Avg.
8/27/75
8/29/75
Avg.
ffi 8/27/75
t 8/29/75
ro
0 Avg.
8/27/75
8/29/75
Avg.
8/27/75
8/29/75
Avg.
8/27/75
8/29/75
Avg.
8/27/75
8/29/75
Avg.
Test Type
FTP
FTP
SET -7
SET -7
SET -7
SET -7
FET
FET
FET
FET
accel 30
accel 30
S/S 30
S/S 30
accel 60
accel 60
S/S 60
S/S 60
Du ration
20 min
20 min
28 min
28 min
12 min
12 min
1 2 min
12 min
20 min
20 min
60 min
60 min
20 min
20 min
20 min
20 min
HC
0.48
0.36
0.42
0.08
0.07
0.08
0.07
0.05
0.06
0,04
0.03
0.04
0.04
0.03
0.04
0.14
0.07
0.11
0.03
0.02
0.03
0.03
0.04
/» - .
0704
0.04
0.02
0.03
g/
CO
11.89
8.43
10.16
3.70
2.43
3.07
3.91
2.23
3.07
1.38
0.88
1.13
1.42
0.41
0.92
1.29
0.19
0.74
0.36
0.04
0.20
0.22
0.45
0. 34
0.26
1.37
0.82
km
NOX
1.29
1.29
1.29
1.26
1.16
1.21
1.23
1. 12
1. 18
1. 15
1. 09
1. 12
1. 09
1.05
1.07
0.23
0.46
0.35
0.29
0.61
0. 45
1.09
1.06
1.08
1.23
0.66
0.95
SO?
0.083
0.119
0.101
a
0.117
0.117
0.140
0.093
0.117
0.126
0.097
0.112
0.123
0.092
0.108
0.028
0.018
0.118
0.162
0.140
0.130
0.146
0.138
mg/km
H7SO4
0.09
0. 18
0.13
0.44
0.39
0.36
0.37
1.21
1.28
1.25
2.41
1.15
1. 78
0.09
2.93
6.53
4.47
5.50
6.72
2.11
4.41
SO2 as
% Fuel S
65.77
94.61
80.19
a
132.02
132.02
152.11
106.24
129.18
151. 73
124.03
137.88
148. 70
123.88
136.29
40.40
12.05
132.60
223.26
177. 93
158.74
194.89
176.82
H2SO4 as
% Fuel S
0.11
0.09
0.10
0.30
0.28
0.27
0.28
0.96
1.07
1.02
1.91
1.01
1.46
0.08
2.97
5.24
4.02
4.63
5.37
1.83
3.60
Total
Becovery
65.87
•94. 70
80.29
152 38
106.51
129.45
152 69
125.10
138.90
150.61
124.89
137.75
40.45
15.02
137. 85
227.28
182.57
164.11
196.72
180.42
sample bubbler broken
-------
Table H-J3. 1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR JEM-3)
Monolithic Catalyst With Air Pump, 0.0415% Sulfur Fuel
Emissions Summary - 8050 Kilometres
ffi
i
tv
g/km
Date
9/2/75
9/4/75
Avg.
9/2/75
9/4/75
Avg.
9/2/75
9/4/75
Avg.
9/2/75
9/4/75
Avg.
9/2/75
9/4/75
Avg.
9/2/75
9/4/75
Avg.
9/2/75
9/4/75
Avg.
9/2/75
9/4/75
Avg.
9/2/75
9/4/75
Avg.
Test Type
FTP
FTP
SET -7
SET -7
SET -7
SET -7
FET
FET
FET
FET
accel 30
accel 30
S/S 30
S/S 30
accel 60
accel 60
S/S 60
S/S 60
Duration
23 min
23 min
23 min
23 min
12 min
12 min
12 min
12 min
20 min
20 min
60 min
60 man
20 min
20 min
20 min
20 min
HC
0.35
0.60
0.48
0.05
0.03
0.04
0.03
0.03
0.03
0,03
0.03
0.03
0.03
0.03
0.03
0.06
0.07
0.07
0.04
0.05
0.05
0.04
0.03
0.04
0.02
0.03
0.03
CO
3.42
5.81
4.62
0.67
0.55
0.61
0.31
0.37
0.34
0.07
0.03
0.05
0.08
0.07
0.08
0.29
0.11
0.20
0.05
0.00
0.03
0.16
0.05
0.11
0.10
0.01
0.06
NOV
0.65
0.67
0.66
0.60
0.41
0.51
0. 57
0.60
0.59
0.49
0.50
0.50
0.43
0.52
0.48
0.67
0.70
0.69
0. 73
0.60
0.67
0.47
0.54
0.51
0.49
0.50
0.50
mg/km
SO-> as H2SO4 as
SOz H?SCU % Fuel S .
0.100
0.125
0.113
0.060
0.074
0.067
0.068
0.083
0.076
0.047
0.054
0.051
0.064
0.076
0.070
0.022
0.024
0.023
0.017
0.017
0.017
0.106
0.019
0.028
0.024
5.71
3.14
4.43
35.44
12.28
23.86
51.44
17.18
34.31
52.48
38.29
45.39
58.39
29.19
43.79
0.37
4.19
2.65
3.42
61.74
19.50
36.48
27.99
85.25
90.90
88.08
63.86
83.32
73.59
71.49
88.74
80.12
62.16
67.67
64.92
88.13
94.31
91.22
33.94
39.85
36.90
29.19
29.19
29.19
150.87
27.53
39.66
33.60
Total
% Fuel S Recovery
3.62
1.55
2.59
24.50
9.05
16.78
35.39
11.94
23.67
45. 52
31. 54
38.53
52.66
23.52
38.09
0.41
4.76
2.95
3.86
57.29
18.41
34.11
26.26
88.87
92.45
90.66
88.35
92.37
90.36
106.88
100.68
103.78
107.68
99.21
103.45
140.79
117.83
129.31
40.25
33.96
32.14
33.05
208.16
45.95
73.77
59.86
-------
TABLE H-14.
1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst, 0.0415% Sulfur Fuel)
Emissions Summary - 8050 Kilometres
8
i
FTP
SET-7
FET
Accel to 48 kph
48 kph
Accel to 96 kph
96 kph
Car
Number
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
EM-1
EM-2
EM-3
EM-4
* air injection system leak
**EGR system inoperative
***Duplicate Tests on Cars EM-1 and Z not averaged
See explanation page 55.
HC Emissions g/km
0 km
0.39
0.49
0.56
0.37
- - _ _
- - - -
_-__
_ . _ .
....
0. 14
0.06
0.04
0. 12
0.03
0.08
0.03
0.04
0.06
0.09
0.03
0.08
0.04
0.01
0.02
0.03
3200 km
0.32
0.40
0.26
0.44
_ . _ -
.
....
0. 11
0.07
0.04
0. 16
0.03
0.03
0.03
0.07
0.08
0.03
0. 05
0. 14
0.02
0.01
0.03
0. 02
8050 km
0. 30
0.42
0.48
1. 12*
0. 12
0.07
0.04
0.95*
0.09
0.04
0.03
0. 35*
0.09
0. 11
0. 07
0.21*
0.02
0.03
0.05
0. 10*
0. 06
0.04
0. 04
0. 15*
0. 03
0.03
0.03
0.01*
16100 km
0.32
0.34
0.49
1.68*
0. 11
0. 11
0.03
1. 18*
0.06
0.05
0. 03
0. 39*
0.09
0.04
0.04
0.21*
0.03
0. 04
0.04
0. 07*
0.05
0.02
0. 04
0. 02*
0.02
0.02
0.02
0. 00-
24100 km
0.25
0.35
0.44
0.42
0.09
0. 12
0.03
0.09
0. 06
0.06
0.03
0. 06
0.03
0.02
0.05
0.08
0.04
0.03
0.05
0. 07
0. 05
0.04
0. 04
0. 06
0. 02
0. 02
0.03
0. 07
32200 km
0. 31
0.39
0.46**
0.27
0. 13
0. 12
0. 06**
0.06
0.07
0.05
0. 04**
0. 04
0. 03
0.03
0. 09**
0. 11
0.03
0. 03
0.09
0. 04**
0. 03
0.05
0. 04**
0. 04
0.03
0.02
0.03**
0. 03
48300 km
B/A
0.49/0.44
0. 36/0.24
0.64/0.41
0.43/0.47
0. 28/0. 39
0. 11/0. 06
0. 17/0.06
0. 12/0. 14
0. 26/0. 31
0.07/0.03
0. 19/0.07
0. 07/0, 10
0. 12/0. 11
0. 03/0. 02
0. 18/0. 10
0. 16/0.40
0. 05/0. 04
0. 03/0. 02
0.24/0. 10
0.05/0.21
0. 09/0. 12
0. 05/0. 05
0. 20/0. 11
0. 10/0. 15
0. 15/0. 04
0. 15/0.02
0. 12/0.09
0. 06/0. 18
64400 km
0.63
0.39
0.57
0.61
0.51
0.27
0. 15
0. 18
0.41
0.20
0.20
0. 13
0. 11
0.43
0.42
0.08
0.05
0. 24
0.22
0.05
0. 19
0.08
0. 15
0. 08
0.68
0. 19
0. 12
0. 09
80500 km'
0.66/0.59
0.80/3.47
0.68
0.60
0.31/0.52
0.34/1.51
0. 13
0. 17
0. 19/0.38
0. 13/1.35
0. 12
0.08
0.09/0. 17
0.05/0. 21
0.53/0.09
0.26
0.06/0.06
0.05/0.04
0. 34/0. 10
0.24
0.08/0.31
0.00/0.45
0. 16
0. 05
0.09/0.81
0.06/0. 02
0.08
0.06
B = Before Maintenance
A = -After Maintenance
FTP Standards: '75 Federal =0.9 g/km
'75 California - 0. o g/km
-------
TABLE H-25.
1975 49-STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolithic Catalyst, 0.0415% Sulfur Fuel
Emissions Summary - 16100 Kilometres
ffi
g/km
Date
8/11/75
8/13/75
Avg,
8/11/75
8/13/75
Avg.
8/11/75
8/13/75
Avg.
8/11/75
8/13/75
Avg.
8/11/75
8/13/75
Avg.
8/11/75
8/13/75
Avg.
8/11/75
8/13/75
Avg.
8/11/75
8/13/75
Avg.
8/11/75
8/13/75
Avg.
Test type
'75 FTP
• 75 FTP
SET- 7
SET- 7
SET -7
SET -7
FET
FET
FET
FET
Accel to
30
S/S 30
S/S 30
Accel to
60
S/S 60
S/S 60
HC
0.40
0.24
0.32
0. 10
0. 10
0.10
0. 13
0.09
0.11
0.04
0.06
0.05
0.05
0.07
0.06
0.08
0.10
0.09
0.03
0.02
0.03
0.04
0.05
0.05
0.02
0.02
0.02
CO
10.16
7.33
8.75
4.31
3.97
4. 14
4.97
4.03
4.50
1.22
1.74
1.48
1.44
2.66
2.05
0.83
0. 52
0.68
0.00
0. 11
0.06
0.31
1.08
0.70
0.77
1.89
1.33
NOX
1.69
1.61
1.65
1.42
1.38
1.40
1.37
1.48
1.43
2.47
1.57
2.02
1.84
1.76
1.80
0.84
1.05
0.95
0.73
0.87
0.80
1.91
2.43
2. 17
1.55
0.93
1.24
S02
0. 130
0. 124
0. 127
0. 136
0.094
0. 115
0. 064
0.086
0.075
0. 103
0. 100
0. 102
0.085
0.083
0.084
0.018
0.027
0.023
0.012
0.011
0.012
0. 147
0. 166
0. 157
0.066
0.053
0.060
mg/km
H2S04
0.61
1.02
0.82
0.25
0.38
0.32
0.08
0.41
0.25
0.07
1. 12
0.60
0. 18
0.65
0.42
0.20
1.50
0.85
0.50
1.15
0.83
18.95
8.06
13.51
1.58
1. 18
1.38
% Fuel S
as S
in SO 2
0.29
0.53
0.41
0. 18
0.29
0.24
0.06
0.31
0. 19
0.06
1.06
0.56
0. 17
0.60
0.39
0.22
1.72
0.97
0.59
1.39
0.99
18.64
9.99
14. 32
1.62
1.50
1.56
% Fuel S
as S
in H2SO4
98.86
97.77
98.32
153. 22
108.26
130. 74
72.62
99. 96
86.29
141.15
144. 22
142.69
121. 56
116.59
119.08
30. 24
48. 12
39. 18
21.38
19.50
20.44
221. 15
314.40
267.78
103.54
103.25
103.40
Total
Recovery
Q9. 14
98.29
• 98.72
153.40
108. 54
130.97
72.67
100. 27
86.47
141.21
145.27
143. 24
121.74
117. 19
U9.46
30.46
49.84
40. 15
21.97
20.89
Zl.43
239. 80
324. 39
282. 10
105. 16
104. 75
104. 96
-------
TABLE H-16. 1975 49-STATE CHEVROLET IMPALA (SwRI CAR EM-2)
Pelleted Catalyst Without Air, 0.0415% Sulfur Fuel
Emissions Summary - 16100 Kilometres
Test
1 & 2
1 & 2
3
3
4
4
5
5
6
6
7
7
8
8
9
9
10
10
Date
9/17/75
9/19/75
9/17/75
9/19/75
9/17/75
9/19/75
9/17/75
9/19/75
9/17/75
9/19/75
9/17/75
9/19/75
9/17/75
9/19/75
9/17/75
9/19/75
9/17/75
9/19/75
Test
Type
FTP
FTP
SET-7
SET-7
SET-7
SET-7
FET
FET
FET
FET
30 mph
accel
30 mph
SS
60 rnph
accel
60 mph
SS
g/km
HC
0.35
0.34
0.34
0. 11
0. 10
0. 10
0. 15
0.08
0. 12
0.05
0.04
0.04
0.08
0.03
0.06
0.04
0.04
0.04
0.04
0.03
0,04
0.02
0.02
0.02
0.02
0.01
0.02
CO
9.92
9.69
9.81
4.37
3.35
3.86
7.08
3.39
5.24
1.78
0.96
1. 37
3.42
0.89
2. 16
0. 14
0.21
0. 18
0.66
0. 01
0.34
0. 11
0.04
0.08
0.62
o.o«
0.35
NOX
1.25
1.38
1.32
1.03
1.28
1. 16
0.99
1.16
1.08
0.91
1. 10
1. 10
0.82
1.08
0. 95
0.47
0.45
0.46
0.31
0.42
0. 36
1.35
0.43
0.89
1.20
1.^5
1.22
SO2
0.097
0.074
0.086
0.090
0.089
0.090
0.093
0.095
0.094
0.056
0.097
0.077
0.087
0.021
0.022
0.022
0.035
-
0.035
0. 106
0. 125
0.116
0. 115
0.115
mg/km
H2SO4
1.50
0.49
1.00
0. 37
0.56
0.46
0.01
0.26
0. 13
0. 36
1.33
0.84
0.03
1.35
0.68
0.01
0.06
0.04
-
3.55
3.55
8.01
_
8.01
2.59
4.59
4.59
% Fuel S
as 5
inH2S04
0.74
0.26
0.50
0.27
0. 39
0. 33
0.01
0. 19
0. 10
0. 30
1.08
0.69
0.02
1. 12
0. 57
0.01
0.06
0.04
.
3.42
3.42
6.59
-
6.59
2.20
3.75
3.75
% Fuel S
as S
inSOz
75.84
56.77
66.31
100. 10
95. 12
97.61
102.41
103.79
103. 10
69.46
130. 05
97.83
113.94
30. 39
31.42
30.91
51. 92
-
51. 92
133. 10
151.63
142. 37
149. 69
149.69
Total
Recovery
76.58
57.03
66.81
100.38
95.51
97.95
102.41
103.98
103.20
70.53
130.07
98.95
114.51
30.41
31.47
30. 95
_
.
