EPA-460/3-74-014
A STUDY OF EMISSIONS
FROM 1967-1974 LIGHT-DUTY
VEHICLES IN NEWARK, NEW JERSEY
Prepared by
A.R. Martin, D.T. Feal, andL. M. Anstey
General Environments Corp.
6840 Industrial Road
Springfield, Virginia 22151
Contract No. 68-03-0389
EPA Project Officer: John T. White III
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Mobile Source Air Pollution Control
Certification and Surveillance Division
Ann Arbor, Michigan 48105
October 1974
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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 - as supplies permit - from the Air
Pollution Technical Information Center, Environmental Protection Agency,
Research Triangle Park, North Carolina 27711; or, for a fee, from the
National Technical Information Service, 5285 Port Royal Road, Springfield,
Virginia 22151.
This report was furnished to the Environmental Protection Agency by
General Environments Corp. , Springfield, Virginia, in fulfillment of
Contract No. 68-03-0389. The contents of this report are reproduced herein
as received from General Environments Corp. 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 Pro-
tection Agency.
Publication No. EPA-460/3-74-014
11
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ABSTRACT
General Environments Corporation under contract to the
Environmental Protection Agency, conducted a comprehensive study of
automotive exhaust emissions on 180, light-duty vehicles in the
metropolitan area of Newark, New Jersey. This study of 1967 through
1974 model-year consumer-owned vehicles was part of a total surveillance
program conducted in six major cities (Denver, Detroit, Houston, Los
Angeles, Newark and St. Louis) in order to determine the impact of
automotive emissions on air quality.
Specifically, vehicles in Newark were tested for exhaust emissions
using the 1975 Federal Test Procedure including the hot-stabilized cycle.
During this basic test an additional analysis was made to determine the
light hydrocarbons and aldehydes of the 180 vehicles. Modal emissions
were determined on 75 vehicles, and the EPA Highway Fuel Economy Test was
conducted on all vehicles. Over 50% of the sample subsequently underwent
idle emission tests conducted through the State of New Jersey Vehicle
Inspection Program. A history of this data was compiled for the purpose
of correlating the laboratory tests with the New Jersey idle tests.
ill
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TABLE OF CONTENTS
1. Introduction
2. Technical Discussion
2.1 Program Objectives 3
2.2 Program Design 3
2.3 Test Vehicle Procurement 4
2.3.1 Test Vehicle Selection 6
2.3.2 Incentives 12
2.3.3 Test Vehicle Handling 14
2.4 Facilities and Equipment 16
2.4.1 Test Location 16
2.4.2 Constant-Volume Sampler 18
2.4.3 Emission-Analysis Console 18
2.4.4 Laboratory Standard Calibration Gases 18
2.4.5 Chassis Dynamometer 19
2.4.6 Equipment for Aldehyde and Light Hydrocarbon 19
Measurement
2.4.7 Miscellaneous Equipment 21
2.5 Equipment Qualification, Calibration and Cross-Check 22
2.5.1 Constant-Volume Sampler 22
2.5.2 Emission-Analysis Console 24
2.5.3 Chassis Dynamometer 26
2.5.4 Evaporative Emissions Equipment 27
2.5.5 Equipment for Special Additional Tests 27
2.6 Test Procedures 30
2.6.1 Vehicle Preparation 30
2.6.2 Equipment Preparation 31
2.6.3 Federal Exhaust Emission Test Procedure 32
2.6.4 Modal Exhaust Emission Test Procedure 34
2.6.5 Aldehydes and Light Hydrocarbon Measurements 37
2.6.6 Daily Test Schedule 38
IV
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TABLE OF CONTENTS (CONT'D)
Page
2.7 Data Handling 41
2.7.1 Data Collection 41
2.7.2 Data Processing 41
2.7.3 Calculation of Results 45
2.7.3.1 Exhaust Emissions 45
2.7.3.2 Modal Emissions 48
2.7.3.3 Fuel Economy 49
2.7.3.4 Aldehyde and Light Hydrocarbon 50
Emissions
3. Test Results 52
3.1 Discussion of Exhaust Emission and Fuel Economy
Test Results 52
3.1.1 Federal Test Procedure 52
3.1.2 Modal Emissions 53
3.1.3 Aldehyde and Light Hydrocarbon Emissions 53
3.2 Discussion of New Jersey Testing 53
4. Acknowledgments 55
5. Appendices
Appendix A: Listing of Vehicle § Test Parameters 72
Appendix B: Listing of Vehicle Use and Maintenance Data 78
Appendix C: Listing of Federal Test Procedure Results
on Individual Vehicles 84
Appendix D: Listing of Modal Emission Results on
Individual Vehicles ]46
Appendix E: Measurement Technique for Light Hydrocarbons
and Aliphatic Aldehydes 185
Appendix F: Test Fuel Inspection Reports 200
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SECTION 1
INTRODUCTION
Since the motor vehicle is still considered to be one of the major
sources of air quality degradation,, the need for a realistic assessment
of emissions from light-duty vehicles in the hands of the motoring public
has been continuously recognized by the Environmental Protection Agency
(EPA). One of the responsibilities of EPA, as provided through the
Clean Air Act, is to determine these emissions factors and provide current
data to quantify the automobile's contribution to atmospheric pollution.
By conducting surveillance programs in major metropolitan areas, average
emission factors for motor vehicles can be developed and supplied to the
National Air Data Branch (NADB) and the Office of Transportation Land Use
Policy (OTLUP) for their use in determining nationwide and metropolitan
area emissions.
EPA's first major surveillance program using the present CVS
technique, which is a mass measurement method of determining exhaust
emissions, was in 1971. Surveillance programs were conducted prior to
this however. A volumetric measurement method, normally called the 7-mode
test, was used to determine the exhaust emissions. The FY 71 program
determined the emissions from 1957-1971 light-duty vehicles. Similarly,
the FY 72 program investigated 1966-1972 vehicles. This program, FY 73,
sampled 1967-1974 light-duty vehicles.
In carrying out its continuing effort, the EPA contracted with
General Environments Corporation to determine and provide emission test
data from a representative sample (180) of vehicles operating in the
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metropolitan area of Newark, New Jersey. This city was one of six areas
to be investigated by EPA. The other U. S. metropolitan cities were
Denver, Detroit, Houston, Los Angeles and St. Louis. This report des-
cribes the performance, procedures and results of the 180 vehicles
sampled in Newark.
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SECTION 2
TECHNICAL DISCUSSION
2.1 PROGRAM OBJECTIVES
The primary objective of this program was to determine the exhaust
emissions of a scientifically valid sample of in-use 1967 through 1974
light-duty, consumer-owned vehicles in the Newark, New Jersey metropolitan
area. This data along with that developed in five other major U. S.
cities will subsequently be used to develop emission factors that will
define the contribution of light-duty vehicles to the national air
pollution inventory. A secondary objective was to determine vehicle fuel
economy and real-time emissions on a modal basis.
2.2 PROGRAM DESIGN
To support the overall objective of this program two major require-
ments existed.
First, it was important that the vehicles truly reflected a
representative sample of the nationwide population and that a selection
process be followed that minimized any bias that could be encountered.
That is to say, at the initiation of the selection process, every
registered vehicle owner in the population should have an equal chance
to be selected. The sample list provided by EPA which was based on
nationwide distribution and miles traveled for each model-year vehicle,
stipulated the number of vehicles in each model-year and the vehicle make
and size, engine type, displacement, transmission type and number of
carburetor Venturis.
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The second major consideration was to perform the various
emission tests with an established methodology of well defined procedures
and qualified calibrated test equipment. This was accomplished using the
constant volume sampling technique in accordance with the 1975 Federal
Test Procedure (FTP). All vehicles were subjected to this test incuding
a full hot-start.
The data obtained allowed computation of emission rates in gms/mile
of hydrocarbon, carbon monoxide, carbon dioxide and oxides of nitrogen
in accordance with both the 1972 and 1975 FTP.
Specific light hydrocarbons (methane, ethane, propane, ethylene
and acetylene) and aliphatic aldehydes were measured during the basic
test.
Fuel economy was calculated for the 1972 and 1975 FTP. In addition,
EPA's Highway Fuel Economy Test (HFET) was conducted on all vehicles and
fuel consumption was determined by the carbon balance method.
1972 through 1974 model-year vehicles were all subjected to EPA's
Surveillance Driving Sequence (SDS) and modal emissions were measured
continuously for various accel/decel/steady-state modes.
2.3 TEST VEHICLE PROCUREMENT
This program required obtaining 180 automobiles that were consumer-
owned and typical in-use vehicles. The number of each make was based
upon the typical vehicle miles traveled for each model-year. The required
number of vehicle makes for Newark is shown in Figure 2-1. A detailed
listing of specific vehicles was provided by EPA which described model-year,
make, displacement, vehicle size, transmission type and number of carburetor
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MAKE
AMC
BUICK
CADILLAC
CAPRI
CHEVROLET
CHRYSLER
DATS UN
DODGE
FORD
LINCOLN
MAZDA
MERCURY
OLDSMOBILE
OPEL
PLYMOUTH
PONTIAC
TOYOTA
VOLKSWAGEN
TOTALS
TOTAL
5
11
4
1
44
4
3
10
37
1
1
7
12
1
12
13
4
10
180
1974 1973
1
1 2
1
1
2 8
1
1
1 2
2 7
-
1
1
1 2
-
1 2
1 2
1
1 2
10 35
1972
-
2
-
-
7
-
1
2
6
1
-
1
2
1
2
2
1
2
30
1971
1
2
1
-
6
1
1
1
5
-
-
1
2
-
2
2
1
1
27
1970 1969 1968 1967
1 1 1
1111
1 1
-
6654
1 - 1
-
1111
5543
_
_
1111
2111
-
2111
2211
1 - - -
1111
22 21 18 17
FIGURE 2-1 VEHICLE LISTING (BY MAKE)
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Venturis. This section describes the methodology and procurement
procedures used in obtaining the necessary vehicles to fit the specific
requirements.
2.3.1 Test Vehicle Selection
To select a qualified sample list several steps were required and
are depicted in Figure 2-2. The first step was to obtain a randomized
registration within the site boundary. This listing was obtained from the
R. L. Polk £ Co. The designated areas of particular interest are shown
Area
Orange
Orange
Orange (West Orange §
Town Center)
South Orange
Elizabeth
Elizabeth
Elizabeth (Roselle)
Elizabeth (Roselle Park)
Elizabeth (Hillside)
Elizabeth
Elizabeth
Elizabeth
Union
Springfield
The list supplied by Polk consisted of mailing labels, an example of which
appears in Figure 2-3.
