United States Office of Mobile Source Air Pollution Control EPA 460/3-85-003
Environmental Protection Emission Control Technology Division December 1985
Agency 2565 Plymouth Road
Ann Arbor, Michigan 48105
Air
c/EPA In-Use Evaporative Canister
Evaluation
H
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rwsre*.
EPA 460/3-85-003
In-Use Evaporative Canister Evaluation
by
Mary Ann Wamer-Selph
Southwest Research Institute
6220 Culebra Road
San Antonio, Texas 78284
Contract No. 68-03-3162
Work Assignment 27
EPA Project Officer. Craig A. Harvey
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Mobile Source Air Pollution Control
Emission Control Technology Division
2565 Plymouth Road
Ann Arbor, Michigan 48105
December 1985
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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, Environmental Protection Agency, 2565 Plymouth Road, Ann Arbor,
Michigan 48105.
This report was furnished to the Environmental Protection Agency by Southwest
Research Institute, 6220 Culebra Road, San Antonio, Texas, in partial
fulfillment of Contract No. 68-03-3162. The contents of this report are
reproduced herein as received from Southwest Research Institute. The
opinions, findings, and conclusions expressed are those of the author and not
necessarily those of the Environmental Protection Agency. Mention of
company product names is not to be considered as an endorsement by the
Environmental Protection Agency.
Publication No. EPA 460/3-85-003
ii
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FOREWORD
This project was conducted for the U.S. Environmental Protection Agency
by the Department of Emissions Research, Southwest Research Institute. The
work was performed between December 198^ and July 1985 under EPA
Contract No. 68-03-3162, Work Assignment 27. It was identified within
Southwest Research Institute as Project 03-7338-027. The EPA Project Officer
was Craig A. Harvey of the Office of Mobile Source Air Pollution Control,
Emission Control Technology Division, Environmental Protection Agency, 2565
Plymouth Road, Ann Arbor, Michigan. The Southwest Research Institute
Project Manager was Charles T. Hare, and the Project Leader was Mary Ann
Warner-Selph.
iii
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ABSTRACT
This program involved the evaluation of 21- samples of charcoal from in-
use evaporative canisters. The Environmental Protection Agency (EPA)
provided the canisters from programs conducted by the EPA, Tennessee Valley
Authority (TVA), and Southwest Research Institute (SwRI) on both alcohol
blend-fueled and unleaded gasoline-fueled vehicles. Ten canisters from alcohol
blend-fueled vehicles, eight from gasoline-fueled vehicles, and six from vehicles
with unknown fuel histories were tested.
A system was developed to remove and collect the effluent from samples
of canister charcoal at room temperature (cold purge) and under heated
conditions (hot purge). Charcoal samples of about 50 g were first cold purged
with dry nitrogen at a flowrate of approximately 1.5 cfm. Butane working
capacity was then measured, and the charcoal was subsequently hot purged at
approximately 355-375°F (180-190°C). The effluent was sampled during
selected cold and hot purge cycles and analyzed for water content, methanol,
ethanol, tertiary butyl alcohol (TBA), total hydrocarbons (THC), and selected
detailed hydrocarbons.
iv
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TABLE OF CONTENTS
Page
FOREWORD iii
ABSTRACT iv
LIST OF FIGURES vii
LIST OF TABLES viii
I. INTRODUCTION 1
II. PROCEDURES AND INSTRUMENTATION 3
A. Handling and Storage of Charcoal Canisters 3
B. Sampling System 5
C. Working Capacity 9
D. Analytical Procedures 9
III. DEVELOPMENT AND VALIDATION OF SAMPLING SYSTEM 13
A. Development of Sampling System 13
B. Practice Cold and Hot Purge Cycles and Working
Capacity Measurement of an In-Use Charcoal Sample 14
C. Validation of the Charcoal Sampling System 17
D. Water Content of New Unused Charcoal 19
E. Surface Area of Unused Charcoal Samples 20
IV. RESULTS 21
A. Water Content 21
B. Methanol, Ethanol, and TBA 27
C. Total Hydrocarbons 29
D. Comparison of Charcoal Weight Loss to the Sum of Water
Content, Alcohols, and Total Hydrocarbons 29
E. Working Capacity 31
F. Detailed Selected Hydrocarbons 31
G. Summary of Results 40
V. QUALITY ASSURANCE 43
REFERENCES 45
V
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TABLE OF CONTENTS (CONPD)
APPENDICES
A. BUTANE WORKING CAPACITY PROCEDURE
B. THE MEASUREMENT OF METHANOL, ETHANOL, AND TERTIARY
BUTYL ALCOHOL IN EXHAUST
C. CALCULATION OF HYDROCARBON RECOVERY (IN GRAMS)
FROM BAG PPMC
D. CHARCOAL WEIGHT LOSS AND CONTINUOUS HC LEVELS DURING
THE PURGE CYCLE (OF DELCO IN-USE CHARCOAL) OF THE
BUTANE WORKING CAPACITY PROCEDURE
E. WORKING CAPACITY FOR INDIVIDUAL WORKING CAPACITY
CYCLES
F. SELECTED DETAILED HYDROCARBONS
vi
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LIST OF FIGURES
Figure
1
2
3
4
5
6
vii
Metal Charcoal Holder 6
Schematic of Charcoal Purge and Sampling System 7
Charcoal Purge and Sampling System 8
Selected Detailed Hydrocarbon Chromatogram for
Canister Number EPA 1480049 Hot Purge Cycle,
Diluted 1 to 10 32
Comparison of the Distribution of Detailed
Hydrocarbon Emissions from Hot Purge Cycles
Averaged by Fleet and by Fuel Type 37
Comparison of the Distribution of Detailed
Hydrocarbon Emissions Sampled from TVA Charcoal
Samples During Cold and Hot Purge Cycles 38
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1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
LIST OF TABLES
Page
Evaporative Charcoal Canisters Evaluated 4
Continuous HC Concentrations and Rate of
Charcoal Weight Loss of In-Use Delco Charcoal
During Cold and Hot Purge Cycles 15
Breakthrough Time of Charcoal Using Butane 16
Butane Working Capacity of In-Use Delco Charcoal 17
Recoveries of Gasoline, Methanol, Ethanol, TBA,
and Water from New Delco and Motorcraft Charcoals 18
Water Content of Unused Charcoal 19
Summary of Results of In-Use Evaporative Canister
Charcoal Testing on 50 g Samples of Charcoal 22
Comparison of Charcoal Hot Purge Cycle Emissions
and Working Capacity by Fleet and Vehicle Fuel
Type for 50 g Samples of Charcoal 23
Comparison of Charcoal Hot Purge Emissions and
Working Capacity by Vehicle Class and Fuel Type
for 50 g Samples of Charcoal 24
Comparison of Cold Purge Cycle and Hot Purge Cycle
TVA Charcoal Sample Emissions for 50 g Samples
of Charcoal 25
Comparison of Charcoal Weight Loss to the Sum of
Water Content, Alcohols, and Total Hydrocarbons 26
Compound Numbers for Selected Detailed
Hydrocarbons 34
Percentage of Each Hydrocarbon Group to Total
Detailed Hydrocarbons 35
Percentage of each Hydrocarbon Group to Total
Detailed Hydrocarbons from Cold and Hot Putge
Cycles of TVA Charcoals 39
Summary of Percentages of Paraffins, Olefins and
Aromatics in Purged Charcoal Effluent from 50 g
Samples from In-Use Evaporatove Canisters 40
Precision, Accuracy, and Completeness 43
viii
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I. INTRODUCTION
The effect of alcohol blends and related co-solvents on evaporative
emissions has been studied in several programs at SwRI. One project involved
the measurement of evaporative emissions during the Sealed Housing for
Evaporative Determinations (SHED) test on vehicles fueled with an alcohol
blend and on vehicles fueled with unleaded Indolene. Another project involved
the laboratory evaluation of reduced-sized charcoal canisters that had been
exposed to a hydrocarbon blend and a simulated alcohol blend. The work
described in this report, which involves the analysis of the effluent from in-use
evaporative canister charcoal, is part of the ongoing research effort to
quantitate the effect of methanol, ethanol, and TBA on charcoal canisters. The
purpose of this work was to determine any differences in the quantity of
specific compounds adsorbed on evaporative canister charcoal from
gasoline/alcohol blend fueled vehicles as compared to those from gasoline
fueled vehicles. To relate any such differences to performance of the charcoal,
butane working capacity tests were also conducted on each charcoal sample.