55.34
139.69
-
139.69
151.89
151.89
-------
TABLE H-17. 1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR F.M-3)
Monolithic Catalyst With Air Pump, 0.0415% Sulfur Fuel
Emissions Summary - 16100 Kilometres
Test
1
1
1
2
2
2
3
3
3
4
4
4
S
5
S
6
6
6
Date
9/30/75
10/2/75
10/3/75
9/30/75
10/2/75
10/3/75
9/30/75
10/2/75
10/3/75
9/30/75
10/2/75
10/3/75
9/30/75
10/2/75
10/3/75
9/30/75
10/2/75
10/3/75
Test
Type
FTP
FTP
FTP
Avg.
SET-7
SET -7
SET- 7
Avg.
SET-7
SET-7
SET-7
Avg.
FET
FET
FET
Avg.
SET-7
SET-7
SET-7
Avg.
SET-7
SET-7
SET-7
Avg.
K/km
HC
0.65
0.39
0.47
0.49
0.04
0.04
0.03
0.04
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
CO
5.54
6.46
5.06
5.69
0. 55
0.42
0.49
0.49
0.29
0.65
0.27
0.40
0.05
0.16
0.07
0.09
0.22
0.31
0.29
0.27
0.74
0.36
0.85
0.65
NOX
0.97
1.01
1.08
1.02
0.71
0.74
0.94
0.80
0.74
0. 78
0.78
0.77
0.60
0.58
0.64
0.61
0.69
0.71
0.70
0.70
0.73
0.76
0. 91
0.80
SO2
0. 118
0.096
0.079
0.098
0.060
0.049
0.064
0.058
0.079
0.081
0.083
0.081
0.038
0.036
0.087
0.054
0.059
0.065
0. 044
0.056
0.072
0.072
0.090
0.078
mg/kxn
H2S04
6.24
6.44
4.55
5.74
10.05
37.41
14.76
20.74
19.25
35.24
23.65
26.05
38.64
59.99
57. 13
51.92
23.86
50.20
37.03
13.37
47.26
18.34
26.32
% Fuel S
as S
in H2SO4
2.70
2.86
1.93
2.50
6.72
24. 59
9.52
13.61
12.96
23.67
15.65
17.43
30.79
46.88
44.79
40.82
16. 19
34.50
25.35
8. 91
32.23
10. 95
17.36
% Fuel S
as S
in SO2
78.
65.
51.
65.
61.
49.
63.
57.
81.
83.
83.
82.
46.
43.
104,
64,
40
14
51
02
32
06
57
98
07
03
66
59
,00
,39
, 30
.56
60.79
68.02
48
59
73
75
82
77
.40
.07
.74
.63
. 18
. 18
Total
Recovery
8i.lO
68.00
53.44
67.52
68.04
73.64
73.09
71.59
94.03
106.71
99.30
100.01
7t,.79
90. 27
149.09
105.38
76.97
102.52
89.75
82.65
107. 87
93.^
94.55
9/30/75
30 mph
accel
0.04
0. 16
0.55
0.013
0.07
0.07
22.01
22.08
9/30/75 30 mph
S/S 0.04 0.22 0.53 0.010
1.75
9/30/75 60 mph
accel 0.04 0.24 0.59 0.065 62.98
1.94
54.82
10 9/30/75 60 mph
S/S 0.02 0.13 0.54 0.022 46.11 43.70
16.88
32.44
18.82
86.85 141.67
76. 15
-------
w
I
Teat
1
1
1
2
2
2
4
4
4
TABLE H-18. 1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst With Air Pumps, 0.0415% Sulfur Fuel
Emissions Summary - 16100 Kilometres
Date
9/2A/75
9/27/75
9/24/75
9/26/75
9/27/75
9/24/75
9/26/75
9/27/75
9/24/75
9/26/75
9/27/75
9/24/75
9/26/75
9/27/75
9/24/75
9/26/75
9/27/75
9/24/75
9/24/75
FTP
FTP
Avg.
SET-7
SET-7
SET-7
Avg.
SET-7
SET-7
SET-7
Avg.
FET
FET
FET
Avg.
SET-7
SET-7
SET-7
Avg.
SET-7
SET-7
SET-7
Avg.
30 mph
accel
30 naph
S/S
HC
0.21
0.07
CO
1.38
0.35
0. 18
NO
17.60 1.19
9.86 0.97
11.73 1. 17
11.40 1.11
0.88
0.66
0.80
0.78
0.15
0.13
S02
0. 140
0.084
0.057
0.066
0.069
0.082
0.082
0.075
0.080
0.054
0.054
0. 050
0.053
0. 074
0.079
OTOT?
0.013
0.009
9 9/24/75 60 mph
accel 0.02 0.14 0.30 0.060
10 9/24/75 60 mph
accel 0.00 0.04 0.30 0.053 13.79
mg/km
H2SO4
0.74
0. 86
0.69
0.72
2.25
1.44
1.70
1.80
1.86
1.59
1. 60
1.68
4. 20
4.69
4.56
4.48
2.76
3. 57
2.28
2.87
3.25
2.91
2. 74
2.97
1.87
7.81
8.35
13.79
% Fuel S
as S
in H2SO4
0. 34
0. 43
0.31
0.32
1.61
1.00
1.15
1.25
1.31
1.09
1.08
1.16
3.29
3. 74
3.49
3. 51
1.88
2.52
1. 55
1. 98
2. 04
1.98
1.83
1.95
1. 52
8.03
7. 04
12.20
% Fuel S
as S
in SC>2
97.02
94.83
95.93
92.06
60.53
68.61
73.73
88.35
86.73
78.07
84.38
64.02
66.19
58.87
63.03
92.57
98. 19
81.00
90. 59
71. 32
81.91
76.62
16.09
13.97
77. 76
72.90
Total
Recovery
97.36
67. 31
69.92
62.36
66. 54
94.45
100.71
82.55
92.57
73. 36
83.89
78.63
17.60
22.00
64.80
85.09
-------
TABLE H-l 9.
J 975 49-STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolithic Catalyst, 0. 0415% Sulfur Fuel
Emissions Summary - 24100 Kilometres
Date
10/15/75
10/17/75
Average
10/15/75
10/17/75
Average
10/15/75
10/17/75
Average
10/15/75
}(\l 1 7/7C
Average
10/15/75
10/17/75
10/15/75
10/17/75
Average
10/15/75
10/17/75
Average
10/15/75
10/17/75
Average
10/15/75
10/17/75
Average
10/15/75
10/17/75
Average
Test Type
FTP
FTP
SET-7
SET-7
SET-7
SET-7
FET
TTTTT
SET-7
SET-7
SET-7
SET-7
30 mph accel
30 mph accel
30 mph S/S
30 mph S/S
60 mph accel
60 mph accel
60 mph S/S
60 mph S/S
Duration
23 min
23 min
23 min
23 min
12 min
23 min
23 min
23 min
23 min
20 min
20 min
60 min
60 min
20 min
20 min
20 min
20 min
HC
0.24
0.26
0.25
0.09
0.09
0.09
0.07
0.08
0.08
0.05
On A
0.06
0.09
0.10
0,10
0.09
0.08
0.09.
0.02
0.04
0. 03
0.03
0.04-
0.04
0.03
0.06
0.05
0.02
0.02
0.02
gA
CO
6.22
7.58
6.90
2.77
2.84
2.81
2.42
2.65
2.54
1.01
1 ^Q
1.30
2.93
3.55
3.24
3.30
2.84
3. 07
0.20
0.14
0.17
0.04
0.02
0.03
0,13
0.15
0.14
0.02
0.17
0.09
:m
NOX
1.97
1.63
1.80
2.06
1.74
1.90
1.70
1.48
1.59
1.76
1 7ft
1.77
1.58
1.44
1.51
2.46
1.39
1.93
0.92
0.88
0.90
0.62
0.67
0.65
1.63
2.25
1.94
1.63
2.89
2.26
SO 2
0.090
0.136
0.113
0.116
0.087
0.102
0.093
0.065
0.079
0.092
0.088
0.095
0.068
0.082
0.093
0.066
0.080
0.022
0.029
0.026
0.008
0.013
0.011
0. 116
0.064
0.090
0.066
0.075
0.071
mg/km
H2SO4
3.29
1. 07
2.18
0.58
0.47
0. 53
0.44
0. 45
0.45
0. 54
0. 54
0.30
0.26
0. 28
0.32
0.47
0.40
0.30
0.43
0.37
1.24
1.54
1.39
58.66
67.02
62.84
22.41
15.08
18.75
H2SO4 as To
of fuel S
1.83
0.62
1.23
0.36
0.37
0.37
0.33
0.36
0.35
0.53
0.53
0.24
0.21
0.23
0.25
0.39
0.32
0.33
0.53
0.43
1.51
1.96
1.74
64.26
63.96
64.11
22. 59
15.83
19.21
SO 2 as %
of fuel S
76.91
120.29
98.50
111. 14
105.75
108.45
108,35
80.18
94.27
137.43
1 23 76
130.60
114.84
86.12
100.48
110.82
83.79
97.31
37.55
54.53
46.04
15.49
24.56
20.03
194.77
92.83
143.80
101.34
121.23
111.29
Total
Recovery
78.74
120.91
99.83
111.50
106.12
108.81
108.69
80.54
94.62
137.96
131.13
115.07
86.33
100.70
111.07
84.18
97.63
37.88
55.06
46.47
17.00
26.53
21.77
259.04
156.79
207.92
123.93
137.06
130.50
-------
TABLE H-20.
1975 49-STATi. OIIZVI^OLET IMPALA (SwRI CAR EM-2)
Pelleted Catalyst, 0.0415% Sulfur Fuel
Emissions Summary - 24100 Kilometres
Date
a
00
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
10/30/75
10/31/75
Average
Test Type
FTP
FTP
SET-7
SET-7
SET-7
SET-7
FET
FET
SET-7
SET-7
SET-7
SET-7
30 mph accel
30 mph accel
30 mpb S/S
30 mph S/S
60 mph accel
60 mph accel
60 mph S/S
60 mph S/S
Duration
23 rnin
23 min
23 min
23 min
12 min
1 2 min
23 min
23 min
23 min
23 min
20 min
20 min
60 min
60 min
20 min
20 min
20 min
20 min
g/km
HC
0.32
0.37
0.35
0.12
0.08
0.10
0.12
0.17
0.15
0.05
0.06
0. 06
0.11
0.15
0.13
0.08
0.15
0.12
0.03
0.01
0.02
0.03
0.03
0.03
0.03
0.04
0.04
CO
10.69
12.88
11.79
6.30
2.45
4.38
6.18
7.93
7.06
1.78
2.35
2.07
5.32
8.39
6.86
4.26
6.96
5.61
0.21
0.26
0.24
0.00
0.00
0.00
0.86
1.41
1.14
NOy
1.48
1.49
1.49
1.52
1.16
1.34
1.37
1.41
1.39
1.50
1.14
1.32
1.38
1.19
1.29
1.32
1.33
1.33
0.53
0.27
0.40
0.52
0.63
0.58
1.32
1.34
1.33
502
0.091
0.118
0.105
0.094
0.087
0.091
0.089.
0.097
0.093
0.099
0.093
0,096
0.086
0.083
0.085
0.079
0.081
0.080
0.018
0.055
0.037
0.013
0.007
0.010
0.075
0.155
0.115
mg/km
H2SO4
1.30
1.21
1.26
1.15
0.48
0.82
0. 78
1.10
0.94
1.96
0. 71
1.34
0.71
0.55
0.63
0. 90
0.49
0.70
0.17
0.11
0.14
3.25
1.52
2.39
35.61
32.98
34.30
HzSO4 as %
of fuel S
0.66
0.63
0.65
0.78
0.37
0.58
0.55
0.80
0.68
1.48
0.58
1.03
0.51
0.40
0.46
0.69
0.35
0.52
0.16
0.11
0.14
3.30
1.58
2. 44
27.41
28.14
27.78
SO2 as %
of J ael S
70.78
94.64
8^.46
97.32
104.24
100.78
95.86
107.46
101.66
11*. 31
116.56
Hi-. 44
93.80
93.08
93.44
91.27
88.70
89.99
26.12
82.59
54.36
19.81
11.53
88.05
202.14
145.10
Total
Recovery
70.93
95.27
83.10
98.10
104.61
101.36
96.41
108.26
102.34
115.79
117.15
116.47
94.31
93.48
93.90
91.96
89.06
90.51
26.29
82.70
54.50
- 23.11
13.11
18. 11
115.46
230.28
172.87
0.01
0.03
0.02
0.02
2.90
1.46
1.23
1.11
1.17
0.073
0.073
7.26
3.68
5.47
5.59
2.67
4.13
85.55
85. 55
91.14
89.68
-------
TABLE H-21. 1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR EM-3)
Monolithic Catalyst With Air Pump, 0.0415% Sulfur Fuel
Emissions Summary - 24100 Kilometres
to
vO
g/km
Date
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
11/3/75
11/5/75
Average
Test Type
FTP
FTP
SET -7
SET -7
SET -7
SET -7
FET
FET
SET -7
SET -7
SET -7
SET-7
30 mph accel
30 mph act-pi
30 mph S/S
30 mph S/S
60 mph accel
60 mph accel
60 mph S/S
60 mph S/S
Duration
23 min
23 min
23 min
23 min
12 min
12 min
23 min
23 min
23 min
23 min
20 min
20 min
60 min
60 min
20 min
20 min
20 min
20 min
HC
0.32
0.55
0.44
0.03
0.04
0.04
0.03
0.03
0.03
0.03
0.02
0.03
0.03
0.04
0.04
0.03
0.03
0. 03
0.04
0.05
0.05
0.04
0.05
0.05
0. 04
0.03
0.04
0.03
0.02
0.03
CO
4.46
10.76-
7.61
0.74
1.10
0.92
0.47
1.06
0.77
0.05
0.09
0.07
0.44
1.68
1.06
0.53
0.78
0.66
0.00
0.08
0.04
0.00
0.08
0.04
0.93
0.51
0.72
0.04
0.02
0.03
NOV
1.00
1.19
1.10
0.79
0.92
0.86
0.87
0.88
0.88
0.68
0.81
0.75
0.83
0.91
0.87
0.80
0.88
0.84
0.78
0.97
0.88
0.75
0.84
0.80
0.77
1,03
0.90
0.72
1.17
0.95
SO2
0.157
0.215
0.186
0.064
0.083
0.074
0.071
0.084
0.078
0.041
Orf051
0.046
0.060
0.115
0.088
0.082
0.087
0.085
0.009
0.018
0.014
0.013
0.017
0.015
0.127
0.092
0.110
0.025
0.026
0.026
mg/km
H?SO4
6.72
4.62
5.67
9.50
5.78
7.64
18.00
5.39
11.70
51.92
24.09
38.01
50.84
8.07
29.46
17.48
7,09
12.29
0.08
0.25
0.17
2.85
2.40
2.63
^3.58
28.43
26.01
26.40
23.25
24.83
H2SO4 as %
of fuel S
2.93
1.94
2.44
6.19
3.69
4.94
11.81
3.69
7.75
4.0.95
17.96
29.46
31.93
5.05
18.49
12.11
4.79
8.45
0.09
0.25
0.17
3.33
2.58
2.96
18.77
21.03
19.90
21.71
19.64
20.68
SO2 as %
of Zuel S
104.62
138.61
121.62
63.54
80.79
72.17
71.33
87.79
79.56
49.49
57.70
53.60
58.08
110.58
84.33
87.26
90.01
88.64
15.55
27.36
21.46
23.44
27.08
25.36
154.63
125.60
140.12
31.34
33.38
32.36
Total
Recovery
107.54
140.56
124.05
69.73
84.48
77.11
83.13
91.48
87.31
90.44
75.67
83.06
90.01
115.63
102.82
99.38
94.80
97.09
15.64
27.61
21.63
26.77
29.86
28.32
173.40
146.63
160.02
53.05
53.02
53.03
-------
TABLE H-22.