A mass mailing of 6000 letters were sent throughout the program to
obtain a prospective candidate list that best fit the sample population
profile. This introductory mailing contained:
o EPA Introductory Letter - Figure 2-4
o GEC Introductory Letter - Figure 2-5
o Response Card - Figure 2-6
below:
Zip Code
07101
07102
07103
07104
07105
07106
07107
07108
07109
07110
07111
07017
07018
07019
Area
Newark
Newark
Newark
Newark
Newark
Newark
Newark
Newark
Newark (Belleville)
Newark (Nut ley)
Newark (Irvington)
East Orange
East Orange
East Orange
Zip Code
07050
07051
07052
07079
07201
07202
07203
07204
07205
07206
07207
07208
07083
07081
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Develop Strategy for Test
Fleet Selection, Procurement
and Logistics
Prepare Mailing
Materials
*Letter § Envelope
*Brochure
*Return Envelope
Design Random Vehicle
Selection Program
*Initial Elimination
*Random Selection Routine
*0ther Selection Criteria
Obtain Registration List
by Test Location
*Make
*Model
*0wner
*Address
*Zip Code
I Select Initial Sample |
Send Mailing to Selected
Vehicle Owners
Follow up Mailing to
Maximize Response
*Phone Calls
*Personal Visits
*0ther
Set up On-Site File for
Keeping Records of
Every Vehicle
Set up Home Office File
For Keeping Records of
Every Vehicle
Quantitatively Evaluate Response
Clarify as Needed. Review for:
*Mileage, Age
*0ther
Select Test Fleet by "Fitting" Test
Vehicles as Closely as Possible to
Proportions of National Vehicle
Population Characteristics Using
This Hierarchy of Criteria:
*Year *CID, Carburetion
*Make *Transmission
Compatible with Our Needs?
If so, List.
FIGURE 2-2
VEHICLE SELECTION PROCEDURE
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MS ESTHER
27 KROTIK
NEWARK NJ
REBARBER
PL
07111
MR JOHN OURKOT
46 DURAND PL
NEWARK NJ
07111
MS WILMA M POMERANTZ
336 STUYVESANT AV
NEWARK NJ 07111
MS GERTRUDE D FDERST
213 MAPLE AV IR
NEWARK NJ C7111
MR CHARLES
17 SHERMAN
NEWARK MJ
D MILLER
PL IR
07111
GEORGE F SINGLETARY JR
198 MUNN AV
NEWARK NJ 07111
MR JOSEPH
17 SUNSET
NEWARK NJ
L COLELLA
TER
07111
MR ANDREW GRANTZGW
115 WESTERN PKWY
NEWARK NJ 07111
MR ANTONI0 SACCA
527 MADIS ON AV
ELIZABETH NJ
C7201
ENRIQUE A LOPEZCALLEJA
822 REBECCA PL
ELIZABETH NJ 07201
MR ROCCO PEPINO XXX
208 CHRIS TINE ST
ELIZABETH NJ C7202
MR GEORGE NICHOLAS
330 BOXWOOD CT
ELIZABETH NJ 07202
FIGURE 2-3 MAILING LABELS
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Form Approved OMB No. 158-R0106
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
A Message to the Vehicle Owner
The U. S. Environmental Protection Agency, in carrying out
the Clean Air Act, has contracted with competent testing
organizations to conduct emission tests on certain randomly-
selected 1967 through 197^ - model vehicles. The purpose of
these tests is to develop emission factors for use in making
nationwide emission estimates. The test results from any
individual vehicle will be used only by the EPA in comparison
with the test results from all similar vehicles. The outcome
of the test on any individual vehicle cannot result in any
adverse action against the vehicle owner.
The enclosed letter to you, from one of these testing
organizations, explains this project in detail, and asks to test
your vehicle. The purpose of this message is to urge that, if
at all possible, you allow your vehicle to be tested in this
program.
To assure valid results from this program, the specific
vehicles that will comprise the sample to be tested are randomly
selected in proportion to a nationwide population average, without
bias, from vehicle registration lists provided by private
research firms. Your vehicle has been tentatively selected by
means of this process. Your participation in the test will
represent a real and significant contribution to the cause of
Clean Air.
Please read the enclosed letter. Note that it says a
follow-up will be made. Should you have an unlisted telephone
number, or if for any other reason it may be difficult for the
testing organization to reach you by phone, please call the number
given in the enclosed letter, from the testing organization, for
your participation.
Sincerely yours,
Eric 0. Stork
Deputy Assistant Administrator
Mobile Source Air Pollution Control
'FIGURE 2-4 EPA INTRODUCTORY LETTER
Form No. AA-101-5
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General Environments Corporation / 109 Aldene Road, Roselle, New Jersey 07293 / (201 ) 245-421 I
Form No. AA-101-3
Form Approved OMB No. 158-R0106
Dear Vehicle Owner:
You may be able to make an important contribution towards controlling the nation's
air pollution problem, and receive at least one, and perhaps two U.S. Savings Bonds
for your cooperation.
The U.S. Environmental Protection Agency is conducting an important testing program
for vehicle exhaust pollution in six major metropolitan areas: Detroit, St. Louis,
Denver, Los Angeles, Houston, and Newark. Our organization has been selected by
the Federal Government to perform these tests in the Newark area. We are writing
you because your vehicle has been randomly selected as a candidate for testing.
Enclosed is a postpaid reply card. If you are willing to participate, please answer
the questions on the card, and mail it at your earliest convenience. We are especi-
ally interested in whether or not your vehicle has undergone the State of New Jersey
exhaust pollution tests this year. If your vehicle is due for an exhaust emission
inspection soon, we would like to test your vehicle before the State of New Jersey
performs its test. For this and a report to us of the results of your State test,
you will receive a $25 U.S. Savings Bond. There is no pass-fail to our test.
Should your vehicle subsequently fail the New Jersey test and you have it tuned up
and successfully retested, we offer you a $50 U.S. Savings Bond to allow us to test
your car again.
All tests will be performed under simulated normal driving conditions. No unusual
operations will be performed on your vehicle, and it will be fully insured while in
our possession.
The Environmental Protection Agency has also authorized us to provide you with a full
tank of fuel after we have finished testing your vehicle; and, if you wish, the use
of a late model, fully-insured loan car while your vehicle is in our possession.
We know you will want to be a part of this important project. Please complete and
return the enclosed postpaid reply card today. We will contact you shortly should
your vehicle meet the requirements of our program.
Sincerely
A. R. Martin
Form No. AA-101-3
FIGURE 2-5 GEC INTRODUCTORY LETTER
10
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Are you willing to volunteer your vehicle for pollution testing? If
so, please provide the following information, and mail this postcard
today.
Name /Telephone
Street /Best Time to
City Zip /call
Make of vehicle (Chev .,Ford,Plym. ,etc.) Year_
Engine size (displacement) Cubic Inches.
(or cubic centimeters)
Carburetor: 1 barrel , 2 barrel , 4 barrel , no barrel
(fuel injection)
Transmission: Automatic ; Manual
Air Conditioning: Factory Installed? Yes ; No
Operational? Yes ; No
During which month is your vehicle scheduled for the New Jersev State
Safety Inspection7 (Month)
Company Use Only
Date of Contact Vol./No.
FORM NO. AA-101-4
FIGURE 2-6 VEHICLE RESPONSE CARD
11
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Concurrently, phone contacts were made in addition to contacting civic
and fraternal organizations, local college groups and rental agencies.
It was important that these other sources be utilized only when
absolutely necessary. Consequently, less than 15 cars were obtained from
these groups, of which 2 were rental vehicles.
Once the original contact was made, a file was established and
maintained by year and make. Information was obtained from car owners
regarding engine size, transmission and carburetor Venturis. If the
vehicle fit the requirements and the owner agreed to participate a tenta-
tive schedule was established. The specific vehicle requirements
established by EPA allowed some flexibility for substitutions. This
listing of required vs. actual is shown in Figure 2-7. If no vehicle
identification is shown in the actual column then this indicates the
required vehicle was obtained and tested. An example of the vehicle
identification is shown below.
350 A 4
4 bbl carb.
automatic trans.
.I.D.
2.3.2 Test Incentives
All participating owners whose vehicle successfully completed the
test program requirements received
o a fully insured loan car while their vehicle was being tested
o a full tank of gas in their car on completion of testing
o a $25 U.S. Savings Bond
12
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i—t Csl r-. o o o o
i o in in to o
r^ co o
13
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Those those particular owners who subsequently had their cars inspected by
the State of New Jersey and failed were given a $50 U. S. Savings Bond
if they:
o had the car tuned up
o successfully retested by the State of New Jersey
o retested by GEC
2.3.3 Test Vehicle Handling
Once a car arrived at the laboratory, a preliminary inspection
was conducted which consisted of an inspection to determine if there were
obvious problems with the exhaust or emission control systems and the
vehicle had the proper engine, transmission, and carburetor combination.
Included in this inspection was general mechanical condition of the
vehicle as well as driveability and safety of operation.
Any replacements to be made due to aborted tests or non-compliance
with the test requirements were contacted from a reserve file.
After the preliminary inspection was conducted, an exchange of
cars and receipts (Figure 2-8) took place. The test vehicle was driven to
the defueling area and the gas tank emptied. The gasoline was deposited
into a 55 gallon drum. The specified volume of test fuel was pumped into
the car's gas tank.
A 10 minute course was set up through the local area and each car
was driven over this course before being placed in the laboratory. The
cars were driven into the laboratory and parked. At this point the date
and tirae were posted on each car's windshield. The owner's drive to the
laboratory and the 10 minute purge run constituted the vehicle preconditioning.
14
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GENERAL ENVIRONMENTS CORPORATION
Date
TO WHOM IT MAY CONCERN:
I certify that I have this date received from General Environments
Corporation (GEC) the following vehicle for my private use while my
car is being tested for exhaust emissions.
Vehicle Make Model Year
License No. Odometer Reading
I further understand that my car will be "in test" for approximately
24 hours and that I will be advised when to pick up my car.
(Signature of Car Owner)
General Environments Corporation hereby acknowledges receipt of
the below described vehicle for the purpose of conducting an exhaust
emissions test.
Vehicle Make Model Year
License No. Odometer Reading_
Remarks:
(GEC Representative)
FIGURE 2-8 TEST VEHICLE RECEIPT
GEC Form 4734-4
15
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The car was hand pushed within the laboratory at all times and
included hand pushing onto the dynamometer to start the test.
The fuel used in all tests was Texaco Indolene 30 test fuel.
A certified analysis of the test fuel is included in Appendix G of
this report.
A final inspection was performed after the car was situated on
the dynamometer before the actual test was begun. It was determined
that the emission controls were connected and that the engine had not
been modified extensively. This ensured vehicles which were representa-
tive of the vehicle population. The technician attached the sampling
boot to the exhaust system.
After the test was completed, the ignition timing, idle speed and
dwell were measured and recorded. The carbon monoxide and hydrocarbons
in the exhaust were measured and recorded while the engine was idling.
