EPA-460/3-76-026
August 1976
ACCELERATED DECAY
OF NON-FUEL
EVAPORATIVE EMISSIONS
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Mobile Source Air Pollution Control
Emission Control Technoloffv Division
Ann Arbor, Michigan
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EPA-460/3-76-026
ACCELERATED DECAY
OF NON-FUEL
EVAPORATIVE EMISSIONS
Task No. 1
by
Automotive Environmental Systems, Inc.
7300 Bolsa Avenue
Westminster, California 92683
Contract No. 68-03-2413
EPA Project Officer: Thomas C. Bejma
EPA Task Officer: Gary Wilson
Prepared for
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
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 (MD-35) , 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
Automotive Environmental Systems, Inc. , 7300 Bolsa Avenue, Westminster,
California 92683, in fulfillment of Contract No. 68-03-2413. The contents
of this report are reproduced herein as receive'd from Automotive Environ-
mental Systems., Inc. 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-460/3-76-026
11
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TABLE OF CONTENTS
ABSTRACT iv
1.0 INTRODUCTION 1
2.0 SUMMARY 2
3.0 TECHNICAL DISCUSSION 5
3.1 Program Objective 5
3.2 Program Design 6
3.3 Test Vehicles 7
•7
3.3.1 Selection and Preparation
3.4 Facilities and Equipment 11
3.4.1 Evaporative Emissions Enclosure 11
3.4.2 Bake Oven 11
3.4.3 Gas Chromatography/Mass Spectrometry • . 15
3.5. Test Procedures 17
3.5il Evaporative Emissions Test Procedure ... 17
3.5.2 Gas Chromatography Test Procedure .... 21
3.5.3 Scheduling 22
4.0 TEST RESULTS 25
4.1 Evaporative Emission Results 25
4.2 Gas Chromatography Results 28
APPENDIX A A-l
ill
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ABSTRACT
The purpose of this program was to determine if driving a vehicle on a
dynamometer or baking a vehicle in a paint oven could accelerate the
normal decay of background hydrocarbon evaporative emissions from new
vehicles. A series of daily background evaporative emission tests were
performed on two groups of three identical Ford LTD's. The tests were
performed in accordance with the procedures outlined in SAE J171a. All
fuel system components were either removed or plugged. The carburetors
were removed and the intake manifolds covered with a plate. An auxiliary
fuel system was used when running each vehicle on the dynamometer.
Daily testing was begun on each vehicle within nine days after manufac-
turing. One vehicle in each group was a control vehicle which soaked
between daily tests. After each daily test, the second vehicle in each
group was driven on the dynamometer for five series of two LA-4 driving
schedules, with a 30-minute soak with the engine off following each series,
It was then soaked until the next test. The third vehicle in each group
was placed in a bake oven at 125°F for 12 hours after each test and then
soaked until the next test.
All initial background emission levels were below 1.5 gms per test. The
cars tested were manufactured in California where the California Air
Resources Board has a rule governing the use of photochemical reactive
solvents. The implementation of this rule has resulted in the use of
paints, sound deadening materials, body fillers, etc., which are non-
photochemical ly reactive. Compliance to this rule may have contributed
to lower vehicle background emissions levels.
The first group of three vehicles had no vinyl roofs, whereas the second
group of three vehicles were equipped with vinyl roofs. The results tend
to indicate that the background emission levels were not affected by the
presence of the vinyl roofs.
iv
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The "dyno" and "oven" vehicles showed more rapid declines in background emis-
sions than the control vehicles. The daily background emission reductions
in "dyno" vehicles were comparable to the daily reductions experienced in the
"oven" vehicles. The results indicate that background emission decay rates
can be accelerated by driving the vehicles on a dynamometer or by baking the
vehicle.
Gas chromatography (GC) and mass spectrometry (GCMS) were used to attempt to
identify and quantify the constituents of the background hydrocarbon emissions
in the enclosure. Toulene was the most prominent constituent ranging from 5% to
56% by weight. Benzene, xylene, methylethylbenzene, and trimethylethylbenzene
were consistently identified and quantified in these California built vehicles,
however, this may not typify nationwide results.
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1.0 INTRODUCTION
The testing project described in this report was undertaken as Task 1 of EPA
Contract No. 68-03-2413. The purpose of this project was to attempt to
accelerate the decay of vehicular non-fuel evaporative emissions. The back-
ground emission levels of new vehicles typically decay very rapidly during
the days following production until eventually a stabilization level is
reached. In order to perform evaporative emission tests on new vehicles, it
is important that the background emissions be reduced to the stabilization
level as rapidly as possible.
In addition to measuring the total hydrocarbon emissions, it was decided to
attempt to use mass spectrometry and gas chromatography (GC and GCMS) to
identify and quantify the constituents of the enclosure atmosphere. The identifi-
cation of the constituents could assist in determining the sources of back-
ground emissions..
Initially one group of three vehicles was to be tested for thirteen consecu-
tive days. But after seven days of testing, the background levels were so
low it was decided to check the results by testing a second set of three
vehicles for seven days.
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2.0 SUMMARY
Non-fuel evaporative emission tests were performed on two groups of three
full size passenger cars to determine if driving and baking the vehicles
would accelerate the decay of non-fuel evaporative emissions.
It would appear, as illustrated in Figures 2-1 and 2-2, that the greatest
decay by mass of non-fuel hydrocarbons was in the first 9 to 10 days after
production. Another observation would be that vinyl interiors and roof do
not significantly contribute to hydrocarbon emissions, as vehicles D, E
and F were so equipped while vehicles A, B and C were not.