1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst, 0. 0415% Sulfur Fuel
Emissions Summary - 24100 Kilometres
g/km
Date
11/4/75
11/6/75
11/7/75
Average
11/4/75
11/6/75
11/7/75
Average
11/4/75
11/6/75
11/7/75
Average
11/4/75
E H/6/75
-------
TABLE H-23. 1975 49-STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolith Catalyst, 0. 0415% Sulfur Fuel
Emissions Summary - 32200 Kilometres
Date
Test Type Duration
12/23/75 FTP
12/23/75 SET-7 23 min
12/23/75 SET-7 23 min
12/23/75 FET 12 min
12/23/75 SET-7 23 min
12/23/75 SET-7 23 min
12/23/75 30;mphaecel 20 min
12/23/75 30 mph S/S 30 min
12/23/75 60mphaccel 20 min
12/23/75 60mphS/S 20 min
/km
mg /km
as SO? as % Total
HC
0.31
0. 13
0.11
0.07
0. 15
0. 11
0.03
0.03
0.03
0.03
CO
10.89
5.92
4.91
2.39
7.67
4.47
0.06
0.01
0.76
1.59
NOX
2.69
2.40
2.47
3.21
1.99
1.87
1. 19
,1. 19
2.58
1.91
SO 2 H2SO4
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
137
198
107
123
107
088
007
014
151
107
0.
2.
0.
0.
0.
0.
0.
1.
6.
0.
69
72
23
99
18
05
00
07
68
,68
% of fuel S
0.
1.
0.
0.
0.
0.
0.
1.
5.
0.
36
94
17
81
12
04
00
22
36
55
of fuel S Recovery
105.
216.
121.
152.
113.
99.
11.
24.
185.
133.
36
46
41
95
87
62
15
07
03
06 -
105. 70
218.41
121. 58
153. 76
113.99
99.65
11. 15
25.29
190.39
133.61
-------
TABLE H-24. 1975 49-STATE CHEVROLET IMPALA (SwRI CAR EM-2)
Pelleted Catalyst, 0. 0415% Sulfur Fuel
Emissions Summary - 32200 Kilometres
g/km
Date
12/22/75
12/22/75
12/22/75
12/22/75
£ 12/22/75
12/22/75
12/22/75
12/22/75
12/22/75
12/22/75
Test Type
FTP
SET-7
SET-7
FET
SET-7
SET-7
30mphaccel
30 mph S/S
60 mphaccel
60 mph S/S
Duration
23 min
23 min
12 min
23 min
23 min
20 min
30 min
20 min
20 min
HC
0.39
0. 12
0. 12
0.05
0. 12
0. 13
0.03
0.03
0.05
0.02
CO
10.04
6.49
5.76
1.42
5.72
5.70
0.20
0.04
2.38
0.54
NOX
2.62
2.08
2. 14
1.99
2.08
1.97
0.70
0.68
2.49
1.98
SO2
0. 123
0. 102
0. 101
0. 130
0.093
0.093
0.028
0.016
0.169
0. 137
mg/km
H?SO4
2.39
0.79
0.65
1.91
2.53
0.75
0.54
1.46
12.07
3.51
H2Sl
% of
1.
0.
0.
1.
1.
0.
0.
1.
8.
2.
04 as
fuel S
21
53
46
63
71
53
51
18
72
88
SO2 as %
of fuel S
95.42
105. 19
108. 87
170.00
96.48
100.43
39.96
19.46
186.39
172. 65
Total
Recovery
96.63
105. 72
109.32
171. 63
98. 19
100.96
40.47
20.63
195. 11
175.53
-------
TABLE H-25. 1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR EM-3)
Monolithic Catalyst, 0.0415% Sulfur Fuel
Emissions Summary - 32200 Kilometres
g/km
S
oo
Date
12/19
12/19
12/19
12/19
Test Type Duration
775
775
775
775
12/19/75
12/19
775
FTP
SET-7
SET-7
FET
SET-7
SET-7
23 min
23 min
12 min
23 min
23 min
HC
0.
0.
0.
0.
0.
0.
46
07
06
04
07
06
CO NOX
3.
0.
0.
0.
0.
o.
55
36
08
08
17
25
3.
3.
3.
3.
2.
2.
26*
09*
18*
38*
94*
79*
SO2
0.224
0.099
0.086
0.075
0.073
0.081
12/19/75 SOmphaccel 20 min
12/19/75 30 mph S/S 30 min
12/19/75 60mphaccel 20 min
12/19/75 60 mph S/S 20 min
0.09 0.02
0.98* 0.024
mg/km
0.09 0.17 0.92* 0.007 0.64
8.02
0.04 0.08 4.22* 0.069 77.11
H2SO4 as SO2 as % Total
% of fuel S of fuel S Recovery
0.03 0.03
3.72* 0.025 32.53
5.91
28.38
37.49
39.33 ._
41.36
24.82
0.68
8.38
68.69
29.28
178.76
112.72
99.00
99.88
81. 11
90.68
11.82
38.69
94.43
33.97
184. 67
141. 10
136.49
139.21
122.47
115. 50
12. 50
47. 07
163. 11
63.24
*Failed Vacuum Amplifier in EGR System
-------
TABLE H-Z6. 1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst, 0.0415% Sulfur Fuel
Emissions Summary - 32200 Kilometres
g/km
Date
12/18/75
12/18/75
12/18/75
12/18/75
12/18/75
£ 12/18/75
12/18/75
12/18/75
12/18/75
12/18/75
Test Type
FTP
SET-7
SET-7
FET
SET-7
SET-7
30 mph Accel
30 mph S/S
60 mph Accel
60 mph S/S
Duration
23 min
23 min
12 min
23 min
23 min
20 min
30 min
20 min
20 min
HC
0. 27
0. 06
0.06
0.04
0. 06
0.07
0. 11
0. 04
0.04
0.03
CO
7.97
1. 08
1.33
0. 11
0.71
0.37
0. 23
0. 02
0. 11
0. 01
NOX
1.
1.
1.
1.
1.
1.
0.
0.
1.
1.
25
54
28
16
23
07
15
18
38
15
S02
0.056
0.072
0. 040
0.064
0.060
0.058
0.031
0.029
0.050
0.017
mg/km
H2S04
16. 15
19. 11
24. 26
16.41
31.42
32.86
8. 26
26.63
66.98
27.20
H2SO4
as % of
Fuel S
7.87
13.21
16.99
13.39
22.43
23.07
7.22
23.48
49.05
22.55
SO2 as
% of
Fuel S
41.50
76.67
43. 20
79.75
65.44
62. 70
41.36
38. 61
55.57
21.73
Total
Recovery
49.37
89. 88
60. 19
93. 15
87. 87
85. 78
48. 58
62.08
104. 63
44. 28
-------
TABLE H-27. 1975 49 STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolithic Catalyst, 0. 0405% Sulfur Fuel
Emissions Summary - 48300 Kilometres
g/km
% Fuel % Fuel
mg/km S as S as Total
Date
2/10/76
2/12/76
2/10/76
2/12/76
2/10/76
2/12/76
2/10/76
B 2/12/76
01 2/10/76
2/12/76
2/10/76
2/12/76
2/10/76
2/12/76
2/10/76
2/12/76
2/10/76
2/12/76
2/10/76
2/12/76
Test Type
FTP
FTP
SET-7
SET-7
SET-7
SET-7
HWFET
HWFET
SET-7
SET-7
SET-7
SET-7
30 mph accel
30 mph accel
30 mph
30 mph
60 mph accel
60 mph accel
60 mph
60 mph
Duration
0
0
0
0
0
0
0
0
0
0
0
0
20 min 0
20 min 0
30 min 0
30 min 0
20 min 0
20 min 0
HC
.49
.44
.26
.21
.30
.32
. 26
.31
. 27
.50
. 27
.51
.12
. 11
.05
.04
.09
.12
20 min 0. 15
20 min 0 . 04
CO
12.57
11. 03
10.34
07. 17
11.88
12.23
11.56
12. 26
11.40
18.69
10.80
20. 18
0.60
0.91
0.00
0.00
3. 17
3.45
9.4.5
1.72
NOX
1.79
2. 02
1.44
2.03
1. 37
1. 52
1.72
1.73
1.44
1.44
1.55
1.45
0.94
0.82
0.98
0.75
1.75
1.63
1.22
1.55
SO2
0.169
0. 110
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
116
067
061
056
059
028
058
060
064
055
016
019
Oil
021
132
116
067
040
H2S04
1.47
1.80
0.93
0. 95
0. 31
0.46
0. 23
0.20
0.44
0.27
0. 26
0. 67
0. 56
0.46
1.20
1.20
1.77
1.39
0.24
0.21
H2S04
0.71
0. 86
0. 64
0.67
0. 22
0. 32
0. 19
0. 17
0. 30
0. 18
0. 18
0.46
0.65
0.51
1.39
1.38
1.52
1.21
0.22
0. 19
SO 2
125.43
79.96
121. 72
71. 19
64. 93
59. 17
75.99
35.73
60. 38
63.21
68.78
58.05
27.96
32. 15
19.57
36.69
173.85
155. 19
91.88
54.61
Recovery
126. 14
80.82
122. 36
71. 86
65. 14
59.49
76. 18
35. 90
60. 68
63.40
68.97
58. 50
28.60
32.66
20.97
38.07
175.37
156.40
92.20
54.80
-------
TABLE H-28. 1975 49-STATE CHEVROLET IMPALA (SwRI CAR EM-2)
Pelleted Catalyst, 0.0405% Sulfur Fuel
Emissions Summary - 48300 Kilometres
a
•
u>
OS.
Date
1/28/76*
1/30/76**
1/28/76
1/30/76
1/28/76
1/30/76
1/28/76
1/30/76
1/28/76
1/30/76
1/28/76
1/30/76
1/28/76
1/30/76
1/28/76
1/30/76
1/28/76
1/30/76
1/28/76
1/30/76
Test Type
L.A-4
LA-4
SET-7
SET-7
SET-7
SET-7
HWFET
HWFET
SET-7
SET -7
SET-7
SET-7
Accel to 30
Accel to 30
S/S 30
S/S 30
Accel to 6O
Accel to 60
S/S 60
S/S 60
g/km
Duration HC
0.36
0.24
0.11
0.06
0.10
0.07
0.07
0.03
0.11
0.07
0.11
0.05
0.03
0.02
0.03
0.02
0.05
0.05
0.15
0.02
CO
9.61
5.22
4.43
1.31
4.23
2.05
3.08
0.67
4.67
2.63
5.39
0.76
0.11
0.04
2.17
0.00
2.28
1.22
16.07
1.10
NOX
1.91
1.60
1.79
1.63
1.69
1.56
1.53
1.41
1.46
1.67
1.56
1.55
0.56
0.61
0.72
0.56
1.65
1.57
1.78
1.04
SO2
0.107
0.078
0.137
0.132
0.126
0.107
0.137
0.100
0.099
0.113
0.099
0.063
0.018
0.015
0.006
0.010
0.177
0. 145
0.113
0.123
mg/km
1.31
0.78
3.17
2.94
1.08
1.47
3.03
2.70
0.48
1.22
0.59
1.87
0.20
0.01
2.29
0.87
16.01
23.05
1.07
3. Or
% fuel S
as S
in H2SO4
0.65
0.42
2.11
2.12
0.75
1.09
2.15
2.28
0.34
0.87
0.40
1.40
0.20
0.01
2.16
0.93
12.37
19.26
0.80
2.67
% fuel S
as S
in SO 2
80.93
63.45
139.45
145.65
132.66
122.61
148.67
128.80
106.00
122.67
102.52
77.60
27.20
23.12
8.49
16.50
208.81
186.02
130.14
166.80
Total
Recovery
81.58
63.87
141.56
147.77
133.41
123.71
150.82
131.08
106.34
123.54
102.91
79.00
27.40
23.13
10.65
17.43
221.18
205.28
130.95
169.46
*Tests on'1/28/76 were done before 30,000 mile maintenance
**Tests on 1/30/76 were done after 30, 000 mile maintenance
-------
TABLE H-29. 1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR EM-3)
Monolithic Catalyst with air injection, 0. 0405% Sulfur Fuel
Emissions Summary - 48300 Kilometres
g/km
Date
2/9/76
2/19/76
2/6/76
2/18/76
2/6/76
2/19/76
2/6/76
£ 2/19/76
oo
2/6/76
2/19/76
2/6/76
2/19/76
2/6/76
2/19/76
2/6/76
2/19/76
2/6/76
2/19/76
2/6/76
2/19/76
Test Type Duration
FTP
FTP
SET -7
SET -7
SET -7
SET -7
HWFET
HWFET
SET-7
SET-7
SET-7
SET-7
30 mph accel 20 min
30 mph accel 20 min
30 mph 30 min
30 mph 30 min
60 mph accel 20 min
60 mph accel 20 min
60 mph 20 min
60 mph 20 min
HC
0.64
0.41
0.19
0.08
0. 17
0.06
0. 19
0.07
0.16
0.05
0. 15
0.06
0. 18
0. 10
0.24
0.10
0.20
0. 11
0. 12
0.09
CO
6.72
5.07
0.93
0.68
0.53
0.70
0.69
0. 14
0.59
0. 59
0.64
0.92
0.27
0.21
0.04
0.03
1.76
1.62
0.05
0.04
NOX
1.07
0.93
0.87
0.81
0.79
0.77
0.87
0.85
0.82
0.76
0.77
0.85
0.79
0.87
0.64
0.74
1.15
1.04
1.17
0.96
SO2
0. 116
0. 169
0.093
0.091
0.093
0.097
0.059
0.045
0. Ill
0. 113
0.089
0. 103
0.013
0.019
0.016
0.022
0.082
0.088
0.030
0.030
mg/km
H2SO4
2.84
4.12
4.23
6.81
11. 19
7. 38
12.93
14. 55
5. 11
6.96
5.95
0.40
0.37
0.91
0.66
24.80
7.25
21. 22
19.66
% Fuel
S as
H2S04
1.33
1.94
2.80
4.34
7.63
4.67
10. 11-
11.42
3.51
4.68
4. 25
0.46
0.42
1.04
0. 77
22.00
6.43
20. 14
17.08
% Fuel
S as
S02
83. 31
122.10
94.04
89.20
97.57
94.53
70.75
54.25
116.71
116.37
96.92
100. 96
22.43
33. 35
27.71
39.56
111.41
118.92
43.86
39.68
Total
Recovery
84.65
124. 04
96.83
93.53
105. 20
99.21
80.87
65.67
120.22
121.06
101. 17
22.89
33.77
28.75
40. 33
133.41
125.35
64.00
56.76
-------
TABLE H-30. 1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst 0. 0405% Sulfur Fuel
Emissions Summary - 48300 Kilometres
% Fuel % Fuel
fi/km
Date
2/3/76
2/5/76
2/3/76
2/5/76
2/3/76
2/5/76
2/3/76
ffi 2/5/76
t
03 2/3/76
2/5/76
2/3/76
2/5/76
2/3/76
2/5/76
2/3/76
2/5/76
2/3/76
2/5/76
2/3/76
2/5/76
Test Type Duration HC
FTP
FTP
SET-7
SET-7
SET-7
SET-7
HWFET
HWFET
SET-7
SET-7
SET-7
SET-7
30 mph accel 20 min
30 mph accel 20 min
30 mph S/S 30 min
30 mph S/S 30 min
60 mph accel 20 min
60 mph accel 20 min
60 mph S/S 20 min
60 mph S/S 20 min
0.43
0.47
0.11
0. 14
0. 12
0. 14
0.07
0. 10
0. 13
0. 13
0. 13
0. 50
0. 16
0,40
0.05
0.21
0. 10
0. 15
0.06
0. 18
CO
9.03
10.37
2.38
4.24
2.78
3. 15
0. 78
1. 50
3.05
3.42
3.83
5.32
1.00
0.65
0.01
0.06
1.75
2.63
0.08
0.05
NOX
1.81
0.99
0. 92
0.91
1,07
0.82
0.86
0.70
0.95
0.80
0.92
0.83
0.48
0.26
0. 34
0.32
0.96
0. 91
0.72
0.86
so?.