This total procedure is shown in Figure 2-9.
2.4 FACILITIES AND EQUIPMENT
2.4.1 Test Location
All testing covered in this report was conducted at GEC's temporary
test site at 109 Aldene Road, Roselle, New Jersey, located within ten
miles of the metropolitan area of Newark at an elevation of 23 feet above
sea level. The facility contains 4400 square feet of laboratory and soak
space with adequate outside parking adjacent to the building. To provide
for adequate cooling a 20 ton air conditioner was installed to maintain
soak area temperatures between 60°-86°F and test area temperatures between
76°-86°F.
16
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Select Test Vehicles
from Consumer Responses
Schedule for
Testing
Perform Participant
Interface
Vehicle Pretest
Inspection
w
w
Vehicle
Rejected
k.
Return to Owner
with Explanation
1
Complete Agreements
Engineering
Diagnostic Procedures
Return to
Participant
FIGURE 2- 9 VEHICLE HANDLING PROCEDURES
17
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2.4.2 Constant Volume Sampler
The constant volume sampler utilized in the performance of this
contract was a Scott Constant Mass Flow Sampler, Model 301, modified
by GEC to meet the specific test requirements. The sampler was specif-
ically designed and constructed to condition and collect automotive
exhaust gases as generated from a light-duty vehicle when operated over
the Federal Test Cycle.
2.4.3 Exhaust Analysis Console
A Scott Exhaust Analysis Console, Model 119 containing the
analyzers for CO and C02 and gas dryer/scrubber was used in conjunction
with a GEC constructed console containing analyzers for HC and NOX. The
plumbing of the consoles was modified to shorten system response time in
order to successfully perform modal analysis. The major components
used were:
o Beckman Model 315 NDIR-CO analyzer with ranges of
0-.3/3/5% CO.
o Beckman Model 315 NDIR-C02 analyzer with a range of 0-4/8% C02
o Beckman Model 400 hydrocarbon analyzer with ranges of
0-300/1000/3000/10,000 ppm C
o Thermo Electron Model 10A chemiluminescence analyzer with
ranges of 0-100/250/1000/2000 ppm NO
o Leeds § Northrup Speedomax XL-600 dual-pen strip-chart
recorders (2)
2.4.4 Laboratory Standard Calibration Gases
A complete set of laboratory standard calibration gases were pro-
cured by GEC for subsequent analysis by the EPA laboratories in Ann Arbor,
Michigan. The "naming" of gases by EPA for all contractors was done
18
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concurrently prior to the start of testing. The number of various gases
stipulated was of such a quantity as to provide a minimum of five points
per range for the CO and C02 analyzers and three points per range
(including zero) for the HC and NOX analyzers. The standard gases and
their nominal concentrations are shown in Figure 2-10. Upon return from
EPA all gas cylinders were fitted with gold caps to ensure easy identi-
fication. Thereafter, all working span gases used in the day-to-day
calibration were analyzed against these "golden standards" for concentra-
tion determination.
All zero gases were analyzed by the specialty gas supplier and
certified to meet the specifications contained in the Federal Register.
2.4.5 Chassis Dynamometer
A Clayton Model ECE-50 chassis dynamometer with a belt driven
variable inertia flywheel assembly was used.
The dynamometer was equipped with 250 Ib. increment inertia weights
and a 0-50 hp power absorption unit. Readout instrumentation included a
speedmeter and a roadload horsepower meter.
2.4.6 Equipment for Aldehyde and Light Hydrocarbon Measurement
The following major equipment was used in determining the specific
light hydrocarbons of interest.
o Perkin-Elmer Model 900 gas chromatograph with Porapak
"Q" column
o Infotronic Model CRS 108 digital integrator with Victor Digimatic
printer
o Leeds 5 Northrup Speedways "W" single channel recorder with
.1-1.0 mv response
19
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FIGURE 2-10 LABORATORY STANDARD CALIBRATION GASES
20
-------
The determination of aldehydes was made with a Bausch £ Lomb
Spectronic 20 Spectrophotometer. Also, a special sampler was fabricated
by GEC which included sample and exhaust manifolds, vacuum pump and a
flow switching control system.
2.4.7 Miscellaneous Equipment
In addition to the major equipment described, various other support
equipment was utilized. A data acquisition and control system using a
Hewlett-Packard 2116A computer was used in conducting analysis of the
acceleration and deceleration modes of the surveillance driving cycle.
Software programs were developed and used for data reduction of: 1) light
hydrocarbon and aldehyde determination; 2) fuel economy calculations;
3) mass emission calculations; 4) propane recovery results; 5) highway
fuel economy calculations and 6) calibration curve development.
Further support is described below.
A Mettler analytical balance, Model H315 was used to weigh propane
cylinders used during propane recovery tests of the CVS. The balance
accuracy was 0.1 milligram and a range of 0-1000 grams.
A Varian Associates Model G-1000 Time/Speed Recorder was employed
to provide a graphic record of the simulated vehicle speed versus the
prescribed driving course. Prior to implementing the test schedule the
chart speed of the driver's aide was determined several times. The chart
speed was determined to be within the +2 second tolerance.
A Penske timing light Model 244.2115 was employed to determine test
vehicle engine timing. A Snap-on Model MT416 primary tach dwell meter was
used to measure point dwell and idle r.p.m.
21
-------
Additional items of equipment included a cooling fan to move air
through the test vehicle radiator, front wheel restraining blocks, vehicle
restraining cables, tire pressure gage (0-50 psi) and miscellaneous tools.
A Meriam Laminar Flow Element (LFE) Model 50MC2-6SF with a range
of 0-1000 SCFM was employed to calibrate the constant volume sampler mass
airflow. The LFE was employed with a Model 310EF10 inlet absolute pressure
gage and a Model 40HE35 differential pressure indicator.
A standard aneroid barometer was used to determine local atmos-
pheric pressure.
A Brown-Honeywell 12-channel temperature recorder was employed to
monitor and record soak area temperature at 30 second intervals.
A Sun Model EPA-75 HC/CO analyzer for measuring idle emissions.
2.5 EQUIPMENT QUALIFICATION, CALIBRATION AND CROSS-CHECK
Instrumentation and equipment were selected to meet the various
types of exhaust emission tests. To insure the integrity of the test
and validity of the data., a comprehensive quality control procedure
was established jointly with EPA. In addition to daily and weekly routine
calibrations all equipment was qualified and approved by EPA prior to the
start of testing and after the completion of the test program. Additionally,
continuing cross-checks were made throughout the performance of the
program. The specific compliance criteria for the analytical console,
chassis dynamometer, constant volume sampler and other equipment are
described in the following paragraphs.
2.5.1 Constant Volume Sampler
The constant volume sampler (CVS) was calibrated in accordance with
established procedures specified in the Federal Register.
22
-------
The mass airflow was determined by means of a Meriam Laminar
Flow element at 10 increments of flow. Incremental flow changes were
effected by means of a valve situated between the laminar flow element
and the CVS. The differential pressure across the mass pump was
recorded for each increment of flow. The standard volume per revolution
of the pump was calculated and plotted against the differential pressure
in accordance with EPA's recommended procedures.
v0 = Qs . Jj, .
406.8
n 530 Pp
where:
Vo = pump flow in SCFM
Qs = absolute flow rate thru LFE in SCFM
n = pump speed in rpm
Tp = absolute air temperature at pump inlet in °R
Pp = absolute pressure at pump inlet in inches of H20
The flow rate (Qs) through the laminar flow element (LFE) was determined
in accordance with the prescribed method set forth by the manufacturer.
Qs = Qi ' TL • _ PL • 1
S * L 406.8
where:
Qi = indicated flow rate thru LFE in SCFM
TL = temperature correction factor in °R
PL = absolute pressure at LFE inlet in inches of H20
23
-------
The CVS calibration curve was checked by injecting known amounts
of propane into the CVS and calculating the propane recovery based upon
the total air volume moved by the CVS pump as shown by the sample calcula-
tion sheet in Figure 2-11, which was used to verify computer data reduction.
2.5.2 Emission Analysis Console
A daily procedure followed by GEC incorporated a leak check of the
CVS bags concurrently with the analytical system. A self-sealing quick
disconnect was used at the junction between the CVS bags and the sample
ports of the CVS. The leak check was first performed on the analytical
system by sealing the sample inlet. A visual observation of analyzer
flow rates and pressure would indicate that a leak was present. In
turn each evacuated CVS bag was subjected to this verification to ensure
a zero flow existed.
The calibration of the analytical instrumentation consisted of
establishing the manufacturer's operational parameters and then intro-
ducing gold standard gases to determine instrument response. The following
ranges were established.
Carbon Monoxide 0-0.3 percent
0-3 percent
0-5 percent
Carbon Dioxide 0-4 percent
0-8 percent
Total Hydrocarbons 0-300 ppm carbon
0-1000 ppm carbon
0-3000 ppm carbon
0-10,000 ppm carbon
Nitrogen Oxides 0-100 ppm NOX
0-250 ppm NOX
0-1000 ppm NOX
0-2000 ppm NOX
Weekly 3-point analytical checks were conducted to assure curve
generation consistency. Additionally, the curves on all ranges were
reconstructed on a monthly basis.
The converter efficiency of the NOX analyzer was checked weekly.
24
-------
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FIGURE 2-11 PROPANE RECOVERY CALCULATION
25
-------
Two dual pen strip chart recorders complete the sample analytical
system. One recorder monitored the output from the CO and C02 analyzers
while the other monitored hydrocarbon and NO/NOX. Each channel of the
recorders provided a full scale deflection with 10 millivolts of input
signal .
2.5.3 Chassis Dynamometer
The chassis dynamometer met the specifications contained in 35
Federal Register 219, Part II, 36 Federal Register 128 and the contract
scope of work. The dynamometer was calibrated both for speed and road
load horsepower.
Speedometer calibration was accomplished by accelerating the
dynamometer to 46.5 miles per hour and measuring roller revolutions with
a strobotach. At 46.5 miles per hour the roller rpm was 1800 as specified
by the manufacturer.
Road load horsepower (RLHP) calibration consisted of warming the
dynamometer for 15 minutes at 30 mph with a non-test vehicle. This
vehicle was then employed to accelerate the dynamometer rollers to 50 mph.
This indicated road load horsepower at 50 mph was recorded. The vehicle
then accelerated to an indicated 60 mph and the drive wheels physically
lifted from the rollers with a pneumatic bumper jack. The coast time from
55 to 45 mph was determined by means of a strobotach and stopwatch. Tripli-
cate runs were conducted for several points over the working range.