The task performed for EPA originally called for the testing of three identical
full-size vehicles, produced at the same assembly plant on the same day and
equipped without vinyl interiors or roofs. These vehicles were built as
requested by Ford Motor Company's Pico Rivera, California assembly plant
and delivered to AESi's test facilities. However, since initial tests pro-
duced hydrocarbon levels much lower than the expected 4 to 6 grams per test,
a second set of three vehicles was requested by EPA to confirm the result of
the initial tests. As illustrated by Figures 2-1 and 2-2, the next series
of tests produced comparable HC concentrations.
An investigation was made in an attempt to find a reason for the low evapora-
tive hydrocarbon emissions experienced with these test vehicles. Previous
background emissions tests were performed by EPA and Ford Motor Company on
vehicles produced in the Detroit area. However, in this program all the
test vehicles were built in California. After extensive research, AESi dis-
covered that the California Air Resources Board (CARB) has Rule 442 governing
the use of photochemically reactive solvents in Los Angeles County. In auto-
mobile assembly this rule applies to paints, sound deadening materials, body
fillers, etc. which must be non-photochemically reactive solvents. The CARB
Rule 442 is presented in Appendix A.
- 2 -
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O = VEH. A - CONTROL
O = VEH. B - DYNO
x = VEH. C - OVEN
DAYS AFTER VEHICLE PRODUCTION
Figure 2-1. NON-FUEL EVAPORATIVE EMISSION TEST
VEHICLE TOTAL MASS HYDROCARBONS PER DAY
- 3 -
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•*.-,
D = VEH. D - CONTROL
0 = VEH. E - DYNO
X = VEH. F - OVEN
M
T-:
00 „.
W
CO
D
X
X
6
I
7
8
Figure 2-2.
I
9
I
10
I
11
I
1 2
DAYS AFTER VEHICLE PRODUCTION
NON-FUEL EVAPORATIVE EMISSION TEST
Vehicle Total Mass Hydrocarbons per Day
1
13
- 4 -
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5.0 TECHNICAL DISCUSSION
3.1 PROGRAM OBJECTIVE
The primary objective of this program was to attempt to find a means of
accelerating the decay of new vehicle background emissions.
Typically a new vehicle must stand for 60 to 90 days before the background
emissions reach acceptable levels. This program was designed to evaluate
two alternate methods of accelerating the decay of these non-fuel background
emissions. The first method involved placing the test vehicle in a paint
bake room. The second method involved accumulating mileage on a vehicle by
operating it on a chassis dynamometer.
A secondary objective of this program was to identify the hydrocarbon con-
stituents of the background emissions. The plan was to enable source identi-
fication by quantifying the hydrocarbon compounds present in the background
emissions. Gas chromatography and mass spectrometry were used to attempt
to identify and quantify the constituents of the background hydrocarbon
emissions.
- 5 -
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3.2 PROGRAM DESIGN
This program was designed to compare the background emission degradation rates
of three identical vehicles receiving different treatments. One vehicle was
randomly selected to be the control vehicle which was only soaked between tests.
Another vehicle was driven on the dynamometer between tests. It was driven
using a series of LA-4 driving schedules. The test sequence consisted of 2 LA-4's
followed by a 30 minute soak. This procedure was replicated five consecutive
times each day. The final vehicle was baked in a paint shop bake oven for 12
hours between tests. Each vehicle was tested daily using the SHED method of
measuring background hydrocarbon emissions.
The data was plotted using "days after vehicle production" as the X axis and
"total hydrocarbon mass emissions" as the Y axis. The degradation rates were
compared to determine if one or both of the treatments would significantly
accelerate the reduction in background emissions.
Samples of the enclosure atmosphere were taken during selected tests and were
analyzed using GCMS .and GC. These samples were collected using a variety of
methods. One of the program goals was to evalute various methods of GCMS
sample collection. A calibration procedure was developed for the GCMS sampl-
ing work.
- 6 -
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3.3 TEST VEHICLES
3.3.1 Selection and Preparation
The test vehicles selected for this program were three, 1976 Ford LTD 2-door
automobiles without vinyl roofs. Each vehicle was equipped with a 351-2V
engine (belonging to the 351m/400 catalyst, EGR/Air family), automatic trans-
mission, air conditioning, power steering and brakes with cloth interiors. All
three vehicles were assembled at Ford Motor Company's Pico Rivera, California
plant on the following dates and times:
Vehicle VIN Assembly Date Time
A (control) 6J62H169231 6/7/76 08:00
C (oven) 6J62H169232 6/7/76 16:00
B (dyno) 6J62H169233 6/8/76 08:00
The vehicles were randomly assigned to the treatments they were to receive.
The vehicles were received at AESi test facilities in Westminster, California
on June 11, 1976 at which time it was noticed that one of the vehicles (VIN:
6J62H169233) was equipped with a vinyl interior. This car was returned to
Ford on June 14 to have the vinyl exchanged for a cloth interior. The mileage
on the:se vehicles when received were as follows:
VIN: 6J62H169231 - 34.0 miles
VIN: 6J62H169232 - 45.5 miles
VIN: 6J62H169233 - 34.4 miles
Each vehicle underwent the same preparation procedure prior to the beginning
of testing. This preparation included the removal or plugging of the items
as follows.
- 7 -
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Items Removed Items Plugged
- Fuel tank - Valve cover vent
- Carburetor - Fuel pump
- Evap. Canister - All vacuum hoses
- Evap. Hoses - Vapor hoses
- Spare tire - Fuel lines
- Trunk mats - PCV
- Intake manifold
- Tailpipe
- Dipstick tubes - engine
- Dipstick tubes - transmission
- Dipstick tubes - P/S
- Radiator over-flow tube
- Differential vent
- Transmission vent
All fuel and vapor lines were purged with nitrogen at 5 psi for 15 minutes.