The first task of the program involved the design and development of a
system to remove and sample the compounds retained by in-use canister
charcoal. A sample pump was used to draw dry nitrogen through the charcoal
sample to purge off hydrocarbons, alcohol, and water. Purging was done at
room temperature (cold purge) and then at approximately 355-375°F (180-
190°C, hot purge). The charcoal effluent was sampled for methanol, ethanol,
TBA, water, THC, and selected detailed hydrocarbons during ail hot purges and
during six cold purge cycles. Purging was separated into cold and hot purges to
determine how much of the adsorbed material would desorb easily versus how
much would tend to remain on the charcoal despite room temperature purging.
Three butane working capacity tests were performed on the charcoal
after cold purging and before heated purging. This involved loading butane onto
the charcoal until a hydrocarbon breakthrough level of 1000 ppmC was reached,
after which the charcoal was cold purged. The charcoal canister was weighed
after butane loading and after purging; the difference in the two weights is
defined as the working capacity. THC and detailed hydrocarbons were
measured on selected cold purges during working capacity tests.
The second task of this project involved the evaluation of 24 evaporative
canister charcoal samples. The charcoal was removed from the canisters as
needed and stored in capped glass bottles. The charcoal was shaken in the
bottle to provide a uniform sample and then approximately 50 g was removed
and placed in a reduced-sized metal canister for testing. Ten charcoal samples
were from vehicles which had been operated with alcohol blends, eight samples
were from vehicles that had been operated with unleaded gasoline, and six
were from vehicles with an unknown fuel history. The charcoal samples were
subjected to three procedures:
• Room temperature (cold) purge with nitrogen until charcoal weight loss is
less than 1 g/hr.
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• Butane working capacity
Load charcoal with butane to 1000 ppmC breakthrough level
Cold purge to weight loss of less than 1 g/hr
Weigh before and after cold purge; difference is working capacity
Repeat two times
• Hot purge at ~355-375°F (~ 180-190QC) with nitrogen until charcoal
weight loss is less than 1 g/hr.
Methanol, ethanol, TBA, water content, THC, and detailed hydrocarbons
were measured during both cold and hot purge cycles for six of the 24 charcoal
samples. THC and detailed hydrocarbons were also measured during the cold
purge cycle of the working capacity procedure for the same six charcoal
samples. The effluent from the remaining charcoal samples was analyzed for
alcohols, water content, THC, and detailed hydrocarbons during the hot purge
only. For these samples, no analyses were performed during the cold purge
cycle of the working capacity procedure.
2
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IL PROCEDURES AND INSTRUMENTATION
The procedures and instrumentation required to sample and analyze
alcohols, water, and hydrocarbons from in-use evaporative charcoal samples are
described in this section. The handling and storage of the evaporative test
canisters is also described. The sampling system was designed to remove
compounds retained on charcoal in a stream of nitrogen. Impingers were used
to sample alcohols, Drierite to sample water, and Tedlar bags for hydrocarbons.
Gas chromatography was used to analyze alcohols and hydrocarbons, and water
content was measured by Drierite weight gain. Butane working capacity of the
charcoal was also measured.
A. Handling and Storage of Charcoal Canisters
Eighteen canisters were shipped to SwRI from the TVA and nine from the
EPA, Ann Arbor. Fourteen canisters were supplied by the EPA to the
Department of Emissions Research, SwRI under Contract Number 68-03-3192,
Work Assignment Number 7, using vehicles that had accumulated mileage under
a DOE program. Twenty-four of these ^1 canisters were selected for testing,
and they are described in Table 1.
The selection of the canisters was based on acquiring charcoal data by
groups of similar vehicle types. Higher priorities were assigned to multiple
canisters from the same engine family. The Work Plan originally called for the
analysis of 3ft canisters. The number was reduced to accommodate an increased
level of work effort. This increased level of work included the addition of a
working capacity cycle and a recovery test on the sampling system.
The canisters from the TVA and EPA were received with tape covering
the port openings, while the canisters from SwRI were provided with stoppers
inserted into the port openings. The canisters were stored at room temperature
prior to testing.
The TVA blend fueled vehicles had been operated for one year, alternating
in six week periods with the blend and with unleaded gasoline. Following this
was six months' operation with gasoline before the canisters were removed for
this test program. The TVA gasoline/alcohol blend fuel was a tailored blend
with a distillation curve very similar to the gasoline and a slightly lower RVP
(e.g. 9.95 psi blend, 10.7 psi gasoline in the summer).
The SwRI (DOE fleet) blend was a splash blend with the base gasoline, and
therefore had a much higher RVP (about 12 vs. 9 psi). These vehicles had been
operated since new (about 14,000 miles) on their respective mileage
accumulation fuels except for (a) one SHED test at about 10,000 miles using a
matched volatility version of the blend in all the vehicles, and (b) a number of
SHED tests with an 11.5 RVP gasoline at the end of the mileage accumulation.
The EPA canisters were from in-use vehicles, so their fueling histories are
unknown.
3
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TABLE 1. EVAPORATIVE CHARCOAL CANISTERS EVALUATED
Source
Canister
Number
Vehicle Description
TV A
2090a
82 Chevy Chevette 98 CID
2099a
82 Chevy Chevette 98 CID
1925
81 Chevy Chevette 98 CID
8887a
81 Ford Fairmont Wagon 140 CID
1991a
82 Chevy Chevette 98 CID
2067a
82 Chevy Chevette 98 CID
1725
8i Chevy Chevette 98 CID
1747
81 Chevy Chevette 98 CID
8961a
81 Ford Fairmont Wagon 140 CID
8902
81 Ford Fairmont Wagon 140 CID
SwRI
201
84 Ford Escort 98 CID
(from DOE
202
84 Ford Escort 98 CID
fleet)
205
84 Ford Escort 98 CID
206
84 Ford Escort 98 CID
101
84 Ford Escort 98 CID
102
84 Ford Escort 98 CID
104
84 Ford Escort 98 CID
106
84 Ford Escort 98 CID
EPA
A1480008
83 Ford DFM3.3VlGXFXd
A1480049
83 Ford DFM3.3VlGXFXd
A1480073
83 Ford DFM3.3VlGXFXd
A1480039
83 Ford DFM3.3VlGXFXd
A1480060
83 Ford DFM3.3VlGEF6d
A1480096
83 Ford DFM3.3VlGEF6d
Vehicle Fuel Type
Gasoline
Gasoline
Gasoline
Gasoline
Gasoline-Alcohol Blend*3
Gasoline-Alcohol Blend'3
Gasoline-Alcohol Blend*3
Gasoline-Alcohol Blend'3
Gasoline-Alcohol Blend*3
Gasoline-Alcohol Blend*3
Gasoline
Gasoline
Gasoline
Gasoline
Gasoline-Alcohol Blendc
Gasoline-Alcohol Blendc
Gasoline-Aicohol Blendc
Gasoline-Alcohol Blendc
e
e
e
e
Gasoline and Oxinol 50*
Total
Charcoal
Weighty
543.4
546.3
583.3
087.3
567.3
567.3
567.2
581.4
520.9
460.9
523.2
539.9
541.3
500.6
533.5
541.1
528.1
542.7
459.2
550.0
513.8
439.5
489.1
539.1
aAdditional analyses during cold purge and working capacity cycles
**5% O2 gasoline-alcohol blend
c4% (vol) methanol, 2% (vol) ethanol, 2% (vol) TBA
^Engine family number
eUnknown
^Unknown, but vehicle was tested (FTP) once with Oxinol 50 prior to canister removal
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B. Sampling System
The charcoal from each test canister was removed and placed in a glass
jar. The jar was shaken to mix the charcoal and to provide a representative
sample for testing. Fifty grams of charcoal was transferred to a metal
container that was screened on the bottom to secure the charcoal. A Swagelok
fitting had been welded to the top of the container to allow nitrogen flow
through the charcoal. Views of the canister are shown in Figure 1. Glass wool
was also placed on the screen and at the fitting to minimize the loss of fine
charcoal particles.