0. 103
0.072
0.069
0.061
0.073
0.062
0.062
0.058
0. 061
0.062
0.077
0.080
0.026
0.019
0.016
0.016
0.103
0.072
0.070
0.062
mg/km
H2S04
11.08
7.58
24.74
11.02
15.04
11.56
13.83
14.81
16.56
11.16
11.36
9.76
7.41
3.72
9.70
45.90
17.92
17.85
18.70
S as
HZS04
5.48
3.64
16. 74
7.26
10.05
7.57
10.65
11.23
11.05
7.38
7.67
6.36
6.82
3.72
9.40
36. 18
13. 94
14.50
15.02
S as
S02
77. 78
53.06
71.07
61.40
74.44
62. 14
73. 52
67.72
62.43
63. 64
79. 31
79.97
39.47
26.44
25.01
23.59
124. 13
85.80
86.57
75.64
Total
Recovery
83.26
56.70
87.81
68.65
84.49
69.72
84. 17
78.95
73.47
71,02
86. 97
86.33
33.27
28. 74
32.99
160.31
99.74
101.06
90.66
-------
TABLE H-31.1975 49 STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolithic Catalyst without Air Injection, 0. 0410% Sulfur Fuel
Emissions Summary - 64400 Kilometres
£/km
Date
3-25-76
3-25-76
3-25-76
3-25-76
3-25-76
? 3-25-76
vO
3-25-76
3-25-76
3-25-76
3-25-76
Test Type
FTP
SET-7
SET-7
HFET
SET-7
SET-7
Accel to 30
30 mph S/S
Accel to 60
60 mph
Duration HC
0.
0.
0.
0.
0.
0.
20 min. 0.
20 min. 0.
20 min. 0.
20 min. 0,
63
45
51
41
55
53
11
05
19
68
CO
15. 58
16.12
19.51
16. 17
20.45
19.63
1.08
0.02
7.87
22. 31
1. 70
1.61
1.61
1.79
1.74
1.52
1.09
0.87
2.09
2.08
SO7
0. 159
0.083
0.069
0.063
0.066
0.075
0.018
0.014
0. 106
0.076
% Fuel
mg / km S as
H2SO4 H2S04
2.77
0.47
0.26
0. 86
0.92
0.88
0.48
0. 75
2. 14
0. 12
1.
0.
0.
0.
0.
0.
0.
0.
1.
0.
37
31
17
65
59
57
51
84
75
09
% Fuel
S as
SO?
120. 93
82.58
68.51
73.52
64.96
74.30
29.25
24.51
132.19
95.16
Total
Recovery
122. 30
82.88
68.67
74.29
65.55
74.87
29.76
25.35
133.94
95.25
-------
TABLE H-32. 1975 49 STATE CHEVROLET IMPALA (SwRI CAR EM-2)
Pelleted Catalyst vrithout Air Injection, 0.0410% Sulfur Fuel
Emissions Summary - 64400 Kilometres
Date
3-10-76
3-10-76
3-10-76
3-10-76
? 3-10-76
o
3-10-76
3-10-76
3-10-76
3-10-76
3-10-76
Test Type
FTP
SET-7
SET-7
HFET
SET-7
SET-7
Accel to 30
30 mph
Accel to 60
60 mph
Duration HC
0.
0.
0.
0.
0.
0.
20 min. 0.
20 min. 0.
20 min 0.
20 min 0.
39
21
24
20
34
29
43
24
08
19
g
CO
11. 91
8. 30
11. 10
10.45
16. 11
13.49
11.27
8.40
5.40
17.88
/km
NOX
1.99
1. 71
1.64
1.45
1.41
1. 22
0. 63
0.79
1. 93
1.45
S02
0. 115
0. 141
0. 128
0. 143
0. 110
0.081
0.057
0.057
0.209
0. 105
mg/km
H2S04
0. 90
0. 84
0.70
0. 83
0. 12
0. 28
0. 98
0. 10
2. 22
0.26
% Fuel
S as
H2S04
0.
0.
0.
0.
0.
0.
0.
0.
1,
0.
46
55
47
60
08
28
89
10
74
20
% Fuel
S as
so2
88.86
140.44
131. 11
158. 10
112.36
87. 97
80.35
83. 53
249. 52
127.02
Total
Recovery
89.31
140.99
131. 58
158.70
112.44
88.26
81,24
83.63
251. 25
127. 23
-------
TABLE H-33. 1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR EM-3)
Monolithic Catalyst with Air Injection 0. 0410% Sulfur Fuel
Emissions Summary - 64400 Kilometre*
% Fuel % Fuel
Date
3-26-76
3-26-76
3-26-76
3-26-76
3-26-76
ffi
,k 3-26-76
i— •
3-26-76
3-26-76
3-26-76
3-26-76
Test Type Duration HC
FTP
SET-7
SET-7
HFET
SET-7
SET-7
30 mph accel
30 mph
60 mph accel
60 mph
0. 57
0.
0.
0.
0.
0.
0.
0.
0.
0.
13
14
20
16
17
42
22
15
12
g/l
CO
5. 52
1.04
0.88
0.21
0.78
0. 76
0.09
0.04
0.06
0.04
cm
NOX
1.98
1. 73
1. 83
1. 11
1.20
1.31
1.07
0. 89
1.33
1.93
so 2
0. 100
0. 157
0. 119
0.067
0. 185
0. 150
0.033
0.029
0.053
0.042
mg/km
H2S04
4. 37
6.87
7. 78
11.41
8.95
6.27
3.18
35.44
49.32
19.76
S as
H2S04
2. 08
4.91
5.06
8. 14
5.65
3.87
2.55
29.68
39.72
16.62
S as
so2
72. 75
171.30
118.87
72.64
178. 73
141. 58
40.33
36. 92
64.85
53.60
Total
Recovery
74.
176.
123.
80.
184.
145.
42,
66.
104.
70.
83
21
93
79
37
45
89
60
58
22
-------
Date
3-16-76
3-16-76
3-16-76
3-16-76
TABLE H-34. 1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst with Air Injection 0.0410% Sulfur Fuel
Emissions Summary - 64400 Kilometres
% Fuel % Fuel
FTP
SET-7
SET-7
HFET
3-16-76 SET-7
Uj. 3-16-76 SET-7
i
1X1 3-16-76 30 mph accel,
3-16-76 30 mph
3-16-76 60 mph accel
3-16-76 60 mph
Duration HC
0.61
0 .14
0. 16
0. 13
0. 21
0.20
OnQ
. Uo
0.05
0.08
K/k
CO
12.92
4. 14
5.60
0. 37
10. 12
7.77
OC.A
0.02
0.27
:m
NOX
1.30
1.19
1.04
1. 10
0.88
0.88
A £ C
U. O D
0.28
1.43
so2
0. 137
0.077
0.078
0.090
0. 135
0.097
0<\") "3.
, \)c,J
0.012
0.078
mg/km
H2SO4
6.27
11. 13
6.97
12.87
8.36
6.91
2.92
24.02
S as
H2S04
2.73
6.60
4. 19
8. 56
5.02
4. 13
2.75
18,01
S as
so2
91.43
69.94
72.22
91.91
123. 69
89.01
1A ">f\
jrt . £,\J
17.05
89. 15
Total
Recovery
94. 15
76.55
76.41
100.48
128.71
93. 14
19.80
107. 16
0.09
0.23
1. 30
0.065
8. 74
6.63
75.05
81.68
-------
TABLE H-35. 1975 49 STATE PLYMOUTH GRAN FURY (SwRI CAR EM-1)
Monolithic Catalyst Without Air Injection 0. 0410% Sulfur Fuel
Emissions Summary - 80500 Kilometres
% Fuel % Fuel
g/km
Date
5/7/76
5/11/76
5/7/76
5/11/76
5/7/76
5/11/76
5/7/76
K 5/11/76
i
w 5/7/76
5/11/76
5/7/76
5/11/76
5/7/76
5/11/76
5/7/76
5/11/76
5/7/76
5/11/76
5/7/76
5/11/76
Test Type Duration
FTP
FTP
SET-7
SET -7
SET-7
SET-7
FET
FET
SET-7
SET-7
SET-7
SET-7
Accel to 30 20 min.
Accel to 30 20 min.
30 mph 30 min.
30 mph 30 min.
Accel to 60 20 min.
Accel to 60 20 min.
60 mph 20 min.
60 mph 20 min.
HC
0.66
0.59
0.26
0.33
0. 29
0.53
0. 19
0.38
0. 32
0. 55
0. 35
0.68
0.09
0. 17
0. 06
0. 06
0.08
0. 31
0.09
0.81
CO
11.77
15. 25
8.21
11.43
9.54
18.30
6.47
13.80
11. 55
19.45
12.73
24.45
0.79
0.89
0.01
0.00
2.70
10.97
20.86
23.70
NOX
2.27
1.97
1.98
2.03
2.23
1.86
2.44
2.01
1.87
1.80
1.88
1.66
0.99
1.23
0.86
0. 94
2.29
2. 12
2.20
2.22
mg/km S as
SO2 H2SO4 H2SO4
0. 167
0.088
0. 118
0.069
0.097
0.042
0.062
0.028
0.084
0.047
0.068
0.058
0.021
0.019
0.009
0.009
0. Ill
0. 083
0.043
0.042
1.80
1.22
0.81
0.61
0.44
0.42
0. 31
0. 19
0. 22
0.21
0. 15
0.40
0.15
0. 14
0.67
0. 51
1. 11
0.76
0. 16
0.08
0.89
0. 58
0. 54
0.39
0.29
0. 28
0. 25
0. 15
0. 15
0.14
0. 10
0.26
0. 17
0. 16
0.78
0.59
0.98
0.61
0. 13
0.07
S as Total
SO2 Recovery
126.33
64.63
119.61
68. 19
97. 14
42.81
74. 94
32. 15
87. 20
46. 16
69.82
57. 24
35.66
32.70
16.47
15.62
150. 39
102. 31
52.51
53.01
127. 22
65.22
120. 14
68. 58
97.42
43.09
75. 19
32. 30
87. 35
46. 30
69.92
57. 50
35.83
32.86
17.25
16. 20
151.37
102. 92
52.64
53.08
-------
TABLE H-36. 1975 49 STATE CHEVROLET IMPALA (SwRI CAR EM-2)
Pelleted Catalyst Without Air Injection 0. 0410% Sulfur.Fuel
Emissions Summary - 80500 Kilometres
% Fuel % Fuel
Date
4/19/76
5/19/76
4/19/76
5/19/76
4/19/76
5/19/76
4/19/76
7 5/19/76
£t
4/19/76
5/19/76
4/19/76
5/19/76
4/19/76
5/19/76
4/19/76
5/19/76
4/19/76
5/19/76
4/19/76
5/19/76
Test Type Duration
FTP
FTP
SET-7
SET-7
SET-7
SET-7
HFET
HFET
SET-7
SET-7
SET-7
SET-7
Accel to 30 20 min.
Accel to 30 20 min.
30 mph 30 min.
30 mph 30 min.
Accel to 60 20 min.
Accel to 60 20 min.
60 mph 20 min.
60 mph 20 min.
1
0.
3,
o
1.
o
1.
0.
0.
0.
1.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
TC
. 80
.47
36
28
38
35
13
64
30
96
30
46
05
21
05
04
00
45
06
02
CC
14.
24.
8
7.
10.
8.
3.
3.
8.
11.
8.
9.
0.
0.
0.
0.
0.
1.
3.
0.
g/k
)
.74
,43
81
92
59
85
56
00
27
83
89
15
07
57
00
02
50
88
73
08
:m
NOX
2.04
1.76
2 35
1.71
2 16
1.66
2.21
1.82
2.06
1.59
2. 50
1.69
0.62
0.53
0.80
0.60
2.26
1.64
1.74
1.49
so2
0. 120
0. 170
0 111
0. 102
0 112
0. 147
0. Ill
0.087
0.090
0. 144
0.093
0. 112
0.028
0.027
0.013
0.017
0. 130
0.077
0.028
0.065
mg/km
H2S04
1. 13
1.56
0. 98
0.96
1.03
1.64
1.68
1.40
2. 10
1.00
0. 36
0. 38
0.96
0. 28
13. 36
12. 31
1.53
5.58
S as
H2S04
0. 55
0.73
0.67
0.63
0.77
1.22
1. 11
0. 94
1.37
0.66
0. 33
0. 37
0.99
0. 28
10.25
10.63
1.19
4.62
S as
so2
89.94
122. 61
tOQ A*5
106. 07
112 74
148. 18
126. 58
98.94
90. 58
147.67
92.26
113. 10
38. 83
41. 24
19.58
26.04
152. 19
101. 86
33. 35
81.94
Total
Recovery
90.49
123.34
106. 73
148.82
127.35
100. 16
91.69
148.60
93.63
113. 76
39. 16
41. 61
20. 56
26.32
162.44
112.49
34. 55
86. 56
-------
TABLE H-37. 1975 CALIFORNIA PLYMOUTH GRAN FURY (SwRI CAR EM-3)
Monolithic Catalyst With Air Injection, 0. 0410% Sulfur Fuel
Emissions Summary - 80500 Kilometres
% Fuel % Fuel
g/km mg/km S as S as Total
Date
5/12/76
5/14/76
5/12/76
5/14/76
5/12/76
5/14/76
5/12/76
5/14/76
5/12/76
5/14/76
5/12/76
5/14/76
5/12/76
5/14/76
5/12/76
5/14/76
5/12/76
5/14/76
5/12/76
5/14/76
Test Type
FTP
FTP
Average
SET-7
SET-7
Average
SET-7
SET-7
Average
FET
FET
Average
SET-7
SET-7
Average
SET-7
SET-7
Average
Accel to 30
Accel to 30
30 mph
30 mph
Accel to 60
Accel to 60
Average
60 mph
60 mph
Average
Duration HC
0.67
0.68
0.68
0.21
0. 15
0. 18
0. 16
0.9
0. 12
0. 18
0.07
0. 12
0. 11
0.09
0. 10
0. 11
0.09
0. 10
20 min. 0. 53
20 min. 0.09
30 min. 0. 34
30 min. 0. 10
20 min. 0. 23
20 min. 0. 09
0. 16
20 min. 0. 12
20 min. 0. 05
0.08
CO
8.11
8.75
8.43
1.22
1.24
1.23
1.22
1.40
1.31
0.17
0.10
0. 14
0.80
1.38
1.09
1. 15
0.97
1.06
0.10
0.08
0.03
0.02
1.59
1.02
1.30
0.03
0.03
0.03
NOy SO2 H?SO4 H>SO,,
1.77
2.23
2.00
2.05
1.77
1.91
2.01
1.72
1.86
2.61
2.03
2.32
2.09
1.80
1.95-
2. 13
1.77
1.95
2. 14
1.37
2.21
1.37
2.95
2.59
2.77
3. 11
2.46
2.79
0.099
0. 182
0. 140
0.097
0.089
0. 093
0.091
0.085
0.088
0.076
0.068
0.072
0. 114
0. 105
0. 110
0. 114
0. Ill
0. 112
0.027
0.018
0.033
0.022
0.101
0.077
0.089
0.037
0.032
0.034
7.98
5.85
6.92
6.86
5.15
6.00
6.13
4.58
5.36
11.37
9.32
10.34
7.00
5.73
6.37
6. 16
3.72
4.94
4.90
0.25
26.62
1.17
20.30
16.57
18.44
11.05
18.61
14.83
3.41
2.49
2.95
4.05
3. 14
3.60
3.86
2.94
3.40
8.08
7.12
7.60
4. 15
3.69
3.92
3.89
2.45
3. 17
3.87
0.27
22.29
1.29
15.78
13.52
14.65
9. 10
16.08
12. 59
SOz
64.78
118.73
91.76
87.23
82.62
84.93
87. 12
83.48
85.30
82.36
79.56
80.96
103.25
103.29
103.27
109.74
111.58
110.66
32.46
30.74
42.92
36.41
120. 12
95.62
107.87
46.97
42.82
44. 90
Recovery
68. 19
121.22
94 71
91. 28
85. 76
88.52
90. 98
86.42
88.70
90.43
86,68
88. 56
107. 39
106.98
107. 18
113.63
114.03
113.83
36.33
M.01
65.20
37.69
135.90
109. 14
122.52
56. 07
58.89
57.48
-------
TABLE H-38. 1975 CALIFORNIA CHEVROLET IMPALA (SwRI CAR EM-4)
Pelleted Catalyst 0. 0405% Sulfur Fuel
Emissions Summary - 80500 Kilometres
g/km
Date
4/27/76
4/29/76
4/27/76
4/29/76
4/27/76
4/29/76
4/27/76
4/29/76
4/27/76
4/29/76
4/27/76
4/29/76
4/27/76
4/29/76
4/27/76
4/29/76
4/27/76
4/29/76
4/27/76
4/29/76
Test Type Duration
FTP
FTP
Average
SET-7
SET-7
Average
SET-7
SET-7
Average
HFET
HFET
Average
SET-7
SET-7
Average
SET-7
SET-7
Average
Accel to 30 20 min.