The windshield washer containers were checked, but not removed since all units
were found to contain water. A check for oil leaks and spills was made. All
leaks were repaired and all spills were cleaned. The catalytic converters and
mufflers were inspected for possible drainholes which would require plugging,
however, none were found.
Vehicle preparation for the LA-4 driving cycle prior to the hot soak evaporative
emission test included reinstalling the vehicle's carburetor and connecting to
an external fuel supply consisting of a long flexible fuel hose and a Chevrolet
Vega fuel tank with integral fuel pump. Electric choke connector, vacuum advance,
EGR and PCV were all reconnected to the carburetor, and the plug in the valve
cover vent was removed. The same procedure was followed for the dyno vehicle
when being prepared for its series of daily LA-4 cycles. In addition the air
cleaner was installed complete with EGR back-pressure valve. The plugs in the
differential and transmission vents and power steering filler tube were also
removed.
- 8 -
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After the LA-4 Cycle the vehicle was re-prepared for the hot soak by
removing the carburetor, sealing the intake manifold opening, and plugging
the various hoses and vents before being moved to the SHED. An elapsed
time of 6 minutes was allowed for this operation. A sniff test was made
with the enclosure FID to identify any fuel spills. The vehicle was then
moved into the enclosure, and after the enclosure was sealed the initial
readings were taken. This 6 minute time period was maintained throughout the
the duration of the task. The allowed time of 6 minutes was a nominal
value derived by a series of practice runs on a non-test vehicle.
A thermocouple was taped to the inside of the oven vehicle so interior tem-
peratures could be recorded during the 12-hour bake period.
Midway into the te.sting. program and at the request of EPA, three more vehicles
were procured from a Ford dealer. The dealer acted immediately on our request
and located three more nearly identical vehicles. The only changes from the
first three vehicles were that these new vehicles had vinyl roofs and that
they were produced on three consecutive days. A description of these
vehicles is as follows: Three 1976 Ford LTD 2 doors with vinyl roofs. Each
was equipped with 400-2V engines (belonging to the 351m/400 catalyst, EGR/air
family), automatic transmissions, air conditioning, power steering and brakes
with vinyl interior. All these vehicles were assembled at Ford Motor Company's
Pico Rivera, California plant on the following dates and times:
Vehicle VIN Assembly Date Time
E (dyno) 6J68S167818 6/16/76 15:00
F (oven) 6J68S167836 6/17/76 17:00
D (control) 6J68S167817 6/18/76 08:00
The mileage on these vehicles as received are as follows:
R".rv!0'l HI LIBRARY
- 9 - E:77ir.3Ii:.:3::TAL PROTECTION
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VIN: 6J68S167817 - 3.3 miles
VIN: 6J68S167818 - 2.2 miles
.VIN: 6J68S167836 - 3.4 miles
It can be noted that vehicle D (VIN: 6J68S167817) was equipped with a full
vinyl roof while vehicles E § F had half vinyl roofs.
These vehicles underwent the same preparation procedures as the first 3
vehicles including both driving and testing preparations.
- 10 -
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3.4 FACILITIES AND EQUIPMENT
3.4.1 Evaporative Emissions Enclosure
An AESi designed and fabricated SHED (Sealed Housing for Evaporative
Determinations), as illustrated by Fig. 3-1, was used to perform the
Evaporative Emission Test Program. The SHED was constructed of light-
gauge aluminum panels providing good heat dissipation. Panels were
bolted together at formed flanges, and the SHED was fitted with windows,
doors, and a ceiling of DuPont Tedlar Pol/vinyl Fluoride Film. The
SHED interior dimensions are approximately 10 feet wide by 21 feet long
by 8 feet high, having a total volume of 1695.3 ft.3. Specially designed
doors seal completely upon.closing, rendering the enclosure leakproof.
Specifications for the SHED were in agreement with all requirements stipulated
in the SAE J171a Evaporative Emission Test Procedure. A Beckman Model 400
Flame lonization Detector was used in conjunction with the SHED to measure
hydrocarbon evaporative emissions. A Leeds and Northrup Speedomax Temper-
ature Recorder was used to record ambient temperature inside the SHED.
3.4.2 Bake Oven
The Oven used for the required baking of vehicles C and F is located at
P 5 R Auto Painting Center, 7601 Garden Grove Blvd., Garden Grove, Cali-
fornia, which is a distance of 2.3 miles from the AESi test facilities.
It was manufactured by West Coast Spray Booth of Bell Gardens, California
and heated by a 200,000 BTU Gaffers S Sattler, Inc. Gas Fired Furnace. As
illustrated by Fig. 3-2, the oven dimensions are 25 ft x 14 ft. x 9 ft. The
oven is equipped with one drive-in door and one personnel door, a 12" purge
fan, one cut-off microswitch located on each door to control the fan and
heater. The heater is pre-set (stipulated by prevailing safety requirements)
to approximately 125°F. The ambient temperature inside the oven and inside
the test vehicle were continuously recorded. A typical temperature recording
during the vehicle bake period is illustrated by Figure 3-3, showing the oven
ambient temperature and temperatures recorded in the vehicle interior.
- 11 -
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ro
FIGURE 3-1, AESi SEALED HOUSING FOR EVAPORATIVE DETERMINATIONS (SHED)
-------
PERSONNEL
DOOR »
OJ
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Figure 3-2. Vehicle Bake Oven
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During Vehicle Bake Period
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3.4.3 Gas Chromatography/Mass Spectrometry
The Gas Chromatography/Mass Spectrometry Tests of new car non-fuel evaporative
emissions was conducted by West Coast Technical Service, Inc., of Cerritos,
California. Founded in 1965 as a mass Spectrometry laboratory, WCTS is a
versatile analytical service organization. WCTS1 3000 ft2 laboratory space
is fully equipped for chemical analysis with special instrument capabilities
as follows:
9 Mass Spectrometry
Gas - Liquid - Solid capability
Mass Range: m/e 1-1800
Resolution.: maximum of 1 part in 2500
Detectability: 1 ppb ultimate
Direct Ion Introduction
• Gas Chromatography
Sample: Gas, liquid or solid
Injector Temperature control for flash vaporization
Column Capabilities: Glass or metal columns,capillary or packed columns
Detectors: Differential flame ionization and thermal conductivity
Isothermal and Temperature Programming to 350° C.