The following calculation was employed to determine the actual road load
horsepower:
HPd = (1/2) (Wi/82.2) (Vi2 - V22/550t)
= 0.06073
26
-------
where: Wj = equivalent inertia in pounds
Vj = initial velocity in ft/sec (55 mph = 80.67 ft/sec)
V2 = final velocity in ft/sec (45 mph = 66.00 ft/sec)
t = elapsed time for rolls to coast from 55 to 45 mph
A plot of the indicated road load horsepower vs. the road load horsepower
is shown in Figure 2-12. This plot was translated to a point-by-point
table and posted by the dynamometer to provide a quick and easy reference.
2.5.4 Evaporative Emissions Equipment
The determination of evaporative emissions was not a requirement
for the Newark test program.
2.5.5 Equipment for Special Additional Tests
2.5.5.1 Light Hydrocarbon Analysis
Utilizing a gas chromatograph (GC) for this analysis it was important
to precisely calibrate the instrument initially with known calibration
gases. This calibration was confirmed on a daily basis. Initial calibra-
tion was made utilizing a set of analyzed standard gases. The specific
gas mixture obtained from Air Products, Inc., was:
o 1.1 ppm CH4 in N2 (methane)
o 1.2 ppm C2H2 in N2 (acetylene)
o 1.1 ppm C2H4 in N2 (ethylene)
o 1.2 ppm C2H$ in N2 (ethane)
o 1.0 ppm C3Hg in N2 (propane)
Peak identification, elution times and area to concentration equiva-
lences were determined from this calibration as shown in Figure 2-13.
Repetitive analyses with the test gas was made to establish mean deviation
and reproducibility.
27
-------
§
1
20
18
16
14
o
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<3J
12
O
PM
w
CO
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4 6 8 10 12 14
INDICATED ROAD LOAD HORSEPOWER @ 50 MPH
16
FIGURE 2-12 ROAD LOAD HORSEPOWER CALIBRATION
28
-------
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29
-------
After five consecutive tests the average count (representing
the area under the curve) for the test gases was determined and the
average count/ppm. These results are shown below.
Compound Counts/test gas Counts/ppm
CH4 4151.6 3774.2
C2H2 7254.8 6045.7
C2H4 4893.6 4448.7
C2H6 3936.0 3936.0
Further, the standard deviation for each compound was also determined.
Compound +_ Counts x 102 +^ PPM x 102
CH4 4.89 12.98
C2H2 1.37 2.28
C2H4 9.48 2.13
C2H6 1.11 4.64
1.05 2.68
2.5.5.2 Aliphatic Aldehyde Analysis
Calibration of this method of analysis was done by injecting
a known amount of reagent grade acetaldehyde vapor into a CVS bag filled
with a metered amount of pure nitrogen. Preparation of the acetaldehyde
can yield a purity greater than 99%. The analysis used is the same as
the 3MBTH method for exhaust gas analysis. The molar absorptivity of
acetaldehyde was near 65,000.
2.6 TEST PROCEDURES
2.6.1 Vehicle Preparation
Upon arrival at the laboratory each vehicle was carefully inspected
for exhaust system continuity, engine size, number of carburetor Venturis,
completeness, condition of existing emission control systems, and drive-
ability. Each item was checked on a list as completed. The vehicle was
30
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then moved to the defuel/fuel area and the contents of the gas tank emptied
into a drum by means of a high capacity fuel pump. Test fuel was then
introduced to a level of 40 percent of tank capacity. Pumping time was
calculated by the equation:
Pump time (min) = (0-4)(tank_capacity)
Pump rate in gal/mm
Upon completion of the fueling each vehicle was driven over a prescribed
10 minute course to remove residual non-test fuel from the fuel lines,
fuel pump, and carburetor. This run to the laboratory and the ten minute
course comprised the initial vehicle preparation.
The vehicles were placed inside the laboratory with the time and
date recorded for the start of the temperature soak period. After 12 hours
the vehicle was pushed onto the dynamometer by hand. Just prior to test
each vehicle was reinspected to ensure that no change had occurred since the
initial inspection. Tires were inflated to 45 pounds per square inch, the
cooling fan positioned and turned on, the hood opened, the tail pipe
connector attached, and the driver's aide placed in the car.
2.6.2 Equipment Preparation
The dynamometer was warmed up prior to each day's testing. The
CVS was turned on at 300 CFM for a minimum of 20 minutes prior to use and
the analytical instrumentation was turned on for at least 30 minutes prior
to system leak checks and prior to conducting the daily propane recovery
test. Flow rates were established for each instrument and zero gas response
verified. Prior to introducing test samples all instruments were zeroed
and spanned to ensure accurate sample response.
31
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2.6.3 Federal Exhaust Emission Test Procedure
Exhaust emission tests were performed in accordance with the
procedures specified in 37 Federal Register 221, November 15, 1972
(sections 85.075-9 through 85.075-24) and 36 Federal Register 128, July
2, 1971 (section 1201.85) Also, as amended in 38 Federal Register 124,
June 28, 1973. The exception was that the hot-start test was run the full
1372 seconds.
2.6.3.1 Pretest Procedures
The analytical instruments were turned onto the range to be
used and allowed to warm up. The analyzers were zeroed and then spanned
to adjust the attenuation of each instrument to the desired range. The
values were then compared to previous readings and adjusted if required
to within one percent of span. The NOX to NO converter was checked for
efficiency by preparing a gas bag of nitric oxide and oxygen. The bag
was mixed and connected to the sample inlet of the NO/NOX analyzer.
Alternately the NO and NOX values were read at one minute intervals for
a period of 12-15 minutes. Routinely the NOX value remained constant
while the NO value reduced with time.
A propane recovery test was conducted daily prior to starting
the vehicle tests. The propane recovery test consisted of injecting
known amounts of propane in the sample inlet of the CVS over a 15 minute
period and collecting an aliquot of the diluted sample in a plastic
(Tedlar) bag. Subsequent analysis of the diluted propane from the sample
bag and a parallel sample from the air bag provided a means of calculating
the recovery percent for the sampling system. A recovery of +^2.0 percent
of propane injected was experienced during the test phase of the program.
This was sufficient to reveal any significant leaks in the CVS system.
32
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The analysis console and the sampling system (CVS) were leak
checked daily to determine that the systems were airtight.
2.6.3.2 Test Procedure
The vehicle was manually placed on the dynamometer with the
drive wheels situated on the rollers. The engine compartment cover
was opened and the cooling fan turned on. The CVS and dynamometer were
in a warmed up condition with the CVS pump running but not sampling and
the heat exchanger steady at 110°F. The sample flow rates were adjusted
and the flexible exhaust tube connected to the tailpipe. At the beginning
of the test the pump revolution counter and sample collection were simul-
taneously started. After 15 seconds the vehicle was placed in gear and
20 seconds after the engine started the driving schedule commenced. At the
505 second point in the driving schedule the sample was directed into a
second bag through the five second period after the final deceleration.
Analysis of the 505 second bag commenced immediately. At the conclusion
of the test the sampling was stopped and the sample and air bags analyzed.
The tail pipe connector was disconnected, the engine compartment cover
closed and the cooling fan turned off. The interval between the cold start
test and the hot start test was 10 minutes. The test procedure was
repeated for the hot start test. Upon completion of the hot start test
the tail pipe connector was removed and the engine timing, idle rpm and
dwell were measured, and recorded. The raw exhaust hydrocarbon and
carbon monoxide levels were determined.
33
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2.6.4 Modal Exhaust Emission Test Procedure
Modal exhaust emissions measurements were comprised of two
separate tests: the steady state and the Surveillance Driving Sequence.
Each test was preceded by a soak period of twenty minutes (max.) from
the last sustained vehicle operation. At the end of the soak period
the vehicle was operated on a chassis dynamometer at 50 mph for three
minutes. During this time the dynamometer road load horsepower setting
was adjusted.
Steady state exhaust emissions were measured at 0, 5, 10, 15,
30, 45 and 60 mph using the CVS dilute bag collection technique. At
each speed, equilibrium was maintained for at least 30 seconds before
sampling was started. A bag sample of two cubic feet was collected over
a period of six minutes.
After another soak and preconditioning period, described above,
the vehicle was operated at idle for one minute before the modal sequence
began. This driving schedule is made up of 32 acceleration and decelera-
tion modes. These modes are combined into a driving schedule established
by EPA and called the Surveillance Driving Sequence (SDS). Figure 2-14
depicts the 32 modes with their average speed and rates of acceleration.
A special computer program was developed for the analysis of the
32 modes.
The mass emissions for the entire sequence were determined from
the mass flow rate of the CVS and concentration of emissions in the bag.
A block diagram of the entire SDS procedure is shown in
Figure 2-15.
34
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Average Speed
Average Accel-
eration Rate
Distance
(sec)
12
16
8
11
13
12
17
12
14
30
26
21
32
23
9
8
22
16
18
19
25
28
15
25
18
10
38
35
18
21
14
13
(mph)
18.05
16.66
9.04
23.07
37.65
38.05
45.80
51.48
52.54
40.40
43.42
33.83
37.27
46.86
23.18
7.81
28.85
31.33
30.55
24.72
38.28
33.88
17.73
45.14
47.23
15.99
38.01
33.87
17.73
44.55
46.63
16.40
(mph/sec)
2.50
-1.88
1.88
1.36
1.15
-1.25
1.76
-1.25
1.07
-1.50
1.73
-2.86
1.88
-1.30
-1.67
-1.88
2.05
-1.88
1.67
-2.37
2.40
-2.14
2.00
1.20
-1.67
-3.00
1.58
-1.71
1.67
1.43
-2.14
-2.31
(miles)
0.0602
0.0741
0.0201
0.0705
0.1360
0.1268
0.2163
0.1716
0.2043
0.3367
0.3136
0.1973
0.3313
0.2994
0.0579
0.0173
0.1759
0.1392
0.1528
0.1304
0.2654
0.2634
0.0737
0.3134
0.2362
0.0444
0.4009
0.3293
0.0886
0.2599
0.1813
0.0592
FIGURE 2-14 SURVEILLANCE DRIVING SEQUENCE
1
Reprinted from EPA Report No. APTD-1497, March 1973
35
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SOAK
(20 MIN. MAX.)
50 MPH - 3 MIN.
ADJ RHP
IDLE
LESS THAN 1 MIN.
NO
YES
EQUILIBRIUM
MIN. 30 SEC.
COLLECT BAG
SAMPLE
2 CU. FT. MIN.
GO TO NEXT
HIGHER SPEED
TEADY STA
COMPLETE?
VEHICLE AT IDLE
FOR 1 MIN.
. NO SAMPLING
FIRST 30 SEC.
. THRU SYSTEM
LAST 30 SEC.
. ADJ. FLOW
START BAG SAMPLE
WITH BEGINNING
OF S.D.S.