Accel t o 30 20 min.
Average
30 mph 30 min.
30 mph 30 min.
Average
Accel to 60 20 min.
Accel to 60 20 min.
Average
60 mph 20 min.
60 mph 20 min.
Average
HC
0.66
0.54
0.60
0. 16
0. 19
0. 18
0. 18
0. 17
0. 18
0.09
0.08
0.08
0. 19
0. 19
0. 16
0. 16
0, 16
0.22
0.30
0.26
0.26
0.23
0.24
0.06
0.04
0.05
0,09
0.04
0.06
CO
12.28
10.58
11.43
4.19
3.49
3.84
5.48
5.35
5.42
1.38
1.35
1.36
3.89
3. 89
4.38
3.88
4. 13
0.20
0.26
0.23
0.04
0.04
0.04
0. 24
0. 12
0. 18
0.26
0.09
0. 18
NOX
1.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
0.
1.
0.
0.
11
94
03
88
85
86
95
85
90
93
83
88
80
86
92
82
87
29
21
25
21
17
19
02
84
93
10
82
96
mg/km
SOz
0.144
0.087
0.116
0.078
0.074
0.076
0.086
0.071
0.078
0.054
0.041
0.048
0.072
0. 076
0.074
0. 070
0.074
0. 072
0.031
0.024
0.028
0. 018
0. 019
0.018
0.047
0.025
0.036
0.049
0.030
0.040
% Fuel
S as
H2SO4 H2SO4
2.54
3.07
2.80
8.44
7.73
8.08
7. 13
4.87
6.00
2.79
2.79
5.21
5.88
5.54
7.27
7.84
7.56
3.82
4.64
4.23
10. 81
10.60
10.70
19. 17
29. 78
24.48
o. 77
11.42
9. 10
1.
1.
1.
5.
4.
4.
4.
3.
3.
2.
2.
3.
3.
4.
5.
4.
3.
3.
3.
9.
9.
9.
14.
23.
19.
5.
9.
f .
13
42
28
04
94
99
39
15
77
03
03
78
78
o9
13
91
23
92
58
21
15
18
58
o4
11
lo
55
36
% Fuel
S as
SO2
97. 92
61.73
79.82
71. 11
72.07
71. 59
81.05
69.93
75.49
55. 82
45. 65
50. 74
74.45
74.45
o9. 55
74. 34
71.95
39.85
31.20
35.53
23. 55
25.40
24.48
55.27
30. 71
42.99
57.48
38.59
48.04
Total
Recovery
99.05
63. 16
81.10
76. 15
77. 00
76. 58
85.44
73.08
79. 26
47. 69
47.69
78.23
78.23
74. 24
79. 47
76. 86
43. 09
35. 12
39. 11
32. 7o
34. 55
33. 66
o9. 85
54. 35
o2 10
^2.64
48. 14
55. 39
-------
APPENDIX I
SUPPORTING INFORMATION FOR
PROCEDURAL, DEVELOPMENT STUDY
-------
SOUTHWEST RESEARCH INSTITUTE
B500 CULEBRA ROAD • POST OFFICE DRAWER 28E,10 • SAN ANIONIO TfcXAS
May 15, 1975
SWRI SULFATE PRECONDITIONING ROUTE
Important: NO WOT Accels - Accels to be PT and uniform, 3 mph/sec
Cumulative
Distance Miles
0
1.030
60 sec idle before leaving Emissions Lab
Emissions Lab N to Culebra Rd maingate @ 20-30 mph
Right turn on Culebra Rd to Callaghan Rd @ 35 mph
Left turn on Callaghan to Millbank
Left turn 1st street and then quick right on street parallel
to Callaghan
Left High Field to Millbank
Right turn on Millbank to Moortown
Right turn on Moortown to Tope raft
Right turn on Topcraft to Callaghan
Right turn on Callaghan, S to Culebra Rd
South on Callaghan to Commerce at 35 mph
Right turn on Commerce, West on Commerce to
Military Dr at 40 mph
Right turn on Military Dr to Loop 410 access Rd
at 40 mph
North on Loop 410 to Culebra Rd
Left turn on Culebra Rd and Left turn back on
Loop 410 S to Marbach Rd at 55 mph
Left turn on Marbach and go East to Military Dr at 30 mph
Idle for three minutes
Right turn on Military Dr to IH 10 at 35 mph
Left turn on IH 10 East to Gen. McMullen Dr at 55 mph
Left turn on Gen. McMullen North to Woodlawn Ave
at 35 mph
Left turn on Woodlawn to Bandera Rd at 30 mph
Right turn on Bandera Rd NW to Loop 410 at 40 mph avg
Left turn on Loop 410 S to Ingram Rd Exit at 55 mph
Loop 410 S access Rd to Culebra Rd at 40 mph
Left on Culebra Rd to main gate SwRI at 40 mph
Right at main gate to Emissions Lab
60 sec Idle at Emissions Lab
28. 935 vs 28. 8 miles of AA precondition
Initial run made in 58 min 45 sec (58. 75 min)
28. 935 miles (60) = 29. 55 mph vs 29. 8 mph of AA preconditioning
58. 75 min
SAN ANTONIO, HOUSTON, CO HP US CHHISTI, ItXAS, AND WASHING TON. P.C.
2.720
3.790
5.739
6. 248
7. 127
10.022
11.179
12.070
16.635
20.236
20.471
23.786
25.554
26.554
27.546
28.935
1-2
-------
Last High Speed (55 mph) = 1. 768
Last Mod Speed (40 mph) = 1. 992
Last Low Speed (25 and 30 mph) = 1. 389^= 3. 381 miles
Total High Speed = 2. 895 miles
4. 565 miles
1. 768 miles
9. 228 miles total
1-3
-------
TABLE 1-1. DATA SUMMARY PART I, SEQUENCE A, 1975 AMC HORNET
(SwRI CAR NO. EM-5) PELLETED CATALYST WITH AIRPUMP, 0.030 PERCENT SULFUR FUEL
Test
Type
Set 7-1
Set 7-2
Set 7-3
Set 7-4
Set 7-1
Set 7-2
Set 7-3
Set 7-4
Set 7-1
Set 7-2
Set 7-3
Set 7-4
Cold LA-4
Hot LA-4
FTP
Cold LA-4
Hot LA-4
FTP
Cold LA-4
Hot LA-4
FTP
FET
FET
FZT
g/km
Date
5/20/75
5/20/75
5/20/75
5/20/75
5/21/75
5/21/75
5/21/75
5/21/75
5/22/75
5/22/75
5/22/75
5/22/75
5/21/75
5/21/75
5/22/75
5/22/75
5/23/75
5/23/75
5/21/75
5/22/75
5/23/75
Run
1
2
3
4
4
5
6
7
4
5
6
7
1
2
1
2
1
2
3
3
3
HC
0.07
0.07
0.08
0.07
0.08
0.08
0.08
0.08
0.06
0.05
0.06
0.06
0.43
0.15
0.27
0,43
0.16
0.28
0.46
0.13
0.27
0.09
0.05
0.05
CO
0.31
0.17
0,15
0.10
0.13
0. 10
0.20
0.16
0.12
0.06
0.11
0.03
5.60
0.64
2. 78
4.81
0.45
2.33
4.81
0.36
2.28
0.25
0.00
0.03
NQy
1.11
1.28
1.21
1.22
1.27
1.31
1.25
1.34
1.23
1.30
1.23
1.28
1.20
1.18
1. 19
1.05
1.07
1.06
1.10
1.17
1.14
1.13
1.24
1.60
SO 2
0.061
0.036
-
0.048
0.045
0.035
0.035
0.035
0. 034
0. 027
0.030
0.024
0. 035
0.044
mg/km
H2SO4
7.97
16.63
47.20
61.00
18.10
21.59
27.70
35.16
33.46
37.87
36,28
45.47
1.61
5.02
3.55
10.35
16.20
13.69
7.96
20.58
13.25
42.06
64.00
77.36
% Fuel S
as H2SO4
8.
17.
50.
65.
19.
23.
29.
38.
36.
42.
39.
50.
1.
4.
8.
13.
6.
17.
61.
75.
86.
34
10
75
23
34
16
83
02
46
25
37
10
24
20
25
90
08
34
17
26
48
% Fuel S
as SO?
97.
61.
57.
79.
76.
41.
45.
41.
36.
53.
63.
74.
07
27
94
90
55
22
21
77
12
15
10
79
Total
Recovery
105.41
97.94
-
119. 27
126.65
42.46
49.41
50. 02
50.02
114.33
138.36
161.28
-------
TABLE 1-2. DATA SUMMARY PART I, SEQUENCE A, 1975 AMC HORNET
(SwRI CAR NO. EM-6) PELLETED CATALYST WITH AIRPUMP, 0.030 PERCENT SULFUR FUEL
Test
Type
Set 7-1
Set 7-2
Set 7-3
Set 7-4
Set 7-1
Set 7-2
Set 7-3
Set 7-4
Set 7-1
Set 7-2
Set 7-3
Set 7-4
Cold LA-4
Hot LA-4
FTP
Cold LA-4
Hot LA-4
FTP
Cold LA-4
Hot LA-4
FTP
FET
FET
FET
g/km
Date
5/20/75
5/20/75
5/20/75
5/20/75
5/21/75
5/21/75
5/21/75
5/21/75
5/22/75
5/22/75
5/22/75
5/22/75
5/21/75
5/21/75
5/22/75
5/22/75
5/23/75
5/23/75
5/21/75
5/22/75
5/23/75
Run
1
2
3
4
4
5
6
7
4
5
6
7
1
2
1
2
1
2
3
3
3
HC
0.08
0. 08
0.08
0.08
0.07
0.07
0.07
0.07
0. 06
0.06
0.06
0.06
0.35
0.15
0.24
0.45
0.14
0.27
0.44
0.14
0.27
0.08
0. 06
0.05
CO
0.50
0.44
0. 14
0.23
0.13
0.44
0. 18
0.33
0.13
0. 04
0. 02
0. 05
4.14
0.63
2.14
4.32
0.43
2.11
3.54
0.34
1.71
0.01
0.01
0.04
NQY
1.38
1.41
1.45
1.43
1.54
1.43
1.45
1.42
1.12
1.22
1.30
1.40
1.28
1.30
1.29
1.21
1.25
1.23
1.29
1.31
1.30
1.70
1.25.
1.48
5Q2
0.062
0.034
0.034
0.035
0.018
0.037
0.040
0.041
0. 034
0.026
0. 033
0.034
0.035
0.035
0.025
0.041
0.028
0.010
mg/km
H2SO4
13.05
14.94
23.19
56.23
39.95
40.51
41.91
40.15
26.35
35. 79
43.10
51.13
3.04
9.58
6.77
10.11
19.64
15.55
10.63
21.40
16.77
52.89
88.00
75.12
% Fuel S
as H2SO4
13.
15.
24.
59.
43.
43.
45.
43.
28.
40.
47.
56.
2.
7.
7.
16.
8.
17.
59.
102.
84.
85
83
45
89
60
78
50
13
95
51
79
70
30
83
59
59
00
17
44
26
06
% Fuel S
as SO?
100.59
55. 72
54.79
57.02
30.21
61.13
65.89
67.56
57.56
45.65
56.64
39.30
44.10
29.05
47.48
48.46
17.80
Total
Recovery
114.43
71.55
79.24
116.91
73. 80
104.91
111. 40
110.69
123.27
106.32
112.07
41.61
51.93
49.80
36.64
55.48
107.90
120.06
-------
TABLE 1-3. DATA SUMMARY PART I, SEQUENCE B, 1975 AMC HORNET
(SwRI CAR NO. EM-5) PELLETED CATALYST WITH AIRPUMP, 0.030 PERCENT SULFUR FUEL
Test
Type
FTP
FTP
FTP
Set
Set
Set
Set
Set
Set
FET
FET
FET
g/km
Date
6/3/75
6/4/75
6/5/75
6/3/75
6/3/75
6/4/75
6/4/75
6/5/75
6/5/75
6/3/75
6/4/75
6/5/75
Run
1
1
1
2
3
2
3
2
3
4
4
4
HC
0.43
0.40
0.42
0.06
0.06
0.11
0.06
0.06
0.06
0.06
0.06
0.06
CO
4.62
4.51
4.62
0.04
0.06
0.14
0.05
0.06
0.09
0.03
0.07
0.06
mg/km
NOV SO2 H2SO4
2.04
1.65
1.88
1.47
1.35
2.05
2.23
1.43
1.46
1.45
1.61
1.81
6.99*
4. 50*
3.22*
15.27
14.42
27.28
20.70
18.94
18.06
23.96
26.08
30.00
% Fuel S % Fuel S Total
as H2SO/C as SO2 Recovery
7.11
4.86
3.41
16.61
15.55
29.91
22.29
21.25
19.72
28.04
31.48
34.90
* Non-weighted based on 11. 09 actual miles run
-------
TABLE 1-4. DATA SUMMARY PART I, SEQUENCE B, 1975 AMC HORNET
(SwRI CAR NO. EM-6) PELLETED CATALYST WITH AIRPUMP, 0.030 PERCENT SULFUR FUEL
Test
Type
FTP
FTP
FTP
Set
Set
Set
Set
Set
Set
FET
FET
FET
g/km
Date
6/3/75
6/4/75
6/5/75
6/3/75
6/3/75
6/4/75
6/4/75
6/5/75
6/5/75
6/3/75
6/4/75
6/5/75
Run
1
1
1
2
3
2
3
2
3
4
4
4
HC
0.36
0.43
0.43
0.06
0.06
0.06
0.06
0.06
0.07
0.05
0.06
0.05
CO
3.42
3.92
3.18
0.03
0.05
0.01
0.01
0.02
0.09
0.01
0.03
0.01
NOy SO;
1.97
2.19
2.16
1.36
1.38
1.48
1.36
1.59
1.51
1.45
1.08
1.58
mg/km
% Fuel S % Fuel S Total
l_ H2SO4 as H2SO4 as SO2 Recovery
9.38*
13.67*
16.24*
29.12
27. 04
32.83
34.65
42.59
26.54
40.82
37.24
42.01
9.80
16.99
14.13
31.48
29.32
34.16
37.27
44.95
29.84
48.14
52.93
50.79
'* Non-weighted based on 11.09 actual miles run
-------
TABLE 1-5. DATA SUMMARY PART I, SEQUENCE C, 1975 AMC HORNET
(SwRI CAR NO. EM-5) PELLETED CATALYST WITH AIRPUMP, 0.030 PERCENT SULFUR FUEL
i
CD
Test
Type
FTP
FTP
FTP
FET
FET
FET
Set
Set
Set
Set
Set
Set
g/km
Date
6/10/75
6/11/75
6/12/75
6/10/75
6/11/75
6/12/75
6/10/75
6/10/75
6/11/75
6/11/75
6/12/75
6/12/75
Run
2
2
3
4
3
4
3
4
HC
0.47
0.46
0.37
0.05
0.04
0. 05
0,07
0. 06
0.07
0. 05
0.07
0.05
CO
4.43
4.42
4.13
0.07
0.03
0.10
0.05
0.23
0.19
0.03
0.08
0. 02
NOY
1.98
2.06
2.09
1.26
1.56
1.50
1.38
1.27
1.50
1.46
1.43
1.60
SO2
0.028
0.023
0.023
0.027
0.026
0.021
0. 045
0.051
0.041
0. 040
0.041
0. 032
mg/km
H2S04
4.61
6.66
3.46
33.24
36.13
24.16
12.92
20.54
12.60
25.48
17.88
25.41
% Fuel S
as H2SO4
4.89
7.01
3.58
40.13
45.53
29.50
15.10
22.34
14.18
28.46
19.78
26.69
% Fuel S Total
as SO 2 Recovery
33.