Direct Integration
• Combined Gas Chromatography - Mass Spectrometry
Sensitivity: 1 x 10~9 grams/second
Minimum scan time: 1 second
Capillary and SCOT columns
Peak detection by total ion monitor
- 15 -
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• Thermal Analysis
Temperature Ranges:
Thermogravimetric Analysis 25°C to 1200°C.
Differential Thermal Analysis- 150°C to 1600°C.
Differential Scanning Calorimetry - 1500C to 600°C.
Heating Rates - 0.5°C to 100°C per minute
Pressure Ambient to High Vacuum
Any noncorrosive or honexplosive atmospheres
• Infrared Spectrophotometry
Spectral Range - 4000 CM"1 to 625 CM'1
(2.5 to 15 microns)
Scale Expansion - 2.5 and 10
Micro sample capability
t Atomic Absorption
Percent to parts per billion range
Lamps for most metals on hand
Flame emission
• UV-Visible Spectrophotometry
Range: 200nm to 975 nm
Resolution: Maximum of 1 part in 2500
- 16 -
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3.5 TEST PROCEDURES
3.5.1 Evaporative Emissions Test Procedure
In this program only non-fuel evaporative emissions were measured using
the SAE Sealed Housing for Evaporative Determination (SHED) method and in
accordance with SAE J171a Appendix C entitled "Measurement Procedure for
Car Background HC Emission." Vehicle preparation for this test included
removal of the fuel tank and carburetor, purging the fuel, vapor lines, and
fuel pump with nitrogen and then plugging all entrances and exits. All
other exits from the engine and exhaust system which could supply a source
of hydrocarbons were plugged.
Prior to each test; the enclosure was purged, instrumentation checked, and the
mixing blower was turned on. A visual check of the test vehicle was made
to ensure all required plugs were installed and no oil leaks existed. Two
or three minutes before the scheduled start time of the cold test, the Flame
lonization Detector (FID) was zeroed and spanned and the test vehicle was
pushed to the front of the enclosure. Then the temperature recorder was started,
the vehicle pushed into the enclosure, and the enclosure sealed. At this point
the initial FID, temperature and barometric pressure readings were taken and
recorded on the Evaporative Emission (SHED) Data Sheet - EPA (XAA-502) 12-74.
This data sheet was supplied by EPA and was completed for each vehicle test.
It included cold/hot soak readings in addition to vehicle I.D., model, model
year, inertia, actual dyno hp, engine information, odometer reading, operator,
test date, wet bulb (°F) , dry bulb (°F), test time, evaporative test number,
etc. During the 60 minute cold soak, the SHED enclosure temperatures and
hydrocarbon emission levels were recorded as well as the barometric pressure
at 10 minute intervals. At 50 minutes into the test, gas samples were drawn
from the enclosure for the Gas Chromatography/Mass Spectrometry Analysis. At
the end of the cold soak period, final enclosure readings were taken and
recorded, the vehicle was removed from the enclosure and pushed onto the chassis
dynamometer. The dynamometer was previously warmed up with a non-test vehicle
- 17 -
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and inertia set at 4500 Ibs and horsepower at 12.7. At this point, the
carburetor connected to an external fuel supply was reinstalled and the
tailpipe unplugged along with all other atmospheric openings required for
engine operation. While the test vehicle ran the single LA-4 cycle, which
was recorded on a driver's aid, the enclosure was being purged for the hot
soak. Upon completion of the driving cycle, the vehicle was moved off the
dynamometer where the engine was then shutdown. The time was recorded at
this point and at the point of initial enclosure atmosphere readings after
enclosure sealing. A six minute elapsed time for this operation was allowed
by EPA. During this allowed time the carburetor was removed and inlet block-
off plate installed, the tailpipe was plugged along with all unplugged
atmospheric openings that were necessary for engine operation. The vehicle
was then pushed to the front of the enclosure where a 15 second (approxi-
mately) sniff sample of the engine compartment was taken with the FID. At
5 minutes 15 seconds the vehicle was pushed into the enclosure, and then
the enclosure was.sealed. The initial readings of hydrocarbon, temperature
and barometric pressure were recorded at this time. As in the cold soak,
enclosure atmopsheric conditions were taken and recorded at 10 minute
intervals and at 50 minutes into the test, gas samples were taken for the
Gas Chromatography/Mass Spectrometry. At 60 minutes the final hydrocarbon
emission level, temperature and barometric pressure were recorded and the
vehicle removed from the enclosure. The test procedure is illustrated in
Figures 3-4 and 3-5..'
An Enclosure Qualification Test was performed before both series of tests
were made in accordance with EPA's Recommended Practice, dated April, 1976.
- 18 -
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VEHICLE TECHNICIAN
START
~T
CHECK VEHICLE
AS
PER
RATION
VEHICLE
FOR TEST
PREPA-
CHECKLIST
VEH.
VEH.
B
C
&
&
E -
F -
1st
3rd
PREP
PREP
ADVISE SUPERVISOR S
START REQUIRED REPAIRS
MOVE VEHICLE TO FRONT
OF SHED. WINDOWS AND
TRUNK OPEN
MOVE VEHICLE INTO SHED
- CLOSE AND SEAL DOORS
VEH. B & E - 8:00 a.m.