The system, which was designed to draw nitrogen through the charcoal,
consisted of two chambers; one for room-temperature and one for heated
purging. A schematic of the sampling system is shown in Figure 2, and views
of the system are shown in Figure 3. Gaseous nitrogen from a liquid nitrogen
cylinder was directed to a Boekel desiccator adapted to gas flow for cold (room
temperature) purging, or to a Blue M oven adapted to gas flow for hot purging.
The heated purge system was also equipped with a sleeve heater on the inlet
line to the oven. Excess nitrogen flow was used to create a slight positive
pressure in the system with the pump "on". This reduced the possibility of room
air being drawn into the purge system.
A Thomas dual-head pump, operating at approximately k2 2,/min (1.5
cfm), directed sample flow to a four-way manifold with a vent to the
atmosphere for excess flow. Four smaller Thomas pumps withdrew samples of
charcoal effluent from the manifold for alcohol, water content, bag
hydrocarbon, and continuous hydrocarbon analyses. Alcohols were sampled in
impingers and water in a Drierite tube at sample flowrates of about £/min;
and bag hydrocarbons were collected at approximately ^ A/min during working
capacity purges, and at approximately 1 2,/min during other purge cycles. A
continuous hydrocarbon analyzer, Beckman Model 400, was operated according
to the manufacturer's specifications to monitor the sample stream for
hydrocarbons.
The charcoal sample was cold or hot purged until the rate of charcoal
weight loss was less than 1 g/hr. A large portion of the weight loss is
attributable to removal of hydrocarbons, and thus the concentration of
hydrocarbons in charcoal effluent provides a good indication of weight loss. A
continuous hydrocarbon level of 300 ppmC was experimentally found to
correspond with a charcoal weight loss of less than 1 g/hr (the calculated value
was OA g/hr)a. Initial charcoal purges were performed to a hydrocarbon level
of 300 ppmC, however, the time required to purge to 300 ppmC was in excess of
1 1/2 hours. Therefore, a 600 ppmC hydrocarbon cut-off level was chosen for
sample purging. A 600 ppmC hydrocarbon level is equivalent to an emission
rate of 0.9 g/hr of hydrocarbons, still less than the maximum desired rate of 1
g/hr. Using the 600 ppmC cut-off level reduced the length of each purge cycle
to less than 1 1/2 hours for most charcoal samples.
^300 ppmC/10b) x(purge rate, 1.5 cfm) x(60 min/hr) x(16.33 g/ft^ HC)
= OA g/hr
5
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Measuring Butane Breakthrough
Weighing Charcoal Holder
Figure 1. Metal charcoal holder
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To Vent Hood
To HC Analyzer
Cold Purge Unit
Tedlar
Bag
Regu Lat ing
Valve
Magnehelic
Charcoal
Container
Pump
Drlerite
Dryer
I- _J
Dry
Gas
Meter
Silica
Gel
Dryer
3-Way Valve
Heated Sample Line
To Vent Hood
Flowmeter
Silica
Gel
Dryer
Liquid
Dry
Gas
Meter
Clta rco.i I
Container
Oven
Impingers
in Ice Bath
Hot Purge Unit
Figure 2. Schematic of charcoal purge and sampling system
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Cold and Hot Purge Units
Sampling Cart
Figure 3. Charcoal purge and sampling system
8
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C. Working Capacity
The working capacity of each charcoal sample was measured after the
cold purge cycle according to a butane working capacity procedure provided by
the EPA Project Officer. The procedure is found in Appendix A. Working
capacity is defined as the difference between the charcoal weight when loaded
with butane (at about 280 m£/min to 1000 ppmC breakthrough level) and the
charcoal weight after cold purging the charcoal to 600 ppmC. Measurement of
working capacity was included in the program at the request of the Project
Officer to provide additional charcoal information. The total number of
charcoal samples originally to be analyzed was reduced to accommodate the
added level of effort.
Butane working capacity is a measure of the charcoal's ability to "hold"
onto butane while loading at 280 m £/min and then to release it during a cold
purge cycle. The charcoal samples typically lost the same amount of weight
from purging as was added during butane loading. Thus, the difference between
working capacities was in the butane loading cycles. Some charcoals were able
to retain butane to a greater degree at the chosen flowrate before butane
vapors "broke through" the charcoal at a measured concentration of 1000 ppmC.
D. Analytical Procedures
Charcoal effluent samples were analyzed by several procedures. Impinger
samples were analyzed for methanol, ethanol, and TBA. A Drierite tube was
weighed before and after testing to determine water content and bag samples
were analyzed for THC and detailed individual hydrocarbons. The procedures
are described in this section.
1. The Measurement of Methanol, Ethanol, and TBA
Methanol, ethanol, and TBA were sampled by bubbling the charcoal
effluent during a cold or hot purge cycle through two glass impingers in series,
each containing 25 m£ of deionized water. The temperature of the impingers
was maintained at 0-5°C by an ice bath, and the flow rate through the
impingers was maintained at k £/min by a sample pump. The impinger alcohol
samples were transferred to polyethylene containers after completion of a cold
or hot purge cycle.
The alcohol samples were analyzed on a Perkin-Elmer 3920B gas
chromatograph (GC) equipped with a flame ionization detector. A 5 portion
of the sample is injected into the GC and analyzed isothermally at 221°F
(105°C) for methanol, at 284°F (140°C) for ethanol, and at 302°F (150°C) for
TBA. Sample peak areas are compared to external standards to obtain alcohol
concentrations in yg/m^. These values are converted to mg of methanol,
ethanol, or TBA using the following equation:
yg/m^ x Purge Flowrate, ft^/min x Purge Length, min. x 0.028317 m^/ft^
x 10~3 mg/ug = mg alcohol
A more detailed version of this procedure is found in Appendix B.
9
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2. The Measurement of Water Content
Water is sampled from the charcoal effluent during the cold or hot
purge cycle using a preweighed ^ inch polyethylene drying tube filled with
Drierite. The tube is weighed after the purge cycle to determine water weight
gain to 0.01 g. Water content of the charcoal sample is calculated using the
following equations:
Equation 1:
Purge Flow Volume, ft3 = Purge Flowrate, ft3/min x Purge Length, min
Equation 2:
Drierite Flow Volume = Measured Flow Through Drierite Tube, ft3 x
Bar. Press., in Hg x 52S°F
29.92 in Hg Temp °F + ^60
Charcoal Sample Water Content, g = Drierite Wt. Gain, g x Equation 1
Equation 2
A test was performed with the dryer tube to determine if Drierite
absorbs alcohol in addition to water. One milliliter of methanol was evaporated
into a stream of dry nitrogen. The methanol vapor was pumped through a
Drierite tube until the methanol was fully evaporated. The drying tube was
weighed before and after the test and was found not to have gained weight, so
methanol was apparently not absorbed onto the Drierite. A water-methanol
sample was not tested to determine the affinity of moist Drierite for methanol.
However, for all but one sample, the weight of methanol in charcoal effluent
was less than or equal to 5 percent of the weight of the measured water.
3. The Measurement of THC
The procedure used for the measurement of bagged total hydrocar-
bons (THC) is similar to that listed in the Code of Federal Regulations.^*
THC's were measured using a heated FID. The procedure included the use of
calibration gases for sample quantification. No corrections were made for the
presence of alcohol.
The Measurement of Detailed Individual Hydrocarbons
Detailed hydrocarbons were analyzed on a bag sample collected at
approximately 1 ijmin during the cold or hot purge cycle or on a bag sample
collected at t Z/min during the working capacity purge cycle (the same sample
was also used for THC analysis). A gas chromatographic system was used to
analyze the bag samples. It permits the quantitative determination of more
than 80 of the hydrocarbons in charcoal effluent, carbon numbers 4 to 10. The
capillary column used to separate these compounds is a Perkin-Elmer F-50
versilube, 150 ft x 0.020 inch WCOT stainless steel column. The column is
initially cooled to -139°F (-95°C) for sample injection. Upon injection, the
temperature is programmed at a 7°F (
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to permit complete column flushing. A flow controller is used to maintain a 1.5
m X,/min carrier flow rate. The 10 nrU sample volume for C^-Cio permits
accurate determination of 0.1 ppm C with the flame ionization detector used
(Perkin-Elmer 3920B). The baseline is re-established at about 60 minutes after
injection, resulting in about 1 1/2 hours of analytical turn-around time.