37.
35.
50.
49.
39.
72.
67.
69.
65.
69.
50.
60
64
76
13
57
61
93
11
94
53
52
95
38.49
44.65
39.34
90.26
95.10
69.11
88.04
89.45
84.12
96.98
89.30
77.64
-------
TABLE 1-6. DATA SUMMARY PART I, SEQUENCE C, 1975 AMC HORNET
(SwRI CAR NO. EM-6) PELLETED CATALYST WITH A1RPUMP, 0.030 PERCENT SULFUR FUEL
Test
Type
FTP
FTP
FTP
FET
FET
FET
Set
Set
Set
Set
Set
Set
g/km
Date Run
6/10/75
6/11/75
6/12/75
6/10/75
6/11/75
6/12/75
6/10/75
6/10/75
6/11/75
6/11/75
6/12/75
6/12/75
2
2
2
3
4
3
4
3
4
HC
0.44
0.48
0.39
0.04
0.05
0.04
0.06
0.06
0.04
0.09
0.05
0.05
CO
3.38
3.38
3.25
0.00
0.07
0.00
0.03
0.03
0.03
0.04
0.02
0.00
2.02
2.08
2.17
1.29
1.56
2.74
1.60
1.35
1.04
1.85
1.59
1.54
mg/km.
S0?
0.030
0.027
0.036
0. 037
0.036
0.038
0. 034
0.030
0.040
0.033
0.031
% Fuel S
H?SO4 as H2SO4
8.44
7.97
12.56
44.30
38.03
46.62
22.33
33.67
12.85
32.83
31.33
43.82
8.89
8.52
12.72
57.04
46.29
58.63
23.31
38.27
25. 12
35.83
33.51
48.83
% Fuel S Total
as SO? Recovery
41.27
43.77
71.
68.
69.
60.
59.
90.
66.
53.
53.
50
64
62
28
95
47
71
97
65
50.16
52.29
128.54
114.93
128.25
83.59
98.22
115.59
102.54
87.49
102.48
-------
TABLE 1-7. DATA SUMMARY PART I, SEQUENCE D, 1975 AMC HORNET
(SwRI CAR NO. EM-5) PELLETED CATALYST WITH AIRPUMP, 0.030 PERCENT SULFUR FUEL
Test
Type
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
^Deleted
Coef.
Coef.
g/km
Date
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
from average
Avg.
Std.Dev.
of Var (%)
Avg.
Std.Dev.
of Var {%)
Run
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
1-20
1-20
1-20
4-20
4-20
4-20
HC
0.35
0.06
0.05
0.05
0.06
0.06
0.05
0.05
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.07
0.06
0.06
0.06
0.06
0.06
CO
* 3.92*
0.13
0.13
0.14
0.05
0.02
0.07
0.09
0.03
0.06
0. 14
0.07
0.08
0. 14
0.07
0.45
0.04
0.14
0.02
0.08
0. 10
0.005 0.09
8. 3
0.06
<0. 01
8.2
88.9
0. 10
0. 10
100.0
NOX
1.26
1.40
1.91
1.22
1.39
1.42
1.42
1.34
1.48
1.57
1.31
1.35
1.48
1.28
1.36
1.23
1.30
1.38
1.31
1.21
1. 50
0. 54
36.4
1.36
0. 10
7.3
SO?,
0. 022
0.028
0.023
0.038
0. 035
0.031
0.032
0. 044
0. 025
0.035
0. 041
0. 028
0. 048
0.055
0.035
0. 060
0.027
0.042
0. 032
0. 044
0.036
0.010
28. 5
0. 038
0. 010
25. 3
mg/km
H2SO4
9.25
25.14
36.02
38.43
37.95
46.41
41.99
36.63
43.53
41.22
41.73
36.11
46.67
25.46
44.55
25.01
37.15
25.61
43. 72
31.39
35. 70
9.46
26.6
37.86
7. 17
18.9
% Fuel S
as H?SO4
9.
26.
39.
44.
42.
51.
46.
40.
47.
45.
46.
39.
50.
28.
49.
28.
•41.
28.
49.
34.
39.
10.
27.
42.
7.
18.
15
99
80
29
04
21
84
79
42
51
26
85
65
33
27
07
40
78
23
35
51
66
0
02
80
6
% Fuel S
as SO2
33.94
46.33
38.97
66.54
58.63
51.69
55.12
74.67
41.58
59.14
69.08
47.87
80.43
93.66
59.62
102.53
45.50
72.91
54.61
73.07
61. 30
17. 97
29. 3
65. 10
16.62
25. 5
Total
Recovery
43.09
73.32
78.77
110.83
100.67
102.90
101.96
115.46
89.01
104.64
115.34
87.72
131.07
121.99
108.90
130.60
86.90
101.69
103.83
107.42
100. 81
20.42
20. 3
107. 11
13. 10
12. 2
-------
TABLE 1-8. DATA SUMMARY PART I, SEQUENCE D, 1975 AMC HORNET
(SwRI CAR NO. EM-6) PELLETED CATALYST WITH AIRPUMP, 0.030 PERCENT SULFUR FUEL
Test
Type
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
g/km
Date
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
Run
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
HC
0.30*
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.06
0.05
0.06
0.07
0.06
0.06
0.06
0.07
0.06
0.07
0.06
CO
3.31*
0.12
0.17
0.03
0.07
0.05
0.11
0.03
0.20
0.06
0.06
0.19
0.23
0.06
0.04
0.29
0.52
0.04
0.22
0.09
NOX
1.20
1.34
1.32
1.26
1.37
1.27
1.27
1.48
1.41
1.23
1.33
1.36
1.32
1.44
1.42
1.33
1.42
1.33
1.27
1.38
SO2
0.067
0.046
0.038
0.034
0.037
0.034
0.037
0. 042
0.049
0.031
T-IT
0.050
0. 084
0.028
0.035
0.040
0.065
0.037
0.035
0.030
mg/km
H2SO4
8.16
21.13
23.90
32.60
33.55
41.89
40.97
53.24
28.56
30.68
42.62
32.92
24.94
43.78
43.67
31.58
24.33
35.23
33.80
37.21
% Fuel S
as H2SO4
8.17
22.90
26.82
35.74
36.04
45.66
45.78
56.46
31.18
33.61
47.03
36.26
27.50
49.48
48.76
35.79
26.85
39.41
37.63
42.52
% Fuel S
as SOz
103.48
76.32
66.11
57.13
60.79
55.78
62.46
67.62
82.03
51.82
*
84.58
141.22
48.17
59.68
70.21
110.38
62.68
59.55
51.61
Total
Recovery
111.65
99.22
92.93
92.87
96.83
101.43
108.24
124.08
113.21
85.43
3*i
120.84
168.72
97.66
108.44
106.00
137.23
102.10
97.18
94.14
^Deleted from average
** Sample
Coef
Coef
Vial Broken
Avg.
Std.Dev.
. ofVar. (%)
Avg.
Std.Dev.
. of Var. (%)
1-20
1-20
1-20
4-20
4-20
4-20
0.06
< 0.01
6.2
0.06
^0.01
7.9
0. 14
0. 13
90.4
0. 13
0. 13
95. 9
1.34
0.07
5.5
1.35
0.07
5.4
0.043
0.015
33.7
0.042
0.015
34.8
33.45
10.28
30.7
35. 97
7.56
21.0
36.68
11.09
30. 2
39. 75
8.20
20. 6
72. 19
23.66
32.8
70.36
24.48
34.8
108. 33
19.25
17.8
109.65
20. 51
18.7
-------
TABLE 1-9. DATA SUMMARY PART I, SEQUENCE E, 1975 AMC HORNET
(SwRI CAR NO. EM-5) PELLETED CATALYST WITH AIR PUMP, 0. 030 PERCENT SULFUR FUEL
Test Type
Set-7
Set-7
Set-7
Set-7
Set-7
Set-7
Set-7
Set-7
Set-7
Set-7
Set-7
Set-7
Date
6/23/75
6/23/75
6/23/75
6/23/75
6/23/75
6/23/75
6/23/75
6/23/75
6/23/75
6/23/75
6/23/75
6/23/75
Run
1
2
3
4
5
6
7
8
9
10
11
12
Fuel
Canister . .,_
connected
connected
connected
connected
connected
connected
disconnected
disconnected
disconnected
disconnected
• disconnected
disconnected
Gaseous Emissions
HC
0.22
0.06
0.06
0.06
0.06
0.07
0.07
0.07
0.06
0.06
0.06
0.06
CO NOX
2.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
40 1.90
07 1.60
03 1.83
04 1.92
08 1.83
06 1.88
00 1.62
08 1.78
04 1.31
07 1.55
10 1.54
10 1 . 96
Average,
Standard
, g/km
SO?
0.050
0.042
0.041
0.036
0.063
0.059
0.026
0.022
0.027
0.035
0.037
0.028
all tests
Deviation
Coefficient of Var.
Average,
Standard
tests 2-5
Deviation
Coefficient of Var.
Average,
Standard
tests 7-12
Deviation
Coefficient of Var.
mg/km
H?SO4
21.75
35.80
38.18
49. 83
36.97
44.08
48. 72
32.63
39.82
45.04
43.95
41.5
5. 7
13.7%
40. 2
6.47
16.1%
42.37
5.55
13.1%
% Fuel S
as H2SO.1
21.50
39.56
39.70
51.89
37.93
46.94
48.37
38.83
43.49
51.62
51.32
% Fuel S
as JO2
75.97
70.91
65.66
57.37
99.12
92.11
42.02
32.70
50.01
59.10
65.35
4°. 21
Total
Recovery
97.47
110.46
105.36
109.26
137.05
88.96
82.07
88.84
102.59
116.97
100.53
-------
u>
TABLE 1-10. SUMMARY OF EMISSION RESULTS, PART II, SEQUENCE A (SET-7 TESTS)
1975 AMC Hornet, EM-5
Pelleted Catalyst With Air, 0. 03 Percent Fuel Sulfur
Test Date 7/23/75, All Tests With One Driver
Test
No.
1
2
3
4
5
6
7
8
9
10
11
12
All Tests
Average
Std. Dev.
Goef. of Var
Tests 4-12
Average
Std. Dev.
Coef. of Var
Gaseous Emissions, g/mi
HC
0.10
0.10
0.10
0.11
0.09
0.10
0.11
0.05
0.09
0.09
0.10
0.10
0.10
0.02
15.7%
0.09
0.02
20.0%
GO
0.06
0.03
0.08
0.08
0.11
0.00
0.07
0.05
0.07
0.06
0.06
0.00
0.06
0.03
53.9%
0.06
0.04
64. 3%
C02
489.0
489.0
483.0
491.0
491.0
482.0
497.0
479.0
488.0
480.0
496.0
487.0
488
5.8
1.2%
488
6.6
1.3%
NOX
2.30
2.15
2.08
1.95
2.09
2.19
2.29
2.32
2.29
2.16
2.23
2.16
2.18
0.11
5.1%
2.19
0.12
5.3%
SO 2,
mg/mi
65. 71
50.85
68.32
53.10
69.51
61.94
81.16
52.10
53.65
66.07
53.15
45.85
60. 12
10.29
17.1%
59.61
11.04
18.5%
H2S04,
mg/mi
37.87
38.42
52.31
58.93
64.89
57.62
61.64
62.13
62.63
59.76
64.38
60.13
56.73
9.29
16.4%
61.35
2.45
4.0%
Avg. Cat.
Temp.
°F
914
914
907
916
913
910
910
908
915
912
912
908
912
2.97
0.3%
912
2.83
0.3%
% of Fuel "S" as
S02
68.68
53.17
72.38
55.26
72.38
65.71
83.54
55. 59
56.24
70.43
54. 77
48.14
63.02
10.61
16.8%
62.45
11.28
18.1%
H2S04
25.87
26.25
36.21
40.06
44.15
39.94
41.46
43.31
42.90
41.62
43.34
41.25
38.86
6.34
16.3%
42.00
1.50
3.6%
Total
Recovery
94.55
79.43
108.58
95.32
116.53
105.64
124.99
98.90
99.14
112.05
98.11
89.40
101.89
12.43
1 2. 2%
104.45
11.38
10.9%
-------
4s-
TABLE I-11. SUMMARY OF EMISSION RESULTS, PART II SEQUENCE B
1975 AMC HORNET, EM-5
Pelleted Catalyst -with air, 0. 03 percent sulfur fuel
Test date 7/24/7
Test
No.
1
2
3
4
5
6
7
Avg. 1-5
Std. Dev.
Coef. of
Avg. 2-5
Std. Dev.
Coef. of
Test
Type
35
mph
35
mph
35
mph
35
mph
35
mph
Set 7
Set 7
1-5
Var. 1-5
2-5
Var. 2-5
Gaseous Emissions, g/mi
HC
0.00
0.08
0.05
0.08
0.08
0.08
0.08
0.06
0.03
58. 2rc
0.07
0.02
28. 6%
CO
0.06
0.02
0.00
0.08
0.02
0.01
0.07
0. 04
0. 03
82. 2%
0.03
0.03
100.0%
CO?
360.0
375.0
354.0
358.0
346.0
495.0
481.0
358.6
10.6
3.0%
358. 3
12.2
3.4
NOX
2.42
2.32
2.28
2.35
2.47
2.80
2.75
2.37
0.08
3.2%
2. 36
0. 08
3.5%
so2
mg/mi
25.00
29. 25
44.19
38.83
46.29
121.83
170.78
36.71
9.29
25. 3%
39.64
7.61
19. 2%
H2S04
mg/mi
14.32
28. 23
30. 28
32.00
37.58
156.56
89.30
28.48
8.65
30. 36
32.02
4.01
12. 5%
Cat.
Temp.
°F
757
736
753
755
753
921
922
751
8.4
1. 1%
749
8.8
1.2%
% of Fuel "S" as
SO?