VEH. A & D - 11:30 a.m.
VEH. C fi F - 3:00 p.m.
PUT A NON-TEST VEHICLE
ON DYNO AND CAKE READY
FOR RUN-IN PERIOD
CHECK TEST VEHICLE
EXTERNAL FUEL TANK
FOR FUEL AND PUMP
OPERATION
IS
THE CARB,
TOOLS, PLUGS, ETC
READY FOR INSTAL-
LATION
MAKE READY AND
ADVISE SUPERVISOR
OF ANY PROBLEMS
CALIBRATE DYNO & RUN-IN
AT 30 MPH FOR 15 MIN -
SET INERTIA S ROADLOAD
HORSEPOWER AT 50 MPH
Continued
MOVE VEHICLE OFF DYNO
SET DRIVER'S AID -
STAMP TRACE AND RECORD
NFORMATION
LE FROM SHED
9:00 a.m.
12:30 p.m.
4:00 p.m.
PUSH ONTO DYNO - INSTALL
CARB. AS PER CHECKLIST.
START FUEL SUPPLY.
START 7.5 MILE DYNO RUN
AT COMPLETION OF DYNO
RUN, SHUT OFF FUEL SUPPLY
REMOVE CARB., INSTALL
INTAKE SEALING PLATE,
PLUG HOSES, TAILPIPE, ETC.
AS PER CHECKLIST
MOVE VEHICLE TO SHED -
TRUNK G WINDOWS OPEN -
HOOD OPEN FOR COMPARTMENT
FID TEST
TIME - 4 MIS ENGINE SHUT-
DOWN TO SHED. 2 MIN FOR
SNIFF TEST, SHED SEALING
AKD INITIAL FID SAMPLE
AFTER FID SAMPLE, CLOSE
HOOD - CLOSE S SEAL
SHED DOORS
Continued
Figure 3-4. Non-Fuel Evaporative Emission Procedure
Vehicle Technician
19
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INSTRUMENT TECHNICIAN
START
TURN ON EQUIPMENT -
CHECK TEMP
SHED INSTR
RECORDER,
POWER
AND WORKING GASES
7:30 a.m.
11:00 a.m.
2:30 p.m.
ADVISE SUPERVISOR
DETERMINE CAUSE
_L
TURN ON SHED MIXING
AND PURGE BLOWERS -
ZERO & SPAN ANALYZER
TURN ON POWER & ALLOW
INSTRUMENTS TO STABILIZE
TURN OFF PURGE BLOWER -
MOVE VEHICLE INTO SHED.
ON HOT TEST TAKE FID
READING OF ENGINE COM-
PARTMENT - THEN TAKE
INITIAL FID ENCLOSURE
READING
ON HOT TESTS PURGE
BLOWER CAN BE DIRECTED
BETWEEN BLDG. S SHED
WALLS FOR COOLING
AT 50 MIN TAKE GAS
SAMPLES FROM SHED
AND LABEL
ZERO £ SPAN FID
IMMEDIATELY PRIOR
TO END OF TEST.
AT 60 MIN ANALYZE
ENCL. ATMOSPHERE S
RECORD TIME
VEHICLE REMOVED FROM
SHED
IS
SHED TEMP
>68F <86F
ADVISE SUPERVISOR
CORRECT CONDITION
BSE- 8:00 a.m.
A S D - 11:30 a.m.
C & F.- 3:00 p.m.
Figure 3-5.
Non-Fuel Evaporative Emission Procedure
Instrument Technician
20
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3.5.2 Gas Chromatograph Test Procedure
To study the feasibility of getting quantitative data, a standard
gas mixture was prepared containing equal parts by weight of methylene
chloride, methy ethyl ketone, 1,1,1-trichloroethane, p-xylene, and an
aliphatic hydrocarbon mixture containing primarily n-decane, n-undecane,
and n-dodecane. Three separate samples were taken at the concentration
levels equivalent to 1, 3 and 6 grams given by EPA as the expected levels
to be found during the testing program. This was accomplished by
weighing these amounts (1, 3 and 6 grams) of the gas standard into beakers.
For each sample, a beaker was placed on a hot plate inside the enclosure,
a corresponding shot of propane in weights of 0.2, 0.6 and 1.2 grams was
introduced through an external port. The circulation fan inside the
enclosure was turned on when the doors were sealed. After 15 minutes the
FID showed a stable reading. Samples were taken from the enclosure with
glass bottles and tenax tubes containing a porous organic polymer. During
the first few tests several different sized samples were taken ranging
from 0.1 to 1.0 liters using a hand operated 100 milliliter Drager Model
31 pump. One stroke of this bellows type pump equals 100 milliliters.
The grab samples were pulled through 125 and 250 milliliter bottles for
3 minutes at 5 CFH and then capped. All samples were labeled as to test
number, initial and final FID readings; temperature and barometric pressure
at time of sample. A 500 milliliter background sample was also taken for
identification purposes by purging the enclosure, sealing it, and allowing
it to sit with the mixing blower on for 15 minutes before taking sample.
In a further attempt to identify the hydrocarbon vapors, three additional
tests were run where one hour samples were taken by using a pump flow
rate of 8 CFH to pull the sample through a large drying column filled with
"Drierite" (calcium sulfate), then passing the gasses through a small
impinger trap cooled in a dry ice-acetone slush bath. Other tenax samples
were taken at the rate of 1 liter/min. for the last 50 minutes of the soak.
Gas .samples were discontinued after June 25 at the request of EPA due to
the low total hydrocarbon concentrations inside the enclosure.
- 21 -
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3.5.3 Scheduling
The following is a summary of the daily scheduling of each vehicle as
illustrated by Fig. 3-6.