RUN S.D.S. CYCLE
ANALYZE BAGS &
RECORDER TRACES
FIGURE 2-15
MODAL EMISSIONS TEST PROCEDURE
36
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2.6.5 Aldehydes and Light Hydrocarbon Measurements
2.6.5.1 Aldehyde Measurements
The 3-methyl 2-benzothiazolinone hydrazone method (3 MBTH) was
used. This is a sensitive colorimetric method for the determination of
water soluble aliphatic aldehydes, measured as acetylaldehyde, in automotive
exhaust. The aliphatic aldehydes react with 3 MBTH in the presence of
ferric chloride to form a blue cationic dye which is read at 635 mu with
a spectrophotometer.
Dilute auto exhaust was sampled directly from the CVS using
fritted samplers. Prior to sampling, however, the sample probes and
manifolds were heated to 150°C. Matched sample bubbles were placed into
an ice bath and connected to the sample manifold. After the sample
solutions were properly chilled the sampler vacuum pump was run to insure
vacuum stability. At the start of the FTP cold test, the dilute auto
exhaust was drawn through the chilled absorbing solution using bubbler
traps connected to a manifold. At the end of the cold-transient portion
of the cycle (505 seconds), the manifold directed the flow of exhaust
sample to a second pair of bubblers. This was the start of the cold-
stabilized portion of the cycle. After 867 seconds, the bubbles were
removed and the same procedure followed for the hot test portion. After
collection, the samplers were allowed to stand at room temperature for
two hours to complete the reaction of the aldehydes with the 3 MBTH.
Aliquots of the sampler were then oxidized with ferric chloride and
diluted to a final volume with acetone and the absorbency measured.
2.6.5.2 Light Hydrocarbon Measurements
Samples of the auto exhaust were collected under controlled
conditions during the basic FTP exhaust emission test. The sample was
37
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drawn from the bag by a vacuum pump through an injection loop (IL) of
the gas chromatograph (GC), see Figure 2-16. After the IL had been
purged by the exhaust gas sample it was introduced into the analytical
column of the GC. Simultaneously, the digital integrator was placed in
the auto mode, preparing the system to record the presence of each
component (methane, acetylene, ethylene, ethane and propane) separated
from the exhaust gas. Following the initial surge the elution from the
column occurred over a six minute interval. At the end of this period
the GC programmer automatically increased the oven temperature to hasten
the elution of long-chain hydrocarbons in order to prepare for the next
analysis.
2.6.6 Daily Test Schedule
The daily test schedule was generated by the Fleet Control
Administrator. Owners were contacted by phone and requested to have their
cars at the laboratory at a specified time. A schedule clerk prepared a
schedule envelope, Figure 2-17, on which the reporting date and time were
indicated. All available vehicle information including the vehicle
inspection checklist was imprinted on the envelope. All recorder tracings
and test documents were placed in this envelope which became the vehicle
file folder. Upon completion of testing for each vehicle the schedule
envelope was returned to the clerk who checked the contents and removed
each car tested from the needed vehicle list.
Normally, two eight-hour shifts were worked for the test phase.
Cars were put into the soak area 12 hours prior to the commencement of
each shift and removed from the laboratory area after testing.
38
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0)
•p
•H
fH
(X
O
o
FIGURE 2-16 GC SYSTEM FOR LIGHT HYDROCARBON ANALYSIS
-------
GENERAL ENVIRONMENTS CORPORATION
6840 INDUSTRIAL ROAD
SPRINGFIELD, VIRGINIA 22151
NAME
VEHICLE NO.
JEST DATE
RUN NO.
CAR MANUFACTURER
CAR MODEL
DESCRIPTION: 2 door ( )
4 door ( )
Convertible ( )
Station Wagon( )
Sedan ( )
Hardtop ( )
Air conditioned Yes ( ) No( )
Transmission
Standard 3 speed ( ) 4 speed( )
Automatic ( )
BOND INFORMATION
Name
Co-Maker
Beneficiary, POD_
Address
SSN
Courtesy Car ( )
OWNER NEEDS
Directions ( )
TEST INFORMATION
Car to be delivered
Car to be picked up_
INSPECTION
1. Engine size agrees with code
2. Exhaust system in good shape
3. Pollution systems appear intact
4. Brakes operative
5. Engine modified
6. Transmission agrees with code
7. No. of carburetor Venturis agrees with code
Remarks
Automatic ( )
Standard ( )
Not needed ( )
_Date/time
Date/time
Yes ( ) No ( )
THIS ENVELOPE MUST CONTAIN:
( ) Computer data sheet
( ) Receipt acknowledge (2)
( ) CO-CO,-, recorder chart
( )
( )
( )
Signed
NOX-THC recorder chart
CVS data sheet
Driver schedule cold start
( ) Driver schedule hot start
FIGURE 2-17 SCHEDULE ENVELOPE
40
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2.7 DATA HANDLING
2.7.1 Data Collection
All required data were collected in worksheet form prior to data
review and final report tabulation. Initial vehicle data (i.e., vehicle
weight, engine CID, transmission type., etc.) and CVS test data were
recorded on the GEC Test Data Sheet, Figure 2-18. Upon completion of
each test, analytical and vehicle data were entered on the Sixbag Test
Computer Input Form, Figure 2-19, and the Highway Fuel Economy Worksheet,
Figure 2-20. These two documents comprised the primary source of input
for the computer data reduction.
2.7.2 Data Processing
The test envelope for each vehicle was delivered to a data clerk
who checked each data input form for accuracy and completeness. The
on-site computer was then employed to calculate the data required for
reporting. The computer output provided data which was recorded in a
"data book" which became the source document for keypunching. A separate
"data book" was generated for each vehicle tested. These were later
sent to a subcontractor for keypunching. Upon receipt at the subcontractor's
facility the data was keypunched and key verified fron this input provided
by GEC. Each card set required in the contract scope of work for submission
to EPA was generated and returned to GEC with the source documents. The
punched cards were checked against the source documents and keypunch errors
and errors of entry were coded for immediate correction. Upon completion
of this review the punched cards were forwarded to EPA and the source
documents placed in the test file. Errors attributable directly to the
testing program were eliminated by retest of the vehicle.
41
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VEHICLE NUMBER_
RUN NUMBER
CVS OPERATOR
GENERAL ENVIRONMENTS CORPORATION
LIGHT DUTY EMISSIONS DATA SHEET
DATE/TIME INTO SOAK_
DATE/TIME TESTED
ANALYSIS SYSTEM OPERATOR_
TEST DRIVER
MANUFACTURER
TRANSMISSION TYPE
ODOMETER READING
FUEL TANK LOCATION_
VEHICLE I.D. NUMBER_
IDLE R.P.M.
TYPES OF EMISSION CONTROLS_
CONDITION OF PCV SYSTEM
VEHICLE
MODEL
NUMBER OF SPEEDS
ENGINE DISPLACEMENT^
AIR COND.
IDLE TIMING
CARBURETOR VENTURIES
YEAR
DWELL
DYNAMOMETER
MAKE MODEL_
ACTUAL ROAD H.P. AT 50 M.P.H. ~
ABSORPTION AT 50 M.P.H.
INERTIA
_SERIAL NO.
INDICATED ROADLOAD POWER
DRIVE WHEEL TIRE PRESSURE
SAMPLING SYSTEM INFORMATION
SERIAL NO.
TYPE
MODEL NO.
MANUFACTURER
TEST
02T
02S
03T
035
ECON
AP
INL
DEP
REVS
N
PUMP
TEMP
BARO
GRAINS
H20
%H
AMB
TEMP
BULB TEMP
WET
DRY
FLOW SCFH
SAMP
AIR
IDEL CO LEVEL
IDLE HC LEVEL
FIGURE 2-18 LIGHT DUTY EMISSIONS TEST DATA SHEET
42
-------
DATE:
C AR NO:
RUN NO:
SAMPLE BAG 1
DP
IN.DEP.
BAR
GR.H20
RH
HC
CO
C02
NOX
DEFLECTIONS
CURVE
1 I
SAMPLE BAG 2
DP
IN.DEP.
BAR
GR.H20
RH
I J
HC
CO
DEFLECTIONS [
CURVE
r r
SAMPLE BAG 5
DP
IN.DEP.
CO 2
NOX
BAR
GR.H20
RH
I 1
HC
CO
DEFLATIONS
CURVE
I I
SAMPLE BAG 4
DP
IN.DEP.
CO 2
NOX
BAR
GR.H20
RH
HC
DEFLECTIONS |_
CURVE [
AIRBAG 5
DEFLECTIONS HC
CURVE
AIRBAG 6
DEFLECTIONS
CURVE
HC
CO
CO
C02
NOX
C02
NOX
CO
C02
NOX
FIGURE 2-19 SIX BAG TEST COMPUTER DATA FORM
43
-------
DATE: VEHICLE NO: RUN NO:
HIGHWAY FUEL ECONOMY
Delta P
In. Dep.
Revs.
Pump T
Baro.
Grains HoO
SAMPLE BAG
HC CO C02 NOX
Deflection
Curve
AIR BAG
Deflection
Curve
FIGURE 2-20 HIGHWAY FUEL ECONOMY COMPUTER WORKSHEET
44
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2.7.3 Calculations of Results
2.7.3.1 Exhaust Emissions
(1) Hydrocarbon Mass:
(2)
(3)
HCmass = Vmix X DensityHC X —•
Carbon Monoxide Mass:
COmass = Vmix X DesnityCO X
Oxides of Nitrogen Mass:
COconc
Too
.._„ ... .. _ . . ,._ v
NOXmass = Vmix X DensityN02 X
NOXconc
QOQ
Meaning of symbols:
HCmass = Hydrocarbon emissions, in grams per vehicle mile.
DensityHC = Density of hydrocarbons in the exhaust gas, assuming
an average carbon to hydrogen ratio of 1:1.85, in
grams per cubic foot at 68°F. and 760 mm Hg pressure
(16.33 gm/cu ft).
HCconc = Hydrocarbon concentration of the dilute exhaust sam-
ple minus hydrocarbon concentration of the dilution air
sample, in ppm carbon equivalent, i.e., equivalent pro-
pane X 3.
COmass = Carbon monoxide emissions, in grams per vehicle mile.
DensityCO = Density of carbon monoxide in grams per cubic foot at
68°F. and 760 mm Hg pressure (32.97 gm/cu ft).
COconc = Carbon monoxide concentration of the dilute exhaust
sample minus the carbon monoxide concentration of the
dilution air sample, in volume percent.
NOXmass = Oxides of nitrogen emissions, in grams per vehicle mile.
DensityNO = Density of oxides of nitrogen in the exhaust gas, as-
suming they are in the form of nitrogen dioxide, in
grams per cubic foot at 68°F. and 760 mmHg pressure
(54.16 gm/cu ft).
NOXconc = Oxides of nitrogen concentration of the dilute exhaust
sample minus the oxides of nitrogen concentration of
the dilution air sample, in ppm.
Vmix = Total dilute exhaust volume in cubic feet per mile, cor-
rected to standard conditions (528°R. and 760 mm Hg).