Calibration of the gas chromatograph is achieved using a benzene
standard traceable to a NBS benzene standard. The per unit response of the
FID for each individual HC component is assumed to be equivalent for
calculations. This assumption was based on a study reported in Basic Gas
Chromatography by McNair and Bonelli which reported relative FID
sensitivities of over 30 paraffin, olefin, and aromatic compounds. The FID
sensitivity responses of the compounds varied 15 percent from maximum to
minimum, while the majority of the responses (>9
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IIL DEVELOPMENT AND VALIDATION OF SAMPLING SYSTEM
The development of the sampling system and the associated operating
procedures involved several steps. First, the design of the sampling system
went through several alterations until it could properly handle in-use
evaporative charcoal samples. After the sampling system was completed, a
practice run on in-use charcoal was performed to further define operating
parameters. In the third step, alcohol, water, and hydrocarbon recovery
experiments were conducted with spiked new charcoal samples to validate the
operation of the sampling system. Fourth, new, unused charcoal samples were
cold and hot purged and the water content determined. For additional
information, the surface areas of unused Delco and Motorcraft charcoals were
measured using the Brunauer, Emmett, and Teller Method (B.E.T.) for surface
area analysis.
A. Development of Sampling System
The initial intent of the program was to test the charcoal from full-size
evaporative canisters, however, a preliminary test using the entire charcoal
contents of an in-use 1980 Mercury Cougar canister indicated a downsized
system would provide a better method for sampling charcoal effluent. The
charcoal, which weighed 476.2 g, was transferred to a metal container. It was
subjected to one 20-minute cold purge, two 20-minute hot purges, and a
shortened 13-minute hot purge. The system became saturated with liquid fuel
which had condensed in the flowmeters, valves, pumps, dryer tubes, and Teflon
lines during the final hot purge. Before the final cycle, the oven temperature
had been elevated and allowed to stabilize with the canister inside the oven.
Apparently fuel evaporated from the canister during the warm-up period and
produced a slug of liquid fuel when purging began. Excessive hydrocarbons were
also produced during the cold and first two hot purge cycles, even without liquid
fuel present. Hydrocarbon levels above 10,000 ppmC, the upper limit of the
detector, were measured in all purge cycles.
Due to the inability of the sampling system to handle the amount of
charcoal effluent produced from the standard size canister tested, the system
had to be expanded and/or the amount of charcoai sample reduced. A larger
purge pump was employed to provide additional dilution of charcoal effluent,
and the amount of charcoai used for testing was reduced to approximately one
tenth of the charcoal in a standard size canister. The larger pump flowed at
about 42 £/min (the original pump flowed at 18 l/min), providing additional
dilution of (42 / 18) x 10 *23 times. The water sampling system was also
scaied down with a smaller, lighter weight sampling tube used to trap water
from the smaller charcoal sample. The lighter tube could be weighed to 0.01 g,
whereas the original water sampling tube could be weighed to only 0.1 g. The
methanol, ethanol, and TBA analytical procedure was still sufficiently sensitive
to the alcohols at the reduced levels.
In addition to downsizing the sampling system, the problem of moist room
air leaking into the system during purging and in the weighing process had to be
addressed. The relatively high humidity level of room air would cause errors in
measuring the water content of charcoal. Excess nitrogen was therefore
13
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directed to the sample chambers to minimize air leakage. The cold purge
system was equipped with a flowmeter connected to a vent, plus a magnehelic
gauge, to monitor excess nitrogen flow out of the desiccator box. The oven in
the hot purge system was not an air-tight unit. It was therefore not possible to
monitor excess nitrogen flow as was done on the cold purge. Inlet nitrogen flow
was adjusted to several different flowrates and bag samples were collected at
each flowrate setting. The bags were measured for oxygen content to
determine the nitrogen flowrate that would minimize air leaks into the system
without unreasonable consumption of nitrogen. The same inlet nitrogen flow
was set for both cold and hot purge cycles.
The weighing process was also a source of air leaks into the system. In
the original cold and hot purge procedures, the charcoal was to be weighed
approximately every 10 minutes until the weight remained constant. Such
frequent interruptions during purging would introduce up to 28 liters of air into
the system each time the charcoal container was removed. In addition, the
integrity of samples collected under such conditions may be questioned. This
would be especially true for hot purge samples in which the heated charcoal
would continue to off-gas during the weighing process and possibly reabsorb
water.
Repetitive charcoal weight measurements also made it impossible to
maintain a stable oven temperature during the hot purge cycle. An alternative
method for determining charcoal weight loss was desirable due to the
drawbacks associated with repetitively weighing the canister. A Beckman 400
hydrocarbon analyzer was used to continuously monitor total hydrocarbons
during charcoal purging. The weight of hydrocarbons being purged from the
canister was calculated from hydrocarbon concentration. A weight
measurement was still taken before and after charcoal purging to obtain total
weight loss.
B. Practice Cold and Hot Purge Cycles and Working Capacity Measurement
of an In-Use Charcoal Sample
A charcoal sample from a Delco canister which was removed from a 1981
Monte Carlo was subjected to cold and hot purge cycles and to several working
capacity cycles. The canister, which was a replacement of the original canister,
had accumulated about 10,000 miles of operation.
A 50 g charcoal sample from the canister was cold-purged for a total of
150 minutes and hot-purged for 96 minutes (at - 355°F or ~ 180°C) at 42
t /minute. The charcoal container was removed from the sampling system and
weighed every 10 minutes during the cold purge. During the hot purge, the
charcoal container was weighed after the continuous HC level dropped below
1000 ppmC, at 500 ppmC, and at 300 ppmC. The number of times weight was
measured was reduced during the hot purge to minimize oven temperature
fluctuations and vapor loss. Hydrocarbon concentrations were monitored
continuously during the cold and hot purges. HC concentration, time elapsed,
charcoal weight loss, and rate of weight loss are reported in Table 2 for cold
and hot purges. The weight loss fell below 1 g/hr at 460 ppmC during the cold
purge and at 500 ppmC during the hot purge.
14
-------
TABLE 2. CONTINUOUS HC CONCENTRATIONS AND RATE OF CHARCOAL
WEIGHT LOSS OF IN-USE DELCO CHARCOAL DURING
COLD AND HOT PURGE CYCLES
Elapsed Continuous Charcoal
Type of Cycle Time, min HC, pproC Weight Loss, g
Rate of Weight
Loss, g/hr
Cold Purge
10
20
30
00
50
1,100
670
460
4 30
350
1.54
0.68
0.15
0.14
0.11
9.2
4.1
0.9
0.8
0.7
Hot Purge
10
20
30
40
50
60
70
80
90
96
10,000
9,300
4,500
2,200
1,300
840
570
500
330
300
~a
„a
__a
__a
__a
__a
__a
..a
—a
__a
10.4
0.2
0.6
__a
aNo measurement taken
Total hydrocarbons were measured on separate bags collected during the
cold and the hot purge. The results are listed below. The equation used to
calculate grams of hydrocarbons is shown in Appendix C .
Eleven percent of the hydrocarbons measured were produced during the cold
purge, and 89 percent were produced during the hot purge. Actual charcoal
weight loss during the cold purge was 2.62 g, and 10.62 g was lost during the hot
purge, a total greater than the recovered hydrocarbons.
Bag hydrocarbon samples were also analyzed on the HC speciation gas
chromatograph. The cold cycle was represented by a predominance of lower
molecular weight hydrocarbons in the C3 to Cg range. Heavier hydrocarbons in
the Cg to Cj| range were predominately purged from the canister during the
hot purge.
Three alcohols were also measured in the cold and hot purge effluent.
The results are given below for methanol, ethanol and TBA:
Cycle
Total Hydrocarbons
Recoveries, g
Cold Purge
Hot Purge
Total
1.16
9.08
10.24 g
15
-------
Alcohol Recoveries from Used Delco Charcoal, mg
Methanol Ethanol TBA
Cold Purge 1.6 «a —a
Hot Purge ~a 2.3
Total 5.3 »a 2.3
aNot found at measurable levels
The charcoal sampling system was capable of handling the reduced
amount of charcoal without saturating the system. The sensitivities of the
alcohol and hydrocarbon analyses were sufficient to measure the concentrations
produced by the charcoal.
Butane working capacity was also measured on the Delco charcoal
according to the procedure outlined by the EPA Project Officer. However, the
working capacity was measured at the conclusion of the hot purge rather than
after the cold purge cycle. The canister was subjected to five butane loading-
purging cycles. The butane flowrate was set at approximately 1 2,/minute for
the first load cycle, but was lowered to approximately 280 mji/minute to obtain
a longer breakthrough time (between 7 and 12 minutes instead of 3 minutes). A
Ford test procedure for measuring butane working capacity^' ltets a butane
loading rate of about 0.6 £/minute, and an ARCO procedure^' calls for a
butane flowrate of about 3 2,/minute. The flowrate of butane that SwRI used is
approximately one-tenth of the ARCO flowrate. This also corresponds to SwRI
using approximately one-tenth of the total charcoal weight to perform charcoal
testing.
Breakthrough times at 100 ppmC, 1000 ppmC, and 10,000 ppmC are listed
in Table 3 for the butane loading portion of the working capacity procedure.
The first three cycles were performed on one day and the fourth and fifth
cycles were performed on the following day. Breakthrough times varied about
20 to 30 percent at each breakthrough level.
TABLE 3. BREAKTHROUGH TIMES OF CHARCOAL USING BUTANE
Breakthrough Breakthrough Time by Cycle, min
Concentration la 2^ 3^ 4° 5^
lOOppmC 2.4 11.6 7.4 6.4 6.6
1000 ppmC 2.8 12.5 7.6 7.1 8.2
10000 ppmC 3.0 13.7 9.4 8.8 11.3
aButane flowrate 1 llmin
''Butane flowrate 280 m2/min
Average of
Cycles 2-5
S.D.
CV.
8.0
2.4
30%
8.8
2.5
28%
10.8
2.2
20%
This canister was cold-purged after breakthrough at 10,000 ppmC (test
canisters were loaded to a 1000 ppmC breakthrough level) until the rate of
weight loss was 1 g/hr or less. The butane working capacity procedure specifies
that the canister should be purged until the rate of weight loss stabilizes to
within 1 g/hr. The cold purge cycle was interrupted at varying intervals and the
canister was weighed. The rate of weight loss and continuous hydrocarbon
concentrations are reported in Appendix D for each of the cycles.
16
-------
Butane working capacities for four of the five working capacity tests are
given in Table 4. The canister was inadvertently not weighed after loading with
TABLE BUTANE WORKING CAPACITY OF IN-USE DELCO CHARCOAL
Working
Capacity
Cycle
1
2
3
4
5
Breakthrough
Time, min.
2.8
12.5
7.6
7.1
3.2
Butane Added to
Breakthrough,g
6.95
5.26
4.98
6.25
Working
Capacity, g
6.94
5.25
4.98
6.20
Percent
Difference From
Higher W.C.
-2496
-5%
+20%
butane during the first cycle. Breakthrough times and the weights of butane
added (measured by the difference in canister weight before and after loading
with butane) are also reported. Butane working capacity is calculated by
subtracting the canister weight (after purging) from the loaded weight. As
defined by the working capacity procedure provided by the EPA Project
Officer, a stable working capacity is achieved when two consecutive working
capacities agree within 10 percent of the higher of the two values. As shown in
Table 4, working capacity varied considerably. Between cycles 3 and 4, the
working capacity repeated within 5 percent. However, since the tests were
performed on two separate days, working capacity was measured a fifth time to
confirm repeatability. Working capacity increased 20 percent from the fourth
test. The data obtained from this canister indicate that a working capacity
stable to within 10 percent may not be achieved within a reasonable number of
cycles as seen in Table 4. Therefore, total of three working capacity cycles
was performed on each test canister. The average of the three cycles was
calculated.
C. Validation of the Charcoal Sampling System
Several recovery experiments were conducted on new Delco and
Motorcraft canister charcoal. Known quantities of gasoline, alcohols, and water
were individually added to dried charcoal samples. The charcoal was then
purged at room temperature and under heated conditions at about 34Q°F
(170°C), and the effluent was collected and analyzed. The recoveries are shown
in Table 5. The gasoline recoveries were somewhat lower than expected, so
additional tests were conducted with no charcoal present. Three gasoline
samples (a 5 ml sample and two 2.5 m£ samples) were subjected to separate
hot purge cycles (oven temperature ~345°F or ~175°C). The gasoline was
pipetted into a 25 m? volumetric flask, the flask was placed in the oven and
purged until it gave a continuous hydrocarbon reading of less than 500 ppmC.
After purging, a gasoline residue remained in the flask; 9 percent of the original
17
-------
TABLE 5. RECOVERIES OF GASOLINE, METHANOL, ETHANOL, TBA,
AND WATER FROM NEW DELCO AND MOTORCRAFT CHARCOALS
Percent Recovered
Added
Delco
Motorcraft
4 mi unleaded gasoline
73%
66%
0.5 m(L methanol^
34
87
2 m& methanol
87
103
2 mil methanol
92
__b
1 m£ ethanol 92 96
i mi ethanol 95 _b
1 m£ TBA 89 71
1 mi TBA 96 -Jb
4 mJl water 106 1 Ok
aThe methanol recovery from Delco charcoal using
0,5 m£ methanol was measured during a hot purge only
"No measurement
5 m£ sample and 14 and 16 percent from the 2.5 m£ gasoline samples. The
fraction of volatilized gasoline recovered is listed below. The calculation for
determining recovery is shown in Appendix C.
Original Amount
of Gasoline, mA
5.0
2.5
2.5
Gasoline
Evaporated. m£
4.5
2.1
2.1
Gasoline
Recovered, mI
3.5
1.7
1.5
Average
Percent Recovered
(no charcoal used)
77%
81%
74%
7796
The recovery without charcoal was higher than recoveries from Delco (73
percent) or Motorcraft (66 percent) charcoals, however, it was not significantly
improved.
Another recovery test was performed using 4 mii of pentane without
charcoal. The pentane was pipetted into a 25 m£ volumetric flask and hot-
purged until all of the pentane evaporated. The recovery of pentane was 89
percent, about 12 percent higher than the recovery of gasoline. The lower
gasoline recovery from the sampling system might be due to the loss of some of
the heavier compounds in gasoline to the walls of the sampling system. The
lower gasoline recoveries from charcoal may be partially due to the gasoline
residue which has a boiling point above the temperature used, and which cannot
be accounted for.
18
-------
A third recovery test was performed using ^ m£ of 4-methyloctane (C9) in
the hot purge system with no charcoal. The test was conducted in a manner
similar to previous recovery tests. The recovery, excluding unevaporated
residue, was 86 percent, only slightly lower than that for pentane. The
sampling system apparently does not retain significantly greater quantities of
the higher molecular weight C9 compound than pentane, a C5 compound.
Validation tests were typically of shorter duration than sample charcoal
tests because the validation tests were characterized by a more rapid
hydrocarbon purge rate than charcoal sample tests. As stated earlier, however,
even through purge length varied, the length of the test was a function of final
hydrocarbon concentration in the effluent. The difference in test length
resulted in validation tests being conducted at a slightly lower temperature
than sample tests (170-175°C versus 180-190°C). This was due to the fact that
the oven temperature gradually increased over time. The purge temperature
was maintained below 200°C because Teflon tubing softens at approximately
200OC.
D. Water Content of New Unused Charcoal
Charcoal from unused evaporative canisters was purged to determine the
water content. The charcoal from two Delco canisters, two Motorcraft
canisters and one Mopar canister was tested. The fraction of water as a
percentage of initial charcoal weight is shown in Table 6.