The "dyno" vehicle (designated B § E) started the daily tests since it
required a technician for the entire working day. It was given a
visual inspection to ensure all necessary plugs were in place and that
there was no evidence of oil leaks. Each day at 0800 hours, the vehicle
was pushed into the enclosure for the cold soak portion of the evaporative
emission test. Upon completion of the cold soak, the vehicle was pushed
from the enclosure onto the dynamometer where the auxiliary fuel system
was connected by installing the carburetor. Then an LA-4 cycle was run.
Within six. minutes after the completion of the LA-4, the auxiliary fuel
system was removed and the vehicle was sealed in the enclosure for the
beginning of the hot soak portion of the test. After the hot soak, the
vehicle was prepared for its series of LA-4 cycles which started at
1130 hours and lasted 6 hours, or un-til 1730 hours. After running on
the dyno, the auxiliary fuel system was removed, the vehicle lines.were
plugged as required for testing, and the vehicle was moved to the
soak area.
The "control" vehicle (designated A § D) was visually inspected and
then placed in the enclosure at 1130 hours to undergo an evaporative
emission test. At the conclusion of the complete tests, (approx. 1415
hours) the control vehicle was returned to the vehicle soak area. This
vehicle received no other treatment and was only driven for the one
LA-4 (required prior to the hot soak test) each day.
The "oven" vehicle (designated C § F) received the same visual inspection
and at 1500 hours was moved into the enclosure for the evaporative emission
- 22 -
-------
test which was completed at approximately 1745 hours. At 1800 hours,
a tow truck picked up the vehicle and delivered it to the bake oven
location at P § R Auto Painting Center, 7601 Garden Grove Blvd., Garden
Grove, California (a distance of 2.3 miles), where at 1830 hours the
vehicle began its 12 hour bake period. At 0630 hours the following day,
the tow truck picked up the vehicle and delivered it back to the AESi
facility where it entered the vehicle soak area for the remainder of
the soak period. This vehicle was only driven during the evaporative
emission tests.
- 23 -
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E/B
SHED
DYNO
SHED
SOAK
B/A
I
ro
F/C
SHED
_•_•. UXNU
*—I SHED
SOAK
SHED
3YNO
SOAK
D
BAKE OVEN
VEHICLE A/D - CONTROL
VEHICLE B/E - DYNO
VEHICLE C/F - OVEN
Figure 3-6. EPA Non-Fuel Evaporative Emission Test — Vehicle Schedule
-------
4.0 TEST RESULTS
4.1 EVAPORATIVE EMISSION RESULTS
The non-fuel evaporative emission test results for the two groups of
test vehicles are presented in Tables 4-1 and 4-2 as well as
Figures 2-1 and 2-2. Tables 4-1 and 4-2 present the mass hyrdrocarbons
measured in both the cold and hot soak portions of the tests as well
as the total mass hydrocarbons per test. Figures 2-1 and 2-2 present
the total measured mass hydrocarbons plotted by number of days after
being built.
Every vehicle tested experienced a reduction in total hydrocarbons with
the passing of time. The "dyno" vehicles and the "oven" vehicles both
showed a more rapid decline than the "control" vehicles. All of the
SHED test results were relatively low compared to what was expected
by EPA.
25
-------
Table 4.1. Non-Fuel Evaporative Emission Test
Date
6/15
6/15
6/15
6/16
6/16
6/16
6/17
6/17
6/17
6/18
6/18
6/18
6/19
6/19
6/19
6/20
6/20
6/20
6/21
6/21
6/21
6/22
Test #
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
DAILY MASS
Veh.
B
A
C
B
A
C
B
A
C
B
A
C
B
A
C
B
A
C
B
A
C
B
HYDROCARBONS PER VEHICLE
Cold Soak
.337
.161
.234
.193
.101
.182
.133
.117
.117
.103
.088
.102
.104
.088
.094
.074
.076
.102
.058
.087
.073
.044
Hot Soak
1.058
.631
.765
.521
.429
.560
.343
.393
.413
.313
.431
.394
.241
.399
.340
.184
.342
.310
.164
.369
.222
.205
Total
1.395
.792
.999
.714
.530
.742
.476
.510
.530
.416
.519
.496
.345
.487
.434
.258
.418
.412
.222
.456
.295
.249
- 26 -
-------
Table 4.2. Non-Fuel Evaporative Emission Test
DAILY MASS HYDROCARBONS PER VEHICLE
Date
6/24
6/24
6/24
6/25
6/25
6/25
6/26
6/26
6/26
6/27
6/27
6/27
6/28
6/28
6/28
6/29
6/29
6/29
6/30
6/30
7/1
Test #
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
Veh.
E
D
F
E
D
F
E
D
F
E
D
F
E
D
F
E
D
F
D
F
D
Cold Soak
.139
.115
.220
.047
.130
.115
.050
.130
.043
.043
.123
.058
.043
.101
.043
.021
.058
.014
.072
.022
.021
Hot Soak
.500
.536
1.002
.338
.566
.509
.229
.564
.321
.169
.557
.233
.131
.451
.166
.097
.295
.123
.359
.110
.303
Tota]
.639
.651
1.222
.385
.696
.624
.279
.694
.364
.212
.680
.291
.174
.552
.209
.118
.353
.137
.431
.132
.324
- 27 -
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4.2 GAS CHROMATOGRAPHY RESULTS
The results from gas chromatography and gas chromatography/mass spectrometry
analyses are summarized in Table 1. The relative concentrations and identity
of each component is listed. The composition of the gas does not appear to
change very much with time or between test vehicles. The identity for each
component was obtained from GCMS analysis of large volume samples. In addi-
tion to the aromatic compounds which predominated the mixture, alkanes and
some alkenes, primarily in the range of CJQ through £\2> were observed.