35.57
39.89
63.85
57.46
68.42
125.81
181.48
53.04
14.6
27. 5%
57.41
12. 51
21.8%
H2S04
13.32
25.15
28.58
29.85
36.29
105. 63
62. 00
26.64
8.47
31. 79
29.97
4.66
15. 5%
Total
Recovery
48.89
65.05
92.43
87.31
104. 71
231.45
243.47
79.68
22.41
28. 13
87.38
16. 58
19.0%
-------
Ul
TABLE 1-12. SUMMARY OF EMISSION RESULTS, PART II, SEQUENCE C
1975 AMC Hornet, EM-5
Pelleted Catalyst With Air, 0.03 Percent Sulfur Fuel
Test Date 7/25/75
Cat.
Test
No.
1
2
3
4
5
6
7
Avg.
Std.
Coef
Avg,
Std.
Coef
Test
Type
50
rnph
50
mpr.
50
rnpr.
50
mpri
50
mpr.
Set 7
Set 7
1-5
Dev.
. of Var.
. 2-5
Dev.
. of Var.
Gaseous Emissions, g/mi
HC
0.06
0.07
0.06
0.05
0.04
0.12
0.10
0.06
0.01
16.7%
0.06
0.01
23.5%
CO
0.06
0.00
0. 03
0.00
0.03
0.15
0.04
0.02
0.03
104.6%
0.02
0.02
115.5%
C02
426.0
426. 0
429.0
426.0
394.0
484.0
491.0
420.2
14.7
3.5
418.8
16.6
4.0
1.67
2.13
1.96
2.10
1.78
2.49
2.58
1.97
0.15
7.6%
1.99
0. 16
8.0%
S02
mg/ mi
33.60
30.67
27.79
39.30
35.79
59.92
71.43
33.43
4.46
13.3%
33.39
5.15
15.4%
H2S04
mg/mi
58.63
66.45
63.39
60.75
61.06
71.96
73.45
62.06
2.98
4.8%
62.91
2.64
4.2%
Temp.
op
970
968
971
963
958
907
904
966
5.4
0.6%
965
5.7
0.6%
-~5 of Fuel !'S" as
S0?
40.30
36.81
33. 16
47.17
46.43
63.32
74.42
40.77
6.06
14.9%
40.89
6.99
17.1%
H2S04
45.94
52. 12
49.41
47.63
51.'76
49.69
50.00
49.37
2.65
5.4%
50.23
2.11
4.2%
Total
Recovery
86. 24
88.93
82. 57
94. 80
98. 19
113.00
124.43
90.15
6.33
7.0%
91.12-
6.87
7.5%
-------
TABLE 1-13. SUMMARY OF EMISSION RESULTS, PART II SEQUENCE D (SET-9 TESTS)
1975 AMC Hornet EM-5
Pelleted Catalysts with air, 0. 03 percent sulfur fuel
Test date 7/30/75
•1
«l
•^
Avg.
Std.
Coef.
Avg.
Std.
Coef.
Test
No.
1
2
3
4
5
6
7
8
9
10
11
12
1-12
Div. 1-12
of Var. 1-12
4-12
Div. 4-12
of Var. 4-12
Gaseous Emissions,
HC
0.27
0.11
0.10
0.09
0.09
0.08
0.09
0.09
0.15
0.11
0.09
0.10
0. 11
0.05
45. 8%
0. 10
0.02
21. 1%
CO
0.43
0.05
0.03
0.06
0.07
0.13
0.00
0.09
0.03
0.04
0.07
0.13
0.09
0. 11
119.7%
0.07
0.04
63.0%
G02
504.0
488.0
473.0
471.0
469.0
463.0
477.0
459.0
482.0
474.0
476.0
497.0
477. 8
.13.2
2.8%
474. 2
11. 1
2. 3%
g/mi
NOX
2.10
2.38
2.27
2.29
2.29
2.21
2.33
2.21
2.36
2.36
2.30
2.48
2. 30
0. 10
4.2%
2. 31
0.08
3.6%
SO 2
mg/mi
9.95
52.25
40.97
50.69
50.05
54.02
50.81
47.55
63.05
41.01
52.19
48.58
46.76
12. 95
27. 8%
50. 88
5.85
11,5%
H2S04
mg/mi
51.40
71.17
58.51
70.50
70.50
75.03
69.93
72.53
62. 74
76.28
70.15
70. 72
68.29
7. 19
10. 5%
70. 93
3. 82
5.4
Avg. Cat.
Temp. °F
921
913
908
909
902
904
904
905
904
903
908
908
907
5. 3
0.6%
905
2.49
0.3%
% of Fuel S as
S02
10.07
54.78
44.28
55.08
54.57
59.70
54.52
53.00
66.90
44.20
56.05
49.97
50. 26
14.06
28. 0%
54. 89
6. 24
11.4%
H2SQ4
33.99
48.75
41.32
50.06
50.23
54.18
49.02
52.81
43.49
53. 71
49.22
47.52
47.86
5.78
12. 1%
50. 02
3. 34
6,7%
Total
Recovery
44.06
103.54
85.60
105.13
104.80
113.88
103.53
105.82
110.39
97.91
105.27
97.49
98. 12
18.44
18. 8%
104. 91
5. 21
5.0%
%02
5.38
5.39
5. 74
5.7.1
5.77
5.61
5.77
5.55
5.63
5.50
5.33
5.30
5. 56
0. 17
3. 1%
5. 57
0. 17
0.03%
-------
TABLE 1-14. SUMMARY OF EMISSION RESULTS, PART II, SEQUENCE E
1975 California Plymouth, EM-3, SET 7
Monolithic Catalyst, 0.0415 Percent Sulfur Fuel
Test Dates 8/1/75, 8/5/75
Test
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Date
8-1-75
8-5-75
Gaseous
HC
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
05
04
04
05
05
05
12
12
10
05
06
04
04
05
04
06
04
04
04
04
04
04
04
04
04
04
04
04
04
03
Emissions g/mi
CO
0
0
0
0
0
0
0
0
0
1
1
0
0
1
0
0
0
0
0
0
0
0
0
0
1
0
0
0
1
0
.47
.68
. 51
.66
.75
.72
.83
.71
.45
.01
. 15
.76
.78
.50
.79
.51
.60
.65
.48
.55
.55
.71
.84
.47
.04
.72
. 53
.68
.27
.54
CO?
607.
647.
615.
613.
639.
630.
629.
620.
629.
636.
599.
614.
618.
649.
616.
682.
664.
658.
658.
659.
639.
648.
636.
658.
645.
623.
632.
625.
634.
620.
Average of
on 8/
1 and
NOX
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
76
85
82
81
84
82
83
81
84
80
83
84
84
91
83
92
97
95
91
92
91
91
88
90
91
86
86
87
91
88
tests 4 to
8/5
Std. Dev. of tests
on 8/
Coef.
on 8/
1 and
8/5
of var. of
1 and
8/5
S02
mg/mi
175
197
153
161
178
160
179
171
152
173
178
167
152
211
163
172
200
168
164
158
139
163
160
149
170
190
140
123
179
194
15
.67
.14
.48
.06
.31
.84
.91
.31
.24
.91
.18
.35
.00
.85
.10
. 12
.86
.07
.43
.63
.74
.93
.23
.93
.57
.26
.64
.08
.66
.46
H2i
504
mg/m:
35.
32.
27.
24.
23.
23.
14.
15.
26.
18.
22.
21.
18.
17.
40.
45.
40.
48.
38.
43.
34.
34.
36.
27.
27.
29.
26.
18.
22.
26.
72
12
33
57
37
72
08
55
03
45
97
63
73
28
08
50
39
55
19
17
52
94
14
31
44
62
08
84
06
66
4 to 15
tests
4 to
15
8.
33.
95
6%
1-17
-------
TABLE 1-14 (Cont'd.) SUMMARY OF EMISSION RESULTS,
PART II, SEQUENCE E
1975 California Plymouth, EM-3, SET 7
Monolithic Catalyst, 0.0415 Percent Sulfur Fuel
Test Dates 8/1/75, 8/5/75
Avg.
Catalyst
Temp. °F
963
965
959
960
963
958
955
951
954
Q54
/ *J*I
968
958
962
950
951
% Fuel "i
S07
110.50
116.24
95.23
100.27
106.45
97.37
109.08
105.38
92.29
104 20
x vs ^r « t*\j
113.32
103.89
93.82
124.22
101.01
S" as
HzSO4
14.68
12.37
11.08
9.99
9.12
9.38
5.58
6.25
10.31
7.67
9.32
8. 72
7.18
6.99
Total
Recovery
125.19
128.61
106.31
110.27
115.57
106.75
114.65
111.63
102.60
120.99
113.20
102.55
131.40
108.01
%Q2
4.36
4.79
4.81
4.74
4.71
4.73
4.73
4.76
4.73
4 Ai
TT « V J.
4.59
4.69
4.64
4.73
4.73
Fuel Wt.
grams
2663
2821
2679
2669
2794
2758
2743
2671
2738
2772
*•» 1 ff t*
2625
2695
2717
2821
2688
Driver
B
B
B
C
A
G
A
A
C
B
B
C
A
B
A
Test
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
940
943
945
937
931
927
926
922
923
919
924
934
927
927
928
96.38
115.42
97.47
95.36
91.82
83.50
96.46
96.05
86.92
100.75
116.52
84.97
75.08
107.94
119.78
14.66
17.08
15.30
18.40
14.44
16.85
13.27
13.68
13.69
10.54
10.98
11.69
10.39
7.40
8.88
111.04
132.50
112.78
113.76
106.27
100.35
109.74
109.73
100.61
111.29
127.50
96.66
85.47
115.34
128.66
4.48
4.81
4.80
4.83
4.87
4.78
4.83
4.86
4.79
4.79
4.68
4.83
4.81
4.63
4.78
3101
3010
2988
2946
2950
2854
2907
2849
2935
2884
2783
2804
2773
2849
2780
C
B
B
C
A
C
A
A
C
B
B
C
A
B
A
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Average of teats
4 to 15 on 8/1 fc 8/5 10.47
Std. Dev. of tests
4 to IS on 8/1 & 8/5 3.31
Coef. of Var. tests
4 to 15 on 8/1 & 8/5 31.6
1-18
-------
APPENDIX J
SUPPORTING INFORMATION FOR BASELINE STUDIES
-------
TABLE J-l. BASELINE EMISSIONS TEST RESULTS
1975 FORD GRANADA, BASELINE CAR 1-3
NO CATALYST, 0.030 PERCENT SULFUR FUEL
g/km
Date
10/23/75
11/6/75
Average
10/23/75
11/6/75
Average
10/23/75
11/6/75
Average
10/23/75
11/6/75
Average
10/23/75
11/6/75
Average
10/23/75
11/6/75
Average
Test Type
FTP
FTP
SET-7
SET-7
SET-7
SET-7
FET
FET
SET-7
SET-7
SET-7
SET-7
Duration
23 min
23 min
23 min
23 min
12 min
12 min
23 min
23 min
23 min
23 min
HC
1.01
0.94
0.98
0.39
0.52
0.46
0.38
0.39
0.39
0.25
0.30
0.28
0.41
0.38
0.40
0.37
0.39
0.38
CO
26.63
24.00
25.32
9.52
9.42
9.47
10.70
9.20
9.95
7.84
5.25
6.55
10.87
9.55
10.21
10.54
10.69
10.62
NOX
1.65
1.60
1.63
1.72
1.92
1.82
1.62
1.85
1.74
1.52
1.78
1.65
1.57
1.71
1.64
1.49
2.68
2.09
S02
0.063
0.069
0.066
0.051
0.060
0.056
0.052
0.043
0.048
0. 055
0.074
0.065
0.057
0.063
0.060
0.054
0.062
0.058
mg/km
H2S04
0.78
0.97
0.88
0.86
0.56
0.71
0.24
0.24
0.24
0.43
0.47
0.45
0.36
0.17
0.27
0.15
0.25
0.20
H2SO4 as %
of fuel S
0.64
0.76
0.70
1.03
0.62
0.83
0.28
0.26
0.27
0.56
0.55
0.56
0.40
0.19
0.30
0.17
0.26
0.22
aO2 as %
of fuel S
79.98
83.08
81.53
94.36
102.47
98.42
91.51
71.62
81.57
110.42
130.68
120.55
98.76
105.09
101.93
93.39
101.47
97.43
Total
Recovery
80.62
83.84
82.23
95.40
103.09
99.25
91.79
71.89
81.84
110.99
131.22
121.11
99.16
105.28
102.22
93.56
101.74
97.65
-------
TABLE J-2. BASELINE EMISSIONS TEST RESULTS
1975 DODGE CORONET, BASELINE CAR 1-4
NO CATALYST, 0.030 PERCENT SULFUR FUEL
g/km
Date
10/28/75
10/29/75
Average
10/28/75
10/29/75
Average
10/28/75
10/29/75
Average
10/28/75
10/29/75
Average
10/28/75
10/29/75
Average
10/28/75
10/29/75
Average
Test Type
FTP
FTP
SET -7
SET -7
SET -7
SET -7
FET
FET
SET -7
SET- 7
SET -7
SET -7
Duration
23 min
23 min
23 min
23 min
1 2 min
1 2 min
23 min
23 min
23 min
23 min
HC
0.85
0.77
0.81
0.51
0.41
0.46
0.41
0.39
0.40
0.44
0.37
0.41
0.45
0.34
0.40
0.44
0.34
0.39
CO
9.03
10.15
9.59
6.02
5.15
5.59
3.53
4.82
4.18
2.04
2.53
2.29
5.04
3.74
4.39
3.01
3.80
3.41
NOX
1.18
1.25
1.22
1.19
1.30
1.25
1.16
1.24
1.20
1.24
1.23
1.24
1.35
1.39
1.37
1.13
1.44
1.29
SOz
0.071
0.074
0. 073
0.052
0.053
0.053
0.054
0.050
0.052
0.052
0.048
0.050
0.058
0.053
0.056
0.059
0.057
0.056
mg/km
H2SO4
0.85
1.25
1.05
1.95
1. 18
1.57
1.52
1.93
1.73
1.63
2.71
2.17
1.52
1.90
1.71
1.56
1.88
1.72
H2SO4 as %
of fuel S
0.58
0.87
0.73
1. 87
1. 15
1. 51
1.51
1.86
1.69
1. 90
3.03
2.47
1.42
1.92
1.67
1. 50
1.83
1.67
SO2 as %
of fuel S
74.01
78.19
76.10
75.81
79.58
77.70
82.34
73.90
78. 12
93.18
81.92
87.55
82.41
81.97
82.19
87.87
77.02
82.45
Total
Recovery
74.59
79.06
76.83
77.68
80.73
79.21
83.86
75. 76
79.81
95.08
84.25
90.02
83.84
83.89
83.87
89.37
78.85
84.11
-------
TABLE J-3. BASELINE EMISSION TEST RESULTS
1975 HORNET SPORTABOUT, BASELINE CAR IIA-1
PELLETED CATALYST WITH AIR PUMP
(0. 030% SULFUR FUEL)
Test
1
1
2
2
3
•3
4
4
5
5
6
6
Date
10/7/75
10/8/75
10/7/75
10/8/75
10/7/75
i n /R/7^
10/7/75
10/8/75
10/7/75
10/8/75
10/7/75
10/8/75
Avg. of 8
Test
Type
FTP
FTP
Avg.
SET-7
SET-7
Avg.
SET-7
ciTT-7
Avg.
FET
FET
Avg.
SET-7
SET-7
Avg.
SET-7
SET-7
Avg.