TABLE 6. WATER CONTENT OF UNUSED CHARCOAL
Charcoal Sample Percent Watera
Delco 1 8%
Delco 2 8%
Motorcraft 1 5%
Motorcraft 2 6%
Mopar 12.5%
aWeight of water as a percent of initial
charcoal weight
The first Delco (CM) charcoal sample was hot-purged (at about 3^0°F or
170°C) at 23 £/min for 22 minutes. The charcoal lost about 29 g of weight and
produced large amounts of water. The weight loss was 8 percent of the original
charcoal weight.
The second Delco charcoal sample was both cold- and hot-purged. The
cold purge was carried out at room temperature, with a nitrogen flowrate of 23
£/min for 30 minutes. The charcoal was then subjected to a heated purge
3^0°F (170°C) at 23 £/min for about 30 minutes. The weight loss during the
cold purge was about 4 g, and weight loss during the hot purge was 31 g, for a
total of 35 g. This mass was 8 percent of the original charcoal weight.
Cold and hot purges were conducted on charcoal from two unused
Motorcraft (Ford) canisters and on charcoal from an unused Mopar (Chrysler)
19
-------
canister. One of the Motorcraft charcoal samples was cold purged (at room
temperature) for 30 minutes, and then hot-purged on two subsequent 30 minute
cycles (~300°F or 150°C) to determine water weight loss. Nitrogen flowing at
about 18 /min was used to purge the canister. The charcoal weight loss during
each cycle is listed below.
Cold Purge 3.1 g
Hot Purge 1 15.3 g
Hot Purge 2 0.7 g
Total 19.1 g
The total weight loss represented 5 percent of total charcoal weight (377.5 g).
Charcoal from the second Motorcraft canister was hot purged for 60
minutes (~330°F or ~165<>C) and it lost 23.4 g of its original 401.7 g mass, or
about 6 percent water weight. The Mopar (Chrysler) charcoal was hot purged
for 40 minutes, and weight loss was 40.3 g of its original 321.4 g mass, or about
12.5 percent water content.
Mopar charcoal had the highest water content of the three charcoal types.
Delco and Motorcraft charcoals had lower, relatively similar water content
values. The water content of unused charcoal was typically higher than that of
the in-use charcoal samples tested by a few percent. Apparently water is
displaced to some degree with fuel vapors when the canister is used on the
evaporative system of vehicles.
E. Surface Area of Unused Charcoal Samples
For added information, two new, unused charcoal samples were also
analyzed for surface area. A Micromeritics Flowsorb II 2300 was used in the
analyses. The surface area of two samples each of Delco and Motorcraft
charcoals were measured. Surface areas are shown below on a per gram basis
and for the charcoal contained in a standard size canister.
Total Surface Area
Average Surface Area, of a Standard
Charcoal Type m^/g Size Canister, a
Delco 1388 0.61 x 106
Motorcraft 1074 0.44 x 10^
aCharcoal weight of a typical standard canister was measured in a previous
EPA Project,™ Delco =438 g, Motorcraft ^407 g
The Delco charcoal surface area per gram of charcoal was 29 percent greater
than the surface area of Motorcraft charcoal. The total surface area of Delco
charcoal in a typical size canister is 39 percent greater than the surface area of
Motorcraft charcoal in a typical size canister.
20
-------
IV. RESULTS
The emissions measured during cold and hot purging of samples of in-use
evaporative canister charcoal are listed and discussed in this section. Water
content, methanol, ethanol, TBA, total hydrocarbons, and selected detailed
hydrocarbons were measured in the effluent sampled from evaporative
charcoal. Charcoal working capacity was also measured using butane. The
analytical and working capacity data are summarized in Table 7. Individual
working capacities are reported in Appendix E. The water, alcohol, total HC,
and working capacity data are compared by canister fleet and fuel type in Table
8, by canister vehicle class and fuel type in Table 9, and by cold purge and hot
purge in Table 10. In addition, total charcoal weight loss is compared to the
sum of water, methanol, ethanol, TBA, and hydrocarbon emissions in Table 11.
The distribution of selected detailed hydrocarbons is also compared by canister
fleet and fuel type and by cold purge and hot purge (Tables 12 and 13).
Fifty-gram charcoal samples from ten TV A canisters, eight DOE
canisters, and six EPA canisters were each subjected to a cold purge cycle,
three butane working capacity cycles, and a hot purge cycle. Effluent
emissions were measured during the cold purge and the third working capacity
cycle of six of the TV A canisters (2090, 2099, 1991, 2067, and 8961). All 24
canister samples had emissions measured during the hot purge cycle.
Emissions in Tables 8, 9, and 10 were averaged, and standard deviations
and coefficients of variation were calculated for the different groupings of
data. Test results from EPA canisters with unknown fuel histories (A 1480008,
0049, 0073, 0039, and 0060) were grouped under the gasoline heading.
Significant overlap between average values occurred at the 95 percent
confidence level. The 95 percent confidence interval is approximately ± 2
standard deviations about the average. Relative comparisons can be made,
however.
A. Water Content
Charcoal water content did not differ significantly between canisters
exposed to gasoline vapors and canisters exposed to an alcohol blend. As seen
in Table 8, 50 g of TV A charcoal produced an average of 1 g of water and 50 g
samples of DOE charcoal an average of 0.5 to 0.6 g of water from each type of
canister. EPA canisters of unknown fuel history produced an average of 0.5 g
of water. An insufficient number of EPA blend charcoal samples were analyzed
to make a comparison.
Average water content of Chevy Chevette (TVA) blend charcoal samples
(1.3 g) was slightly higher than that from gasoline charcoal samples (1.1 g) as
shown in Table 9. Ford Escort (DOE fleet) gasoline and blend charcoals
produced nearly equivalent levels of water (0.6 and 0.5 g). An insufficient
number of gasoline and blend charcoal samples from the Ford Fairmonts (TVA
fleet) and 83 Fords (EPA fleet) were analyzed to make comparisons. Between
vehicle classes, gasoline Chevy Chevette (TVA fleet) charcoal had the highest
water content (1.1 g), followed by Ford Escort (DOE fleet) charcoal (0.6 g), and
83 Ford with DFM3.31GXFX (EPA fleet) charcoal (0.3 g). Among blend vehicle
21
-------
TABLE 7. SUMMARY OF RESULTS OF (N-USE EVAPORATIVE CANISTER CHARCOAL TESTING
ON 50 g SAMPLES OF CHARCOAL
Vehicle
Fuel
Type
Gasoline
Blend
Ni
to
Canister
Number
TVA
2090
2099
1925
8887
1991
2067
1725
1747
8961
8902
Gasoline
Blend
Unknown
A1480008
A1480019
A1480073
A 1480039
A1480060
Cold Purge Cycle
Alcohols, mg
Total
Total
Water.n
Methanol
Ethanol
TBA
hc,r
0.70
1.19
3
2
<1
<1
11
25
Ml
1.49
1.31
1.19
0.57
I
<1
8
1.21
1.51
1.08
0.74
3
4
c|
<1
68
27
1.48
1.43
2.00
1.02
0.40
4
^ 1
12
3.27
1.00
Working
Capacity Cycle
Average
Working
Capacity.R
Blend
A1480096
2.41
2.39
2.19
1.55
2.18
2.48
2.41
1.66
1.37
1.55
2.07
1.9)
2.01
1.34
1.43
1.77
2.11
1.90
1.24
1.54
1.75
1.82
2.22
1.73
1.59
1.48
0.20
0.74
1.48
1.16
1.72
0.88
0.59
0.48
0.30
0.39
1.17
0.38
0.49
0.20
0.67
0.58
__b
0.29
0.40
0.30
0.81
0.70
Hot Puree Cycle
Total
Water.R Methanol Ethanol TBA HC. g
Alcohols, mg
19
20
5
9
65
34
4
34
20
17
I
3
10
12
23
42
31
31
15
1
1
2
38
32
8
<1
43
95
14.22
11.50
<1
12
9.18
<1
2
3.74
<1
71
11.69
<1
43
16.48
<1
< 1
8 21
<1
9
18.90
<1
1
7.68
<1
1
6.9 4
1
1
6.98
<1
7
6.95
2
1
7.81
2
5
6.13
4
2
6.58
8
3
6.81
9
5
6.13
8
2
„b
<1
< 1
5.55
20
< 1
5.58
38
< 1
6.56
1
2
5.82
16
46
6.26
2
27
6.84
aNot measured
^No Data
-------
TABLE 8. COMPARISON OF CHARCOAL HOT PURGE CYCLE EMISSIONS AND WORKING CAPACITY
BY FLEET AND VEHICLE FUEL TYPE FOR 50 g SAMPLES OF CHARCOAL
Gasoline
Average
Alcohols, mt
Total
Working
Fleet
Water ,r
Methanol Ethanol
TBA
HC.r
Capacity,r
TVA
Avg.