However, these were not present in high enough concentration to fully
characterize. Samples analyzed using a DC-200 column gave excellent sepa-
ration of the major components. "Grab" samples showed that there were no
detectable C\ through Cg hydrocarbons produced. The detection limit was
less than 0.1 grams of propane in the SHED. Typical gas chromatograph and
graphs are illustrated by Figures 4-5 through 4-9.
The following table relates the test number to the vehicle and test date:
Test No. Date Tested Vehicle Code Type
4 6/16 B Dyno
5 6/16 A Control
6 6/16 C Oven
7 6/17 B Dyno
8 6/17 A Control
9 6/17 C Oven
21 6/21 C Oven
23 6/24 E Dyno
24 6/24 D Control
25 6/24 F Oven
26 6/25 F Dyno
27 6/25 D Control
28 6/25 F Oven
- 28 -
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WEST COAST TECHNICAL S€RV1C€ INC.
Automotive Environmental Systems
Mr. Tim Runner
July 13, 1976
Page 4
13 An *t An A
Den.iene
Toluene
Xylene
Xylene + Styrene +
Alkane *
Methylethylbenzene
Trimethylbenzene
f* o • i \* 0 *4 fri i+A*4 T3 «n •* A n A
04 oUDSututeo. Benzene
FNi 4 1« 1 tl» 1L* ^ >*
uimeinyietnyiDenzene
Total Other Components
Benzene
Toluene
Xylene
Xylene + Styrene +
Alkane *
Methylethylbenzene
Trimethylbenzene
/"* O LK «J * 4. ~J D
04 oUDStitutea cenzene
rx* &L& i *w 1 w M#WK^«
L/imetnyieinyiDenzene
Total Other Components
Test H
Cold
60
.0
28.9
8.8
6.8
5.8
1.6
Oc
.0
OQ
. O
40.4
Test #7
Cold
1.1
33.1
15.6
16.2
6.4
2.5
25.1
Table 1
Test #4
Hot
8C
. 0
25.6
8.0
5.6
3.2
2.2
46.9
Test #7
Hot
1.1
22.2
11.4
14.5
12.5
10.3
5 A
.4
2 A
.U
20.6
Weight
Test #5
Cold
43.0
9.6
5.5
4.1
2.4
•\ i
i . i
i i
i . i
33.2
Test #8
Cold
2.0
31.1
16.9
14.8
7.9
5.4
3D
. 3
2C
. O
15.4
Percent
Test #5
Hot
31
. i
56.0
10.9
4.5
5.2
3.1
•« c
1 .0
10
. O
14.4
Test #8
Hot
4.6
34.1
17.0
8.8
7.3
5.1
2C
.0
27
. /
17.8
Test #6
Cold
57
. /
33.0
10.8
5.9
3.9
2.1
i C
1 . D
i n
1 . L
35.8
Test #9
Cold
0.3
29.1
15.2
10.0
7.5
6.4
30
. t.
3f)
. t.
25.1
Test #6
Hot
6r
. 0
35.7
11.6
4.0
4.0
2.2
Oc
.0
07
. /
34.7
Test #9
Hot
3.8
34.8
17.6
7.3
5.9
3.4
1 C
1 . 0
1 Q
i .y
23.8
* Probably a CIQ or Cjj alkane
- 29 -
-------
WEST COAST TECHNICAL SERVICE INC.
Automotive Environmental Systems
Mr. Tim Runner
July 13, 1976
Page 5
T3 An yono
Deil&cire
T^rtl i iAn A
loiuene
Xylene
«. i g §
Ayiene, otyrene,
Alkane *
Methylethylbenzene
Trimethylbenzene
04 Substituted Benzene
Dimethylethylbenzene
and alkane
Total Other Components
Test #21
Hot (1)
00
. If
HA
. I
25.1
Ui
. i
15.1
7.6
8.3
8.9
12.3
Test #23
Hot (1)
1 C
1 . O
10 o
10. o
16.0
in A
1U. ft
13.4
16.0
8.1
8.8
12.0
Test #24
Hot (1,2)
2.4
12.1
17.7
21.2
22.1
24.5
Test #25
Hot (1)
1 c
1 .0
19 Q
1Z. 0
27.4
80
. o
12.3
12.2
6.6
7.5
10.8
(1) large sample analyzed by GCMS
(2). bad sample
Back-
ground
Test #26 Test #27 Test #28 on
Hot Hot Hot 6/16/76
Benzene
Toluene
Xylene
Xylene, Styrene-,
Alkane *
Methylethylbenzene
Trimethylbenzene
04 Substituted Benzene
Dimethylethylbenzene
Total Other Components
4.9
6.9
8.0
1.5
17.1
18.2
7.2
22.8
16.7
8.7
3.2
14.3
5.4
6.6
7.6
10.8
12.3
11.5
38.0
9.2
9.2
6.6
8.5
22.5
6.7
6.8
5.5
4.4
28.4
70.5
* Probably a CJQ or Cjj alkane
Back-
ground
on
6/25/76
100
The chromatograms are enclosed for your reference. If we can be of any
further service, please do not hesitate to contact us.
Respectfully submitted,
WEST COAST TECHNICAL SERVICE INC.
D.J. Northington, Ph.D.