P
Vmix = K X V X N X -£
45
-------
ro Q °p
Where: Kl = 760 nun Hg X 7. 5 miles ' °'09263
V = Volume of gas pumped by the positive displacement pump, in
cubic feet per revolution. This volume is dependent on the
pressure differential across the positive displacement pump.
N = Number of revolutions of the positive displacement pump
during the test while samples are being collected.
P = Absolute pressure of the dilute exhaust entering the positive
" displacement pump, in mm Hg, i.e., barometric pressure minus
the pressure depression below atmospheric of the mixture enter-
ing the positive displacement pump.
T = Average temperature of dilute exhaust entering positive dis-
P placement pump during test while samples are being collected,
in degrees Rankin.
K = Humidity correction factor,
H
K., =
H 1 - 0.0047 (H - 75)
where: H = Absolute humidity in grains of water per pound of dry air.
Example calculation of mass emission values:
Assume V = 0.265 cu ft per revolution; N = 20,250 revolutions;
H = 85 grains per Ib of dry air; P = 730 mm Hg; T = 550°R. ;
HCconc = 160 ppm carbon equivalent; COconc = 0.09%; and NOX cone
= 70 ppm.
Then: Vmix = (0.09263) (0.265) (20,250) (730/550) = 659.8 cu ft per mile.
KH = 1 - 0.0047 (85 - 75) = 1 ' °49
(1) For a 1972 light-duty vehicle.
HCmass = 659.8 X 16.33 X --- =1.72 grams per vehicle mile
J. j \J\J\J j \J\J\J
NOXmass * 659.8 X 54.16 X nnn nnn X 1 • °49 = 2'62 Erams per vehicle mile
J. ) \J\j\j f \J\J\J
(2) For a 1972 utility vehicle.
COmass = 659.8 X 32.97 X O-09^0-85 =16.6 grams per vehicle mile.
36 Federal Register 128, 2 July 1971
46
-------
Calculations for 1975 Light Duty Vehicles
(a) For light-duty vehicles:
Ywm = (0.43Yct + 0.57Yht + Ys)/7.5
where: Ywm = Weighted mass emissions of each pollutant, i.e., HC, CO, or
NOX, in grams per vehicle mile.
Yet = Mass emissions as calculated from the "transient" phase of
the cold start test, in grams per test phase.
Yht = Mass emissions as calculated from the "transient" phase of
the hot start test, in grams per test phase.
Ys = Mass emissions as calculated from the "stabilized" phase
of the cold start test, in grams per test phase.
The mass of each pollutant for each phase of both the cold start
test and the hot start test is the same as defined in the 1972
Federal Test Procedure.
37 Federal Register 221, 15 November 1972
47
-------
2.7.3.2 Modal Emissions
Values for each compound were calculated for each mode by
the following method:
(1) Avg. Rin = area of mode (in^)
mode base length (in)
and Avg. Rdiv = Rin x divisions/inch
where R = recorder response
(2) Volume of mixture (Vmix) for each compound was calculated for
each mode as follows:
vmix = -6947368 x N x Mode Seconds ^PB " Pi^ x Vo
Tp
where N = pump revolutions/sec.
(3) Yconc f°r eacn compound was calculated for each mode by the
following method:
(3.1) Y = a(Rdiv)2 + b(Rdiv)
where a and b are calibration curve coefficients
Then for HC and NOX
Y
(3.2) Yconc = Vmix x density x Ij000j000
For NOXC
(3.3) Yconc = Y^nc (NOX) x KH
For CO and C02
Y
(3.4) Yconc = Vmix x density x
Then
(3.5) ^gm/nile for model = Yconcj _
miles for model
48
-------
Values for HC, CO, C02, and NOXC were determined for a
bagged sample collected during the Surveillance Driving
Sequence and were compared to the combined steady state
levels and mode values obtained from eq. (3.6) for each
compound.
i;32
(3.6) 2 = 2^ (Ygm/mile for modei -j x miles for mode i -j)
i=l
where Z = total grams of compound for test
Finally, the average grams per mile for each compound was
determined by dividing the total grams of compound by the miles traveled
during all modes.
2.7.3.3 Fuel Economy
The Highway Fuel Economy in miles per gallon was calculated
for each test vehicle by the following:
1. Calculation of total sample volume of the mixture
Vmix = V0 x K! x N x !E
'P
where Vo = volume of gas pumped by the positive displace-
ment pump in CFM
KI = Standard Temp x I
Standard Pressure
N = Revolutions of the pump during the test while
samples are collected
Pp = Absolute Pressure of the dilute exhaust entering
the pump in mmHg
Tp = Average temperature of dilute exhaust entering
the pump in degrees Rankin
49
-------
HCconc, COCQnc, C02 CQnc, and NOXc(mc were calculated as
described in 2.7.3.1. Then the Highway Fuel Economy was
calculated by:
2425
MPG = HC CO co
0.866 x grams + 0.429 x grams + 0.273 x 2 grams
10.242 10.242 10.242
where 10.242 = miles driven during test.
2.7.3.4 Aldehyde and Light Hydrocarbon Emissions
2.7.3.4.1 Aliphatic Aldehyde Emissions
The ppm aldehyde concentrations were determined by the
following equation.
ppm = (TSAH1/0.60 X22.4) x 1.2 x 273 x ^
where:
TSA = Total Sample Absorbence
TSA = TEA #1 + TEA #2
TSA = total sample absorbence
TEA = total bubbler absorbence
TEA = absorbency read per sample multiplied by the aliquot
per sample
e.g. bubbler #1: 25 cc sample volume, 10 cc aliquot
TEA #1 = Abs x 2.5
bubbler #2: 25 cc sample volume, 10 cc aliquot
TEA #2 = Abs x 2.5
TSA = Abs #1 x 2.5 + Abs #2 x 2.5
SFR = sample flow rate
50
-------
ts = sample time
Ts = sample temperature °K
ps = PB - PI
P = 760 mmHg
Final computation of grams per mile was accomplished as
described in section 2.6.5.2.
2.7.3.4.2 Light Hydrocarbon Emissions
Hydrocarbon concentrations were calculated by the following
equations :
(1)
B
where: Cs = sample counts from integrator
B = counts per part per million
then
(2) HCmass = Vmix x Density x HCPpm
1,000,000
Final gram per mile values for each light hydrocarbon was then
calculated as described in section 2.6.5.2. Ethylene and acetylene
were not separated by the GC column and are reported as C2 unsaturates
using ethylene density. The calculated light hydrocarbon densities were
computed from values obtained from the Handbook of Chemistry and Physics,
46th Edition (1965-66).
Compound Density @ 20°C 5 760 mmHg
Methane 37.9435 gm/cu. ft.
Acetylene 61.1626 gm/cu. ft.
Ethylene (Ethene) 66.2596 gm/cu. ft.
Ethane 70.7901 gm/cu. ft.
Propane 103.637 gm/cu. ft.
51
-------
SECTION 3
TEST RESULTS
3.1 DISCUSSION OF EXHAUST EMISSION AND FUEL ECONOMY RESULTS
3.1.1 Federal Test Procedure
A review of current vehicle emissions for model years 1967 through
1974 exhibits a continuing decrease in mass emission rates. When contrasted
with current emission rates for 1967 model year vehicles, emission rates
for 1974 model year vehicles were lower by 72 percent for HC, 73 percent
for CO and 36 percent for NOXC.
Carbon dioxide emissions, while not considered a pollutant, were
29 percent greater.
Also, over the same period, fuel economy as determined by the
carbon balance method from the Federal Test Procedure demonstrates a
7 percent lower fuel economy during the urban driving cycle. The cur-
rent highway fuel economy remained at 20 miles per gallon for 1967 and
1974 model year vehicles.
Of all the vehicles tested, 21.7 percent were found to be in com-
pliance with the 1972 Federal Emission Standards for HC and CO, 10 percent
were in compliance with the 1973/1974 Federal Emission Standards for HC,
CO and NOXC, while only one vehicle was able to meet the 1975 Federal
Emission Standards.
During this program 36.7 percent of 1972 model year vehicles were
in compliance with the 1972 Standards, 20 percent of the 1973 model year
vehicles were in compliance with the 1973 Standards and 60 percent of the
1974 model year vehicles were in compliance with the 1974 Standards.
52
-------
3.1.2 Modal Emissions
During the steady-state portion of the modal emissions test the
highest average peak fuel economy occurred at the mph steady-state mode.
Over the spread of the three model years tested (1972, 1973 and 1974)
the current average emission rates for HC, CO, and NOXC as determined
during the Surveillance Driving Sequence, were lower by 23 percent, 13 per-
cent and 43 percent respectively. The calculated fuel economy was 12.5
percent lower during the same period while the CC>2 emission rate was 12
percent higher.
3.1.3 Aldehyde and Light Hydrocarbon Emissions
Light hydrocarbon emission rates for methane, ethane and C2 un-
saturates (ethylene and acetylene) were 79 percent lower, 74 percent lower
and 52 percent lower respectively for 1974 model year vehicle when com-
pared to current 1972 model year vehicle emission rates.
Aliphatic aldehyde emissions were 37 percent lower during this
same model year period,
3.2 DISCUSSION OF NEW JERSEY TESTING
Vehicles registered in New Jersey were required to meet the follow-
ing exhaust emission standards:
Carbon Monoxide Hydrocarbon
Vehicle Model Year % (ppm)
1967 and older 10.0 1600
1968 and 1969 8.0 800
1970 through 1974 6.0 600
Undiluted measurements are made with a portable garage-type tester with
the vehicle at idle.
53
-------
The use of a postage reply card for New Jersey inspection stations
to report emission levels observed during the state inspection failed to
provide complete and consistent data with which to adequately evaluate
the New Jersey inspection program. Of the cars tested by GEC which sub-
sequently underwent state inspection, 54 percent failed to meet the HC
or CO state standard, or both. Of the vehicles which subsequently failed
the state inspection, 75 percent did not return for additional testing
by GEC.
54
-------
SECTION 4
ACKNOWLEDGMENTS
The support of this program by the EPA, Division of Certification
and Surveillance, is acknowledged. A very special acknowledgment
to Mr. Charles Domke, Mr. John White, III, EPA Project Officer,
and Messrs. Fred Dindoffer, Matt Macocha, Tom Bejma and John Shelton
for their prompt and courteous assistance.