1.00
13
2
38
9.66
2.14
S.D.a
0.65
7
4
42
4.45
0.40
C.V b
65%
56%
200%
110%
46%
19%
DOE
Avg.
0.56
6
1
4
6.97
1.83
S.D.a
0.41
5
I
3
0.69
0.33
C.V.b
73%
89%
80%
75%
10%
18%
EPA
Avg.
0.1(5
11
15
10
5.95
1.71
S.D.a
0.25
16
16
20
0.44
0.3
C.V.b
54%
146%
104%
200%
7%
21%
to
aS.D. = standard deviation
bc.V. = coefficient of variation as a percent
insufficient number of samples to calculate standard deviation
and coefficient of variation
Blend
Average
Alcohols, me
Total
Working
Water ,r
Methanol
Ethanol
TBA
HC(fi
Capacity, R
1.05
29
1
21
11.6
1.94
0.49
21
0
30
5.0
0.47
47%
72%
0%
141%
43%
24%
0.49
32
7
3
6.51
1.80
0.20
8
2
1
0.35
0.29
42%
24%
31%
47%
5%
16%
0.70
32
2
27
6.84
1.73
c
c
-------
TABLE 9. COMPARISON OF CHARCOAL HOT PURGE EMISSIONS AND WORKINC. CAPACITY BY VEHICLE CLASS AND FUEL TYPE
FOR 50 g SAMPLES OF CHARCOAL
Casoline
Blend
fa
Vehicle Description
Canister
Humber Water.R Methanol Ethanol TBA
Alcohols, mg
Ave rage
Tntal Working
HC, g Capacity
81, 82 Chevy
TVA
2090
1.59
19
8
43
14.22
2.41
Clievetie 96 CIU
TVA
2099
1.48
20
<1
95
11.50
2.39
IVA
1925
0.20
5
<1
12
9.18
2.19
Avg.
S.O,
81 ! .1 I ll 1 t I I IU >!>(.
U.igim I '<0 Iff)
C V.
1VA 883 7
Aug
S-D"h
C. V.
84 lord Escort 98 tID DOB 201
DOE 202
DOE 205
DOE 206
Avg.
S.D
c.v.1
I» 1 ord IHM3. 3V1C.XFX
B3 Kord DFH3. 3VLCEF6
EPA
A1480008
0049
0073
0039
Avg.
S-D'h
C.V.
EPA
A1480060
1.09
0.77
712
0 74
O. 74
15
8
563;
3
5
1542
< 1
< L
50
42
842
11.6
2.5
222
3. 74
3. 74
2. 33
0.12
51
1.55
1 .55
0. 30
I
1
1
6.98
2.07
0.39
3
<1
7
6.95
1.9 J
1.17
10
2
1
7.81
2.01
0.38
L2
2
_5
6.13
1.34
0.56
6
1
4
6.97
1.83
0. 41
5
1
3
0.69
0.33
73*
892
962
752
102
182
__il
15
<1
<1
5.55
1.24
0.29
1
20
<1
5.58
1.54
0.40
1
38
<1
6.56
1.75
0.J0
_2
1
2^
5 ¦ 82
1.82
0.33
5
15
<1
5.88
J . S9
0.06
7
18
1
0.47
0.26
182
1372
1202
2002
82
162
0.81
38
16
46
6.26
2.22
Canister
Numbe r
TVA 1991
TVA 2067
TVA 1725
IVA 1747
IVA 896 L
TVA 8902
DOE 101
UOE 102
DOE 104
DOE 106
EPA
A1480096 0.70
Average
Alcohols, (QR
Tot al
Work;ng
icerjs
Methanol
Ethanol
TBA
hct fi
Capac11 y
1.48
65
< I
71
11.69
2.18
1.1b
34
<1
43
16.48
2.48
1.32
4
< I
<1
8.21
2.41
o.aa
34
<1
__9
18.90
1.66
1.31
34
< 1
31
13.8
2.18
0.37
25
0
33
4.8
0.37
282
7 32
0
1052
352
172
0.59
20
< 1
1
7.68
1.37
0.48
J_7
<1
6.94
1.55
0.54
18
< 1
1
7 . 31
1.46
c
c
c
c
c
c
c
c
c
c
c
c
0.49
23
4
2
6.58
1.43
0.20
42
8
3
6.81
1. 77
0.67
31
9
5
6. 13
2.11
0.58
21
8
_2
—J
1.90
0.49
32
7
3
6.51
1.80
0.20
8
2
1
0.35
0.29
422
242
312
472
52
16 i
32
27
6.64
1.73
^S.D. = standard deviation
C.V. - coefficient of variation as a percenr
Insufficient data to calculate standard deviation or coefficient of variation
No Data
-------
TABLE 10. COMPARISON OF COLD PURGE CYCLE AND HOT PURGE CYCLE TYA
CHARCOAL SAMPLE EMISSIONS FOR 50 g SAMPLES OF CHARCOAL3
Vehicle Cold Purge Cycle Hot Purge Cycle
Canister
Fuel
Type
Water,g
Alcohols, me
Total
HC,r
Water.g
Alcohols, mg
Total
HC.r
Methanol
Ethanol
TBA
Methanol
Ethanol
TBA
TVA 2090
Gasoline
0.70
3
1
11
1.11
1.59
19
8
43
14.22
TVA 2099
Gasoline
1.19
2
1
25
1.49
1.48
20
1
95
11.50
TVA 8887
Gasoline
0.57
1
1
_8
1.21
0.74
9
1
_2
3.74
Avg.
0.82
2
1
15
1.27
1.27
16
3
47
9.82
S.D.b
0.33
1
0
9
0.20
0.46
6
5
47
5.44
C.V.c
40%
50%
0
60%
16%
36%
38%
2
100%
55%
TVA 1991
Blend
1.08
3
1
68
1.48
1.48
65
1
71
11.69
TVA 2067
Blend
0.74
4
1
27
1.43
1.16
34
1
43
16.48
TVA 8961
Blend
0.40
4
12
3.27
0.59
20
I
J_
7.68
Avg.
0.74
4
1
36
2.06
1.06
40
1
38
11.95
S.D.b
0.3k
1
0
29
1.05
0.45
23
0
35
4.41
C.V.C
46%
14%
0
81%
51%
42%
58%
0
93%
37%
aThis table includes only charcoal samples that received both cold purge and hot purge analyses.