Assistant Technical Director
- 30 -
DJN/kd
-------
SOLTEC
H-25-1
-------
3456
XYLENE, MICROGRAMS
Figure 4-6. Xylene (Gas Standard Calibration Curve)
-------
CO
00
2.0 3.0
HYDROCARBONS, MICROGRAMS
Figure 4-7. Hydrocarbon (Gas Standard Calibration Curve)
4.0
-------
I
CO
456
METHYLENE CHLORIDE MICROGRAMS
Figure 4-8. Methylene Chloride (Gas Standard Calibration Curve)
-------
CO
en
CM
o
15
10
0.2
0.4
0.8 1.0 1.2
PROPANE, GRAMS IN SHED
Figure 4-9. Propane (Gas Standard Calibration Curve)
-------
APPENDIX A
RULE 442. Usage of Solvents
(a) A person shall not discharge organic materials into the
atmosphere from equipment in which organic solvents or materials
containing organic solvents are used, unless such emissions have been
reduced by at least 85% or to the following:
(1) Organic materials that come into contact with flame
or are baked, heat cured or heat polymerized, are limited to
1.4 kilograms (3.1 pounds) per hour not to exceed 6.5 kilograms
(14.3 pounds) per day.
(2) Organic materials emitted into the atmosphere from
the use of photochemically reactive solvents are limited to
3.6 kilograms (7.9 pounds) per hour, not to exceed 18 kilograms
(39.6 pounds) per day, except as provided in subsection (a)
(1). All organic materials emitted for a drying period of
12 hours following their application shall be included in
this limit.
(3) Organic materials emitted into the atmosphere from
the use of non-photochemically reactive solvents are limited
to 180 kilograms (396 pounds) per hour not to exceed 1350
kilograms (2970 pounds) per day, except as provided in sub-
section (a) (1). All organic materials emitted for a drying
period of 12 hours following their application shall be
included in this limit.
(b) Equipment designed for processing a continuous web, strip
or wire which emit organic materials shall be collectively subject to
the limitations stated in subsection (a).
A-l
-------
(c) Emissions of organic materials into the atmosphere required
to be controlled by subsection (a) shall be reduced by:
(1) Incineration, provided that 90 percent or more of the
carbon in the organic material being incinerated is oxidized to
non-organic materials, or
(2) Incineration, provided that the concentration of organic
material following incineration is less than 50 ppm, calculated as
carbon and with no dilution or
(3) Absorption, or
(4) Processing in a manner determined by the Air Pollution
Control Officer to be not less effective than (1) or (3) above.
(d) A person shall not use any organic solvent containing a total
of 4 percent or more by volume of the materials described in Rule 102
under PHOTOCHEMICALLY REACTIVE SOLVENT for the commercial cleaning of
garments and fabrics unless the emission of organic materials into the
atmosphere has been reduced by at least 90 percent by weight.
(e) A person shall not use photochemically reactive solvent to
thin, reduce or dilute industrial and commercial metal surface coatings
unless the emission of organic materials into the atmosphere has been
reduced by at least 85 percent by weight.
(f) A person shall not use photochemically reactive solvent in
industrial and commercial surface cleaning or degreasing operations unless
the emission of organic materials into the atmosphere has been reduced
by at least 85 percent by weight.
A-2
-------
(g) A person shall not during any one day dispose of a total of
more than 5 liters (1.3 gallons) of any photocheraically reactive solvent,
or of any material containing more than 5 liters (1.3 gallons) of any
photochemically reactive solvent by any means which will permit the
evaporation of such solvent into the atmosphere.
(h) A person shall not use, sell or offer for sale for use in the
District, in containers of 0.94 liter (one quart) capacity or larger,
any architectural coating containing photochemically reactive solvent.
(i) A person shall not thin or dilute any architectural coating
with a photochemically reactive solvent.
(j) The provisions of this rule shall not apply to:
(1) The manufacture of organic solvents, or the transport or
storage of organic solvents, or the transport or storage of materials
containing organic solvents.
(2) The use of equipment for which other requirements are
specified by Rules.. 461, 462, 463, or 464 or which are exempt from air
pollution control requirements by said rules.
(3) Tfie spraying or other employment of organic solvents as
insecticides, pesticides or herbicides.
(4) The use of water reducible materials, provided that:
(A) the volatile content of such material is not
photochemically reactive and consists of at least 80
percent water by volume, and
A-3
-------
(B) more than 50 percent by volume of such volatile
material is evaporated before entering a chamber heated
above ambient application temperature, and
(C) the organic solvent or any material containing
organic solvent does not come into contact with flame.
(6) The use of ultra high solid materials, provided that:
(A) the volatile content of such material is not
photochemically reactive and does not exceed 5 percent
by volume of said material, and
(B) the organic solvent or any material containing
organic solvent does not come into contact with flame.
A-4
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-460/3- 76-026
3. RECIPIENT'S ACCESSIOWNO.
4. TITLE AND SUBTITLE
Accelerated Decay of Non-Fuel Evaporative Emissions
5. REPORT DATE
August 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Automotive Environmental Systems, Inc.
7300Bolsa Ave.
Westminster, California 92683
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-2413
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
2565 Plymouth Road
Ann Arbor. Michigan 48105
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This program was designed to determine whether driving a vehicle on a dynamometer or
baking a vehicle in a paint oven could accelerate the normal decay of background hydro-
carbon evaporative emissions from new vehicles. Daily background evaporative emission
tests were performed on two groups of three identical Ford LTD's in accordance with the
procedures outlined in SAE J171a. All fuel system components were either removed or
plugged. The carburetors were removed and the intake manifolds covered with a plate.
An auxiliary fuel system was used when running each vehicle on the dynamometer. Daily
testing was begun on each vehicle within nine days after manufacturing. One vehicle in
each group was a control vehicle, which soaked between daily tests . After each daily test,
the second vehicle in each group was driven on the dynamometer for five series of two
LA-4 driving schedules, with a 30-minute soak with the engine off following each series.
It was then soaked until the next test. The third vehicle in each group was placed in a
bake oven at 125°F for 12 hours after each test and then soaked until the next test.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATl Field/Croup
Air Pollution
Motor Vehicles
Evaporative Emissions
18. DISTRIBUTION STATEMENT
UNLIMITED
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
46
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
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