SET-7's
HC
0.33
0. 35
0. 34
0. 10
0. 11
0. 10
0.08
n OR
0.08
0.07
0.06
0.06
0. 12
0.09
0. 10
0. 12
0. 11
0. 12
0. 10
i
CO
2.28
3.06
2.67
0. 18
0.25
0.22
0.11
n n
0.11
0.05
0.01
0.03
0.33
0.40
0.36
0. 11
0.11
0.21
;/km
NOX
1.43
1.38
1.41
1.64
1.79
1.72
1.74
1 75
1.74
1.81
1.55
1.68
2. 28
1.75
2.02
1.59
1.65
1.62
1.77
S02
0.030
0.047
0.038
0.055
0.036
0.046
0.036
0.036
0.032
0.041
0.036
0.082
0.037
0.060
0.041
0.060
0.050
0.050
mg/km
H2S04
9.93
7.41
8.67
9.71
20.94
15.32
13.92
27 4R
20.70
31.47
44.55
38.01
13.48
16.46
14.97
9.77
18.14
13.96
16.24
% Fuel S
as S
in H2SO4
9.49
7.27
8.38
13.48
27.03
20.26
18.84
37 81
28.32
42.13
69.56
55.84
13.81
23.35
18.58
12. 74
23.95
18.34
21. 38
% Fuel S
as S
in SO2
44. 43
71. 19
57.81
116.79
70.63
93.71
75.31
75. 31
66.45
97. 11
81.78
128.48
80. 99
104. 74
82. 11
121.71
101.91
96. 57
Total
Recovery
53.91
78.46
66.19
130.27
97.66
113.96
94.15
94.15
108.58
166.67
137.62
142.29
104.34
123.32
94. 86
145.66
120.26
115.60
-------
TABLE J-4. BASELINE EMISSION TEST RESULTS
1975 CALIFORNIA CHEVROLET IMPALA, BASELINE CAR IIB-1
PELLETED CATALYST WITH AIR PUMP, 0.0415 PERCENT SULFUR FUEL
g/km
Date
11/6/75
11/7/75
Average
11/6/75
11/7/75
Average
11/6/75
11/7/75
Average
11/6/75
11/7/75
Average
11/6/75
11/7/75
Average
11/6/75
11/7/75
Average
Test Type
FTP
FTP
SET -7
SET -7
SET -7
SET -7
FET
FET
SET -7
SET -7
SET-7
SET -7
Duration
23 min
23 min
23 min
23 min
12 min
12 min
23 min
23 min
23 min
23 min
HC
0.37
0.40
0.39
0. 09
0.10
0. 10
0.10
0.09
0.10
0.07
0.05
0.06
0.11
0.09
0.10
0.09
0.09
0.09
CO
10.83
10.28
10.56
2.82
3.41
3.12
4.31
3.20
3.76
1.47
0.73
1.10
4.62
3.28
3.95
2.84
2.20
2.52
NOX
1.19
1.14
1.17
1.09
0.88
0.99
1.05
0.99
1.02
0.94
0.84
0.89
1.04
0.94
0.99
1.01
0.99
1.00
SO?,
0.136
0.082
0.109
0.068
0.064
0.066
0.110
0.076
0.093
0.064
0.051
0.058
0. 085
0.091
0.088
0.075
0.068
0.072
mg/km
1.49
4. 74
3.12
8.39
6.77
7.58
8.01
10.03
9.02
7.23
12.94
10.09
7.33
10.35
8.84
9.79
14. 75
12.27
H2SO4 as %
of fuel S
0.66
2.16
1.41
5.26
4.60
4.93
5.10
6.88
5.99
4.99
9.36
7.18
4.44
7.01
5.73
6.41
9.52
7.97
SOz as %
of fuel S
91.43
56.71
74.07
65.51
66.81
66.16
106.87
80.14
93.51
67.55
56.47
62.01
79.09
94.47
86.78
75.14
67.28
71.21
Total
Recovery
92.09
58.86
75.48
70.77
71.41
71. 09
111.97
87.02
99.50
72.54
65.83
69.19
83.54
101.48
92.51
81. 56
76. 80
79. 18
-------
TABLE J-5. BASELINE EMISSIONS TEST RESULTS
1975 CALIFORNIA PLYMOUTH GRAN FURY, BASELINE GAR IIB-6
MONOLITHIC CATALYST WITH AIR PUMP (0. 0415% SULFUR FUEL)
Test
1
1
2
2
3
3
4
4
5
5
6
6
Date
10/2/75
10/3/75
10/2/75
10/3/75
10/2/75
10/3/75
10/2/75
10/3/75
10/2/75
10/3/75
10/2/75
10/3/75
Avg. of 8
Test
Type
FTP
FTP
Avg
SET -7
SET -7
Avg.
SET -7
SET -7
Avg.
FET
FET
Avg.
SET -7
SET -7
Avg.
SET-7
SET-7
Avg.
SET-7 's
HC
0.39
0.42
0.40
0.04
0.03
0.04
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
i
CO
6.46
5.06
5.76
0.42
0.49
0.46
0.65
0.27
0.46
0. 16
0.07
0. 12
0.31
0.28
0.30
0.36
0.85
0.60
0.45
?/km
NOX
1.01
1.08
1.04
0.74
0.94
0.84
0.78
0.78
0.78
0.58
0.64
0.61
0,71
0.70
0.70
0.76
0.91
0.84
0.79
S02
0.096
0.079
0.088
0.049
0.064
0.057
0.081
0.083
0.082
0.036
0.087
0.062
0.065
0.044
0.054
0. 072
0.090
0.081
0.068
mg/km
H2S04
6.44
4.55
5.50
37.41
14.76
26.09
35.24
23.65
29.45
59. 99
57.13
58.56
50.20
50.20
47.26
18. 34
32. 80
32.41
% Fuel S
as S
in H2SO4
2.86
1.93
2.40
24.59
9.52
17.06
23.67
15.65
19.66
46.88
44.79
45.84
34.50
34.50
32.23
10.95
21.59
21.59
% Fuel S
as S
in SO 2
65. 14
51.51
58. 33
49.06
63.57
56.28
83.03
83.66
83. 34
43.39
104. 30
73.85
68.02
48.40
58.21
75.63
82.18
78.91
69.19
Total
Recovery
68.00
53.44
60.73
73.64
73.09
73.37
106.71
99.30
103.00
90.27
149.09
119.68
102. 52
102. 52
107.87
93. 13
100. 50
93.75
-------
TABLE J-6. BASELINE EMISSIONS TEST RESULTS
197X FORD PINTO, BASELINE CAR IV-4
DEGUSSA 3-WAY CATALYST PLUS OXIDATION CATALYST WITH AIR
(0.030% FUEL SULFUR)
% Fuel S % Fuel S
Test
1
1
2
2
3
3
4
4
5
5
6
6
Date
10/6/75
10/7/75
10/6/75
10/7/75
10/6/75
10/7/75
10/6/75
10/7/75
10/6/75
10/7/75
10/6/75
10/7/75
Avg. of 8
Test
Type
FTP
FTP
Avg.
SET-7
SET-7
Avg.
SET-7
SET-7
Avg.
FET
FET
Avg.
SET-7
SET-7
Avg.
SET-7
SET-7
Avg.
SET-7's
HC
0.09
0. 11
0. 10
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
<0.01
0.01
0.00
<0.01
0.01
gl
CO
1.05
0.97
1.01
0.09
0. 10
0. 10
0.01
0.09
0.05
0.00
0.02
0.02
0.09
0.03
0.06
0.01
0. 11
0.06
0.07
/km
NOX
0.43
0. 37
0.40
0.61
0.59
0.60
0. 53
0. 54
0.54
0.66
0.84
0.75
0.69
0. 57
0.63
0.57
0.48
0.52
0. 57
SO2
0.048
0.021
0. 034
0.047
0.039
0.043
0.032
0. 040
0.036
0.037
0.033
0.035
0.032
0.032
0.021
0.025
0.023
0.034
mg/km
HzSO4
35.08
13.84
24.46
63.87
61.64
62.63
58.64
46.56
52.60
43.58
59.90
51.74
39. 55
57.64
48.60
37.20
42.51
39.86
50.95
as S
in H2SO4
38.99
16.99
27.99
96.08
97.96
97.02
87.40
72.22
79.81
70.79
98.83
84.81
59.46
91.76
75.61
58.98
65.49
62.24
78.67
as S
in SO 2
82.21
40.30
61. 26
107. 94
93.98
100. 96
73.65
95.30
84.48
91.07
83.05
87.06
74.72
74. 72
51.71
58.94
55.33
79.46
Total
Recovery
121.20
57.29
89.25
204.02
191.94
197.98
161.05
167.51
164.28
161.86
181.89
171.87
134. 18
134. 18
110.68
124.44
117.56
156.26
-------
TABLE J-7. BASELINE EMISSION TEST RESULTS
197X PINTO, BASELINE CAR IV-17
TWC-9 3-WAY CATALYST, NO AIR INJECTION, 0.030 PERCENT SULFUR FUEL
Date
10/28/75
10/29/75
Average
10/28/75
10/29/75
Average
10/28/75
10/29/75
Average
10/28/75
«-i 10/29/75
<5o Average
10/28/75
10/29/75
Average
10/28/75
10/29/75
Average
Test Type
FTP
FTP
SET-7
SET-7
SET-7
SET-7
FET
FET
SET-7
SET-7
SET-7
SET-7
Duration
23 min
23 min
23 min
23 min
12 min
12 min
23 min
23 min
23 min
23 min
HC
0.30
026
0.28
0.09
0.08
0.09
0.08
0.08
0. 08
0.06
0.04
0.05
0.09
0.08
0.09
0.08
0.08
0.08
g
CO
4.63
5 01
4.82
1.79
1.46
1.63
1.53
1.45
1.49
0. 73
0.49
0.61
1.64
1.36
1.50
1.31
1.23
1.27
/km
NOV
0. 71
0 72
0.72
0.18
0.66
0.42
0.68
0.67
0.68
0.73
0.68
0.71
0. 74
0. 74
0.74
0.69
0.72
0.71
S02
0.051
0 OSS
0.053
0.049
0.053
0.051
0.048
0.051
0.050
0.043
0.056
0.050
0.049
0.057
0.053
0.053
0.050
0.052
mg/km
H2SO4
0.53
0.53
0.06
0.15
0.11
0.14
0.04
0.09
0.14
0.16
0.15
0.03
0.21
0.12
0.11
0.08
0.10
H2SO4 as %
of fuel S
0.58
0.58
0.09
0.22
0.16
0.20
0.06
0.13
0.23
0.27
0.25
0.05
0.33
0.19
0.18
0.12
0. 15
SO2 as %
of fuel S
86.74
Q4 Qft
90.82
113.35
123.40
118.38
110.39
119.96
115.18
106.98
152.02
129.50
114.99
136.88
125.94
128.16
125.27
126.69
Total
Recovery
87,33
91.40
113.44
123.62
118.53
110.60
120.02
115.31
107.21
152.29
129.75
115.03
137.21
126.12
128.34
125.39
126.87
-------
TABLE J-8. BASELINE EMISSION TEST RESULTS
1975 MERCEDES 240D, BASELINE CAR III-7
DIESEL POWERED, NO CATALYST, 0.23 PERCENT SULFUR FUEL
g/km
Date
11/18/75
11/19/75
Average
11/18/75
11/19/75
Average
11/18/75
11/19/75
Average
11/18/75
11/19/75
Average
11/18/75
11/19/75
Average
11/18/75
11/19/75
Average
Test Type
FTP
FTP
SET-7
SET-7
SET-7
SET-7
FET
FET
SET-7
SET-7
SET-7
SET-7
Duration
23 min
23 min
23 min
23 min
12 min
12 min
23 min
23 min
23 min
23 min
HC
0.23
0.05
0. 14
0. 10
0.04
0.07
0.05
0.02
0.04
0.04
0.05
0.05
0.08
0.06
0.07
0.05
0.01
0.03
CO
0.43
0.49
0.46
0.36
0.38
0.37
0.34
0.37
0.36
0.31
0.31
0.31
0.38
0.33
0.36
0.33
0.36
0.35
NOy
0.78
0.77
0.78
0.74
0.90
0.82
0.71
0.83
0.77
0.71
0.82
0.77
0.71
0.82
0.77
0.78
0.81
0.80
SO2
0.392
0.283
0.338
0.363
0.324
0.344
0.213
0.277
0.245
0.356
0.296
0.326
0.315
0.310
0.313
0.342
0.277
0.310
mg/km
H2S04
9.35
12.77
11.06
9.75
11.48
10.62
10.05
11.02
10.54
9.39
9.61
9.50
10.22
11.03
10.63
11.42
11.70
11.56
H2S04
as % of
Fuel S
1.78
2.32
2. 05
2. 17
2.50
2.34
2.29
2.37
2.33
2.33
2.24
2.29
2.32
2.44
2.38
2.56
2.58
2.57
SO2 as
% of
Fuel S
113.91
78.72
96.32
123.70
108.35
116.03
74.23
90.88
82.56
134.97
105.65
120.31
109.57
104.74
107. 16
117.56
93.54
105.55
Total
Recovery
115.68
81.04
98.36
125.86
110.86
118.36
76.53
93.24
84.89
137.30
107. 89
122.60
111.89
107. 18
109.54
120. 13
96.12
108. 13
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
BPA-460/3-76-015
2.
3. RECIPIENT'S ACCESSIOONO.
4. TITLE AND SUBTITLE
"Measurement of Sulfate and Sulfur Dioxide
in Automotive Exhaust"
5. REPORT DATE
June 1976 fdate of
6. PERFORMING ORGANIZATION CODE
11-4015
7. AUTHOR(S)
Melvin N. Ingalls and Karl J. Springer
8. PERFORMING ORGANIZATION REPORT NO
AR-1124
9. PERFORMING ORG \NIZATION NAME AND ADDRESS
Southwest Research Institute
8500 Culebra Road
San Antonio, TExas 78284
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-2118
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Mobile Source Air Pollution Control
2565 Plymouth Road
Ann Arbor, Michigan 48105
13. TYPE OF REPORT AND PERIOD COVERED
Final 6-28-74 thru 8-31-76
14. SPONSORING AGENCY CODE
18. SUPPLEMENTARY NOTES
16. ABSTRACT
This report describes the testing of four groups of cars for sulfate and
sulfur dioxide exhaust emissions. The collection and analytical techniques used
for sulfate and sulfur dioxide are described. Emissions rates in grains per kilo-
metre are presented for a variety of test cycles. In addition to sulfates and
sulfur dioxide, gaseous emissions of hydrocarbons (HC), carbon monoxide (CO) and
oxides of nitrogen (NOX). are reported in grams per kilometre. Total particulate
weight on the sulfate filter was determined on two of the groups of cars. For these
same two groups of cars, the sampling tunnel residue from each test car was ex-
amined by X-ray fluorescent techniques.
The first of the car groups was tested to characterize sulfate
eight automobiles. Four of these were gasoline powered catalyst
gasoline powered noncatalyst cars, and one was diesel powered.
four catalyst cars, was operated for 80,500 km (50,000 miles) to
effect of distance accumulation on sulfate emissions. The third
production catalyst cars, was part of the EPA sulfate procedural
The last group, eight cars, was part of the EPA sulfate baseline,
six were production 1975 models (including one diesel), and two
cars with three-way catalysts.
emissions from
cars, three were
The second group,
determine the
group, two 1975
development testing
Of these cars,
were experimental
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Air Pollution
Exhaust Emissions
Catalytic Converters
Sulfuric Acid
Sulfur Dioxide
Sulfates
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Federal Test Procedure
Sulfate Emission Test
Highway Fuel Economy Test
3. DISTRIBUTION STATEMENT
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19. SECURITY CLASS (This Report)
21. NO. OF PAGES
315
20. SECURITY CLASS (This page)
22. PRICE
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17. KEY WORDS AND DOCUMENT ANALYSIS
ci^fo^^^^^ "<"« "- "-** «« «**
(c) COSATI FIELD GROUP - Field and group assignments are to be taken from the 1965 COSATI Subject Category List. Since the ma-
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EPA Form 2220-1 {9-73J (Reverse) Inspected
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15
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