Table 7 shows individual sample data for these as well as the samples that received only hot
purge analyses.
bji.D. = standard deviation
CC.V. = coefficient of variation as a percent
-------
TABLE 11. COMPARISON OF CHARCOAL WEIGHT LOSS AND TOTAL
RECOVERED WEIGHT DURING COLD AND HOT PURGE
CYCLES FOR 50 g SAMPLES OF CHARCOALa
Cold Purge
Hot Purge
Vehicle
Charcoal
Total
Percent
Charcoal
Total
Percent
Fuel
Canister
Weight
Recovered
Differ-
Weight
Recovered
Differ-
Type
Number
Loss, g
Weight, g
ence*5
Loss, g
Weight, g
ence'3
Gasoline
TVA 2090
1.87
1.82
-3
10.16
15.88
+56
TVA 2099
2.16
2.71
+25
9.82
13.10
+33
TVA 1925
2.13
„c
8.78
9.40
+7
TVA 8887
1.39
1.79
+29
7.97
4.49
-44
Blend
TVA 1991
2.15
2.63
+22
10.78
13.31
+24
TVA 2067
2.29
2.20
-4
10.72
17.72
+65
TVA 1725
2.93
„c
8.88
9.93
+ 12
TVA 1747
3.48
__c
9.24
19.82
+ 114
TVA 8961
3.34
3.69
+ 11
7.63
8.29
+9
TVA 8902
0.75
__c
7.49
7.43
-1
Gasoline
DOE 201
5.3 d
__c
7.14
7.28
+2
DOE 202
6.63
__c
6.81
7.35
+8
DOE 205
5.33
__c
7.81
8.99
+ 15
DOE 206
6.34
„c
6.31
6.53
+4
Blend
DOE 101
6.42
__c
6.72
7.10
+6
DOE 102
6.31
__c
6.85
7.06
+3
DOE 104
7.93
„c
6.67
6.85
+3
DOE 106
5.19
__c
7.19
__e
Unknown
EPA 1480008
4.91
__c
5.69
__f
EPA 1480049
4.88
__c
6.12
5.89
-4
EPA 1480073
4.19
__c
6.53
7.00
+7
EPA 1480039
3.52
-_C
6.37
6.13
-4
EPA 1480060
3.89
„c
6.52
7.17
+ 10
Blend
EPA 1480096
6.04
__c
6.83
7.60
+ 11
aRecovered weight = sum of the weights of water, methanol, ethanol,
TBA, and total HC purged from charcoal samples
bPercent difference calculated relative to charcoal weight loss
cNot measured
^Measured to one decimal place only
eTotal hydrocarbons not measured
* Water content not measured
26
-------
classes with a sufficient number of individual charcoal samples to make
comparisons, Chevy Chevette charcoal had a higher water content than Ford
Escort charcoal, 1.3 g and 0.5 g, respectively. There was no apparent
difference in hot purge to cold purge water ratio between Chevette (CM)
charcoal and Fairmont (Ford) charcoal.
Hot purge cycle water emissions were somewhat higher than cold purge
water emissions for the TV A canisters shown in Table 10 for both gasoline and
blend samples. Water content from gasoline hot purge averaged 1.3 g, while
cold purge water content averaged 0.8 g. Blend hot purge water content was
1.1 g versus 0.7 g from the cold purge.
B. Methanol, Ethanol, and TBA
Varying amounts and proportions of the three alcohols were found in
charcoal effluent samples. As shown in Table 7, methanol was measured in all
samples in quantities ranging from 1 to 65 mg. Less than 1 mg of ethanol was
present in 17 of 30 analyses. In the remaining samples, ethanol was measured
at levels from 1 to 38 mg. Measurable quantities of TBA were found in all but 4
samples, with amounts ranging from 1 to 95 mg. Considerable variation from
the mean value occurred for most groups of samples. In addition, the ranges of
values at the 95 percent confidence level overlapped for most sample groups.
Quantities of methanol, ethanol, and TBA were averaged by fleet and fuel
type. Standard deviations and coefficients of variation were also calculated.
These values are reported in Table 8. A method for determining the extent of
alcohol "contamination" of evaporative charcoal consists of a comparison of the
alcohol content in the charcoal effluent relative to the alcohol content in the
fuel. Enrichment of alcohol in the charcoal effluent indicates charcoal
retention and "contamination." The blend TVA canisters had been tested using
a 5 percent O2 gasoline-alcohol blend. The oxygen content of effluent on the
TVA blend charcoal samples due to methanol, ethanol, and TBA was
approximately OA percent (of total hydrocarbons). The alcohol content of the
blend fuel used on the DOE blend vehicles was 9 percent by weight. The
fraction of alcohol measured on the DOE blend charcoal effluents was only 0.6
percent of total measured hydrocarbons. Enrichment of alcohols on the blend
TVA and DOE charcoals apparently did not occur. Since the fuel history of the
EPA canisters was not known, similar enrichment comparisons could not be
made.
Methanol, ethanol, and TBA were also found in measurable quantities on
gasoline-exposed charcoal samples. This situation was particularly noticeable
with the TVA charcoals, in which roughly equivalent levels of total alcohols
were found on both gasoline and blend charcoals (53 mg and 50 mg,
respectively). TBA made up 72 percent of total alcohols present in TVA
gasoline charcoals, whereas TBA from DOE gasoline charcoals was 36 percent
of total alcohols. The presence of alcohols on the gasoline charcoals can be an
indication of vehicle cross-fueling, or possibly the accumulation of low levels of
alcohol from gasoline over an extended period of time. All DOE canisters had
been subjected to a SHED test using a gasoline-blend fuel. The total alcohol
content of DOE blend charcoals was approximately four times that of DOE
gasoline charcoals (^2 mg versus 11 mg). Average methanol was about five
27
-------
times higher (32 mg versus 6 mg) and average ethanol was about seven times
higher (7 mg versus 1 mg) than from DOE gasoline charcoals. TBA emissions
did not vary appreciably between blend and gasoline charcoals, 3 mg and 4 mg,
respectively.
The EPA canister charcoals produced alcohols in proportions that may be
an indicator of fueling histories. As shown in Table 7, A1480008 charcoal
effluent emitted 15 mg of methanol and unmeasurable amounts of ethanol and
TBA. Samples A1480049 and A1480073 produced 20 mg and 38 mg of ethanol
but negligible levels of methanol and TBA. Sample A1480039 emitted 2 mg or
less of the three alcohols, while sample A1480060 produced measurable amounts
of each alcohol. A1480096 charcoal, which was from a vehicle known to have
been fueled at least briefly with a gasoline/methanol/TBA blend, produced
larger amounts of methanol and TBA, 32 mg and 27 mg respectively, than
ethanol (2 mg).
As seen in Table 9, charcoal samples from the gasoline Chevy Chevettes
(TVA fleet) emitted, on average, higher levels of methanol (15 mg vs. 6 mg) and
TBA (50 mg vs. 4 mg) than charcoal samples from the gasoline Ford Ecorts
(DOE fleet). Average ethanol purge emissions were similar for the Chevettes (3
mg) and the Escorts (1 mg). With the blend samples, the Chevette and Escort
charcoals produced nearly equal amounts of methanol (34 mg and 32 mg) when
purged. Charcoals from blend Chevette canisters emitted unmeasurable levels
of ethanol and an average of 31 mg of TBA when purged. The Escort charcoals
produced an average of 7 mg of ethanol and 3 mg of TBA. Overall, the
Chevette gasoline and blend charcoals produced total alcohols in excess of
Escort gasoline and blend charcoals during purging. A comparison of average
alcohol values for charcoal samples from the 1983 Fords with DFM3.3V1GXFX
engines and DFM3.3V1GEF6 engines would not be informative because of the
widely varying alcohol levels produced.
Alcohols were measured during the cold purge cycle of six of the TVA
charcoals, and from the hot purge cycle of all TVA charcoals. The cold purge
and hot purge alcohol emissions are compared in Table 10. Total alcohols
produced during the hot purge cycle of gasoline charcoals were almost four
times higher than the alcohols emitted during cold purging (66 mg versus 17
mg). The higher hot purge alcohol level relative to the cold purge level was due
mainly to higher methanol (16 mg versus 2 mg) and TBA (47 mg versus 15 mg)
emissions. Hot purge alcohol emissions from blend samples also exceeded cold
purge alcohol emissions by a factor of two (78 mg versus 40 mg). This
difference was primarily due to higher methanol emissions (40 mg compared to
4 mg produced during the cold purge cycle).
Comparing gasoline and blend total alcohol emissions during purges, blend
charcoals emitted higher levels of alcohols during both the cold and hot purge
cycles than the gasoline charcoal samples. Total alcohols from blend charcoals
were almost 20 percent higher than from gasoline charcoals. Methanol levels
averaged 40 mg versus 16 mg from the gasoline samples, but the amount of TBA
averaged 38 mg versus 47 mg from the gasoline samples. The difference was
greater in the cold purge, when blend alcohol emissions were approximately