55
-------
INDEX OF TABLES
Table No. Title^
1 Summary of Vehicle Makes
2 Summary of Test Vehicle Characteristics by
Model Year
3 Exhaust Emissions Test Results Vs. Model Year
4 Vehicles Meeting Federal Standards
5 1972 Vehicles Meeting 1972 Federal Standards
6 1973 Vehicles Meeting 1973 Federal Standards
7 1974 Vehicles Meeting 1974 Federal Standards
8 Summary of Modal Emission Results on Thirty
1972 Model Year Vehicles
9 Summary of Modal Emission Results on Thirty-
five 1973 Model Year Vehicles
10 Summary of Modal Emission Results on Ten
1974 Model Year Vehicles
11 Light Hydrocarbon Exhaust Emission Test Results
Vs. Model Year
12 Results of New Jersey State Inspection
56
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APPENDIX E
THE 3-METHYL 2-BENZOTHIAZOLINONE HYDRAZONE TEST METHOD
FOR ALIPHATIC ALDEHYDES IN AUTOMOTIVE EXHAUST
1. Principle and Applicability
1.1 3-methyl 2-benzothiazolinone hydrazone (3MBTH) is a sensitive colori-
metric method for the determination of water soluble aliphatic alde-
hydes, measured as formaldehyde, in auto exhaust. Aliphatic aldehydes
react with 3 MBTH in the presence of ferric chloride to form a blue
cationic dye which is stable for hours and is read at 635 my with
a suitable spectrophotometer.
1.2 Auto exhaust is sampled directly from the dilution tunnel of a con-
stant volume sampler (CVS) using fritted samplers.
The exhaust is drawn through chilled absorbing solution using bubbler
traps. After collection the samples are allowed to stand for two
hours at room temperature to complete the reaction of the aldehydes
with the 3 MBTH. Aliquots of the samples are then oxidized with
ferric chloride and diluted to a final volume with acetone. The
samples are then read at 635 my on a spectrophotometer.
2. Range and Sensitivity
2.1 The range concentration for aldehydes in CVS diluted samples using
the Federal Test Procedure falls into three categories.
2.1.1 Pre-1968 cars: Aldehydes from CVS diluted samples range
from 5 to 10 PPM aldehyde.
2.1.2 1968 to 1974 without catalyst: Aldehydes from CVS diluted
samples range from 2 to 5 PPM aldehyde.
w.l.3 Catalyst cars and special clean air cars: Aldehydes from
CVS diluted samples range from +.1 or less to 2 PPM aldehyde,
the cold unstable cycle being highest in aldehyde and the
cold stabilized lowest in aldehyde.
2.2 Sensitivity. By varying the sample absorbing solution volume and/or
by varying the sample volume taken, adequate sensitivity can be ob-
tained for all the above ranges.
3. Interference
3.1 Sulfur dioxide (S02) causes a negative response. The extent of the
interference has not yet been fully determined and only becomes
apparent when analyzing exhaust from catalytic systems using gaso-
line with a changing percentage of sulfur content.
185
-------
3.2 Nitrogen oxides (NOX) were a minor positive interference when run
with a calibrating aldehyde. Sulfur dioxide was not present during
the test.
4. Precision, Accuracy, and Stability
4.1 Precision. Relative standard deviation of .03 for a mean of .320
absorbance units was obtained.
4.2 Accuracy. No direct method for determining accuracy as applied to
auto exhaust is presently available: e.g. Section 3.1.
4.3 Stability of Reagents
4.3.1 3 MBTH solution is stable for approximately one week but it
is desirable to prepare it before each day's runs.
4.3.2 Ferric chloride without acid added is unstable and should
be prepared fresh daily.
4.3.3 Acetone should be kept stoppered in glass bottles or metal
containers. Acetone kept in plastic containers causes
clouding of the final solution.
4.3.4 Distilled water should be used.
4.4 Stability of Reaction
4.4.1 A two-hour reaction time is necessary to change 95% of the
aldehydes to hydrazones.
4.4.2 Five minutes oxidation time is used to develop color.
4.4.3 After dilution with acetone the sample is stable for at
least 40 minutes.
5. Apparatus
5.1 Metering Devices
5.1.1 The sampler (Figure 1) was developed by this lab for direct
wet sampling of aldehydes in CVS diluted auto exhaust. The
instrument consists of five major parts: Sample manifolds,
sampling area, exhaust manifolds, a vacuum pump, and a flow
switching control system.
5.1.2 Rotometers. 500 to 3000 cc per min. air metering range.
5.1.3 Wet Test Meter. 3 liters per revolution.
5.1.4 Spectrophotometer
186
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5.2 Miscellaneous
5.2.1 Fritted bubblers with 12/5 ball socket fittings. Inner
member is a coarse variety frit, (A) with (145-175) pore.
5.2.2 Sample probe. Type 316 stainless steel, 1/4" O.D., fitted
with a Swagelok fitting at one end for connection to sampler
inlet, wrapped with a 1/4" silicone heater tape electrically
controlled by a variable transformer and the heater tape
covered with three turns of asbestos cord.
5.2.3 Pump. Carbon vane type.
5.2.4 Rubber bulbs, oval shape, for pipetting. One to be fitted
with 12/5 male ball fitting for flushing inlet stem of frit.
5.2.5 Glass stoppered bottles, 60 cc volume, for holding samples.
5.2.6 100 cc volumetric flasks.
5.2.7 Pipettes. 5, 10, 20, 50 cc volumes.
5.2.8 Plastic drying tubes.
5.2.9 Desiccant, indicating silica gel.
5.2.10 Stopwatch.
6. Reagents
6.1 The various reagents are prepared on a weight volume basis. All
chemicals are analytical reagent grade. Distilled water is used
with all preparation.
6.2 3-methyl 2-benzothiazolinone hydrazone hydrochloride solution (0.2%).
Dissolve 2 grams of 3 MBTH in distilled water and dilute to one liter.
The solution may be stable for a few days but should be made fresh
daily. If samples are collected in water, weigh just enough 3 MBTH
for each sample collected.
6.3 Oxidizing reagent FeCl3-6H2 (without sulfamic acid). Dissolve
two grams of FeCl3.6H20 in distilled water and dilute to one liter.
This solution is unstable and must be prepared daily.
6.4 Acetone. Acetone should be kept stoppered in glass or metal con-
tainer. Acetone kept in polyethylene will cause clouding of the
final solution.
187
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7. Procedure
7.1 Sampling. The fritted bubbler method for sampling aldehyde in
auto exhaust is described.
7.2 Add 25 cc of .2% 3MBTH or H20 to the primary and back-up bubblers.
The collecting volume in the primary may be changed according to
the concentration of aldehyde in auto exhaust. The back-up bubbler
may be eliminated once the percent breakthrough has been established.
Add the percent breakthrough to the results.
7.3 Preparation for Sampling
7.3.1 Attach the end of the sample probe to the CVS tunnel and
the other end to the sampler. Preheat sample probe and
sample manifolds to about 150°C.
7.3.2 Connect the primary and back-up bubblers and position for
placement in the sampling train. The bubblers will be
connected to the sample manifold seconds before sampling
starts.
7.3.3 The flexible (Teflon) exhaust manifold lines with 12/5
female ball fittings are connected to the bubblers.
7.4 Sampling
7.4.1 Federal Test Procedure sampling. Three discrete samples
are collected directly from the CVS dilution tunnel.
Before sampling, heat the sample probe and the sample mani-
folds to about 150°C. Place matched sample bubblers in ice
baths and connect to the sampler. Make sure the sample sol-
utions are chilled to ice temperature before sampling. Start
the sampler vacuum pump before the run to insure vacuum
stability. At the start of the 505 cold unstabilized cycle,
the auto exhaust sample passes into the bubblers attached
to the manifold. The flow rates are adjusted if needed.
At the end of the 505 cold unstabilized cycle, the manifold
starts the flow of sample to a second pair of bubblers con-
nected to manifold. This is the start of the 867 cold stabi-
lized cycle. The flow rates are adjusted if needed. After
867 seconds, the bubblers are removed and the collecting
solution is drawn up into the frit inlet sidearm of the bubbler
with the aid of a 12/5 male socket fitted to a one ounce rubber
bulb. Then the liquid is forced back down into the bubbler
base. This washes all the samples condensed into the sample
and mixes it. This procedure is repeated several times for
each bubbler. The bubblers with samples are set aside and a
new set of pre-chilled bubblers are put in place. After the
188
-------
ten minute soak period is completed, the final hot transit
cycle of 505 seconds starts. Flow rates are adjusted. After
505 seconds the cycle ends. The bubblers are removed and the
above sample handling procedure repeated. After sampling is
complete, the solutions are transferred to appropriate con-
tainers for analysis. The bubblers are rinsed clean with tap
water and given a final rinse with distilled water and dried.
7.5 Sample Work-up
After a series of samples has been taken, the bubblers are taken to
the laboratory for analysis.
7.5.1 Pour the solutions from the bubblers into 60 ml glass
stoppered bottles and give a sample number. If the col-
lecting solution is 3 MBTH, nothing further need be added.
If the solution is H20, then add 0.2% by weight of 3 MBTH
to the sample. Shake the sample frequently to dissolve and
mix the 3 MBTH.
7.5.2 Pipetting may begin after the samples have reached room
temperature and after all the 3 MBTH has dissolved in the
solution, preferably two hours after sampling. 10 ml of
each sample is pipetted into 100 ml volumetric flasks.
Also, 10 ml of 0.2% MBTH is pipetted into a 100 ml volumetric
flash for use as a blank.
7.5.3 All the flasks are stoppered and allowed to stand until two
hours have elapsed since sampling.
7.5.4 A solution of 0.2% FeCl3 is prepared. After the two hours
have elapsed, 25 ml of 0.2% FeCl3, measured with a graduate
cylinder, is added to each sample.
7.5.5 The time of each addition is noted, so that after five
minutes has elapsed, acetone is added to the samples and
mixed.
7.5.6 After all samples have had acetone added, adjust to the
mark with acetone and mix again.
7.5.7 The samples are then read at a wave length of 635 mu with
a suitable spectrophotometer.
7.5.8 The absorbance is recorded for calculations.
189
-------
8. Calibration
Method Used for Calibration of 3 MBTH Method Standard bag sample
method is used to calibrate the 3 MBTH method. For this method
acetaldehyde is used. The procedure for calibrating with acetalde-
hyde is :
8.1.1 Obtain reagent grade acetaldehyde. Remove cap and replace
it with a rubber septum. With a large volume syringe remove
the air from above the liquid by sampling through the septum
several times. After the air has been removed from above
the liquid acetaldehyde, the remaining gas in the bottle is
99% acetaldehyde. Since the boiling point of acetaldehyde
is 21°C, the room temperature should be kept at a temperature
of 21°C+. This creates a slight positive pressure above
atmospheric, 760 mm, in the bottle. The bottle of acetalde-
hyde is now ready for preparing standard aldehyde bags. When
the bottle is not in use, store it in a hood. Do not store
it in a refrigerator or freezer. Storing in refrigerators
causes excessive polymerization of the aldehyde forming the
trimer .
8.1.2 To prepare a standard bag, meter the desired volume of N2
needed for the test. From the acetaldehyde bottle remove
the number of y 1 of acetaldehyde vapor needed to produce
the PPM desired for the standard; e.g. 1 y 1 vapor in 1 liter
of N2 equals 1 PPM. Insert the syringe needle through the
wall of the bag and inject the acetaldehyde into the bag
with a smooth stroke. Withdraw the syringe without moving
the plunger. Tape the needle hole closed with transparent tape.
8.1.3 The bag of acetaldehyde is sampled using the same procedure
set forth in 7.4.
8.1.4 Sample work-up is the same as in 7.5.
8.1.5 Calculation of molar absorptivity
Molar absorptivity = e = •prr
where
A = absorbance of the final dye solution
C = concentration in moles of aldehyde per liter of
final dye solution
1 = optical path length of 1 cm
Molar absorptivity of acetaldehyde should be 65,000.
190
-------
9. Calculations
9.1 Total Bubbler Absorbancy (TEA) = the absorbancy read per sample
multiplied by the aliquot per sample; e.g. bubbler #1 25 cc
sample volume 10 cc aliquot. TEA = Abs. x 2.5.
Bubbler #2 25 cc sample volume 10 cc aliquot. TEA = Abs. x 2.5.
9.2 Total Sample Absorbance (TSA) = the additive total bubbler absorbancy (TEA)
TSA = TEA #1 + TEA #2
e.g. TSA = Abs. #1 x 2.5 + Abs. #2 x 2.5.
9.3 Calculation of PPM Aldehyde
ppw = (TSA) (I/.60 x 22.4) (1.2) (275°K) (P sample)
(SFR in liters/min.) (sampling time) (sample temp K) (P Std.)
191
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GAS CHROMATOGRAPHIC ANALYSIS
OF LIGHT HYDROCARBONS FROM AUTOMOBILE EXHAUST
General Concepts:
Samples of auto exhaust are collected under controlled conditions
during the Federal Urban Driving Cycle. Both the transient and stabi-
lized portions of the driving cycle are tested for cold and hot start
conditions. These samples, diluted with known amounts of ambient air,
are collected in Tedlar plastic bags; after equilibration, a sample is
withdrawn from the bag by a vacuum pump through an injection loop of the
gas chromatograph (Fig. 1). When the injection loop has been purged by
the sample gas, the loop is connected in series to the analytical column
of the gas chromatograph (GC) by means of a two-way valve. The GC
analyzes the exhaust sample gas for the following components: Methane
(CH4), acetylene (C2H2), ethylene (C2H4), ethane (^H^) and propane
(C3Hg). The results of the analysis are produced as a chromatogram and
a digital print-out of the areas under the curves of the chromatogram.
By comparing the test results with identical analyses of known pure gases
it is possible to identify and measure the amounts of each component of
interest in the exhaust gas samples.
Instrumentation:
Gas Chromatograph - Perkin-Elmer Model 900 with Porapak "Q" column
(6' x 1/16" I.D.) and F.I.D.
Digital Integrator - Infotronic Model CRS 108 with Victor Digit Matic
printer unit.
Recorder - Leeds § Northrup Speedways "W" single channel (response
0.1-1.0 mv)
Carrier Gas - Helium, scientific grade 6
Fuel Gas - Hydrogen scientific grade 6
Air - Zero air with <0.5 ppm CO
Procedure:
After the injector loop (IL) has been purged by the exhaust gas
sample, the two-way valve (V) is positioned to introduce the contents
of IL into the analytical column of the gas chromatograph (GC). Simul-
taneously, the digital integrator (Int.) is placed in the auto mode, pre-
paring the system to record the presence of each component separated from
the exhaust gas. Following an initial pressure surge the components elute
from the column over approximately six (6) minutes. At the end of this
six (6) minute period the GC auto temp, programmer increases the oven temp.
to hasten the elution of long-chain hydrocarbons prior to the next analysis.
192
-------
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Initial calibration was made utilizing a standard gas mixture supplied
by Air Products, Allentown, Pa. The gas assay was:
CH4 1.1 ppm
C2H2 1.2 ppm
C2H4 1.1 ppm
C2H6 1.2 ppm
C3H8 1.0 ppm
(N2 balance gas)
Peak identification, elution times and area to concentration equiva-
lences are determined from this calibration (Fig. 2 and calculations section)
Repetitive analyses with the test gas were used to establish mean
deviation and reproducibility (see calcualtion sect.). The operating
parameters of the GC were determined following the above repetitive
analyses and optimization procedures outlined in Perkin-Elmer operating
manual #990-9679 (Figs. 3 and 4).
Parameters:
Temperatures - GC oven: 60°C isothermal conditions for initial six
(6) minutes of analysis; then increased to 110°C at 24°C/min. The
final temperature of 110°C is held for four (4) minutes, then returned
to 60°C at the rate of 50°C/min. The GC injector and manifold are
at 125°C constant.
Gas flows and pressures - Helium carrier gas - 46 psig on instrument
regulator, 5.5 units on rotameter producing 31.6 ml/min flow at column
outlet.
Hydrogen fuel gas - 19 psig on instrument regulator, as determined
from optimization curve (Fig. 3) using test gas containing 100 ppm
Methane in Helium.
Zero Air (<0.5 ppm CO) - 30 psig on instrument regulator, as determined
from optimization curve (Fig. 4).
Attenuation factors - During calibration and standardization the GC
attenuation setting was X2 to reduce base-line noise on the recorder;
all other attenuation factors were XI (Fig. 2). During actual auto
emission tests it has been demonstrated that a total attenuation of
X10 will be required to keep peaks within the limits of the graph paper.
Calculations:
Five consecutive tests were conducted to establish a field of data for
calculations of counts per part per million (ppm) of component compounds and
standard deviation values. (Fig. 2)
194
-------
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195
-------
FIGURE 3 HYDROGEN OPTIMIZATION (SAMPLE GAS: 100 PPM METHANE IN HELIUM)
•FIGURE 4 AIR OPTIMIZATION (SAMPLE GAS: 100 PPM METHANE IN HELIUM)
196
-------
To calculate average counts:
7 _ IX
A -
n
where X = average count
EX = sum of test counts for a specific hydrocarbon
n = number of tests
Compound )(
CH4 4151.6
C2H2 7254.8
C2H4 4893.6
C2H6 2886.0
C3H8 3936.0
The following equation was used to calculate average counts per ppm:
C =
ppm where C = average counts/ppm
(con. of st'd gas)
Compound C
CH4 3774.2
C2H2 6045.7
C2H4 4448.7
C2H6 2405.0
C3Hg 3936.0
The standard deviation of the counts for each compound was calculated by:
c -
n(n-l)
where S = standard deviation
X = sample values
n = number of samples
197
-------
Compound Counts
CH4 +4.8989 x
C2H2 +1.3784 x
C2H4 +9.4868 x
C0H. +1.1158 x
-£ U —
C_H0 +1.0548 x
38 —
To calculate Hydrocarbon Mass values:
HP — V Y n
-------
HC
-— • is the value of the individual Hydrocarbon component,
J. j UUU j W\J U
e.g., Methane, as determined by Gas Chromatographic analysis.
Density values are obtained from the "Handbook of Chemistry
§ Physics", 46th Edition (1965-66)
Compound Density @ 20°C £, 760 mmHg
Methane 6.7 x 10"4 gm/ml
Acetylene 1.08 x 10~3 gm/ml
Ethylene (Ethene) 1.17 x 10~3 gm/ml
Ethane 1.25 x 10~3 gm/ml
Propane 1.83 x 1CT3 gm/ml
199
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Laboratory Services Division
APPENDIX F
CERTIFICATE OF ANALYSIS
PRODUCT - INDOLENE H.O. MOTOR FUEL III
Batch No. 2 Date Tested 4-6-74
PRODUCT ANALYSIS
Tank No. 529
TEST
API Gravity
Distillation % F
Initial Boiling Point
10% Evap,
50% Evap.
90% Evap.
Maximum
10% Slope
Reid Vapor Pressure
Oxidation Stability Minutes
GUM, mg/100 ml
Lead Content gms/gal.
Sulfur, Weight %
Olefin, %
Aromatic, %
Saturates, %
Octane Research (Clear)
Octane Research (3cc TEL/gal)
Sensitivity (Clear)
Sensitivity (3cc TEL/gal)
Phosphorus, gms/gal
ASTM METHOD
D287
D86
D86
D86
D86
D86
D86
D86
D323
D525
D381
D526
D1266
D1319
D1319
D1319
D2699
D2699
ACM 21.00
SPECIFICATION
CONTROL LIMIT
58.0-61.0
75-95
120-135
200-230
300-325
NMT 415
NMT 3.2
8.7-9.2
NLT 600
NMT 4.0
Nil
NMT 0.10
NMT 10
NMT 35
Remainder
96.0-98.5
NLT 103.0
7.0-10.5
NMT 9.0
NMT 0.01
TEST RESULTS
59.2
89
133
219
321
405
2.9
9.1
600+
1.8
0.001
0.01
5.1
29.8
65.1
98.2
104.8
10.9
9.8
0.00
J. A. GRANT, Manager-Laboratory
Services Division
per s/I. G. Dubeck
DATE; APRIL 10, 1974
200
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing/
1 REPORT NO.
EPA-460/3-74-014
2.
3. RECIPIENT'S ACCESSIOr+NO.
PB-224 316/AS
4. TITLE AND SUBTITLE
A Study of Emissions from 1967-1974 Light-Duty
Vehicles in Newark, New Jersey
5. REPORT DATE
October 1974
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
A. R. Martin, L. M. Anstey, D. Seal
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
General Environments Corporation
6840 Industrial Road
Springfield, Virginia 22151
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-0389
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Office of Mobile Source Pollution Control
Office of Air and Waste Management Programs
Ann Arbor, Michigan 48105
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
General Environments Corporation (GEC) of Springfield, Virginia was selected
to participate in the FY73 Emission Factors Program by the Environmental
Protection Agency (EPA). One hundred eighty privately owned light-duty
vehicles from the metropolitan Newark, New Jersey area were tested for
exhaust emission levels of total hydrocarbons, carbon monoxide, carbon
dioxide, oxides of nitrogen, light hydrocarbons, and aliphatic aldehydes
according to the 1975 Federal Test Procedure. All vehicles were also
tested for highway fuel economy and vehicles from 1972 through 1974 were
tested for modal emissions. The test results were used to compute emission
factors based on both the 1972 and 1975 Federal Test Procedures,
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Exhaust Emissions
Automobiles
Light-Duty Trucks
Hydrocarbons
Carbon Monoxide
Oxides of Nitroger
Gasoline
Fuel Economy
13B
13. DISTRIBUTION STATEMENT
UNLIMITED
19. SECURITY CLASS (Tins Report)
UNCLASSIFIED
21. NO. OF PAGES
207
2O. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
201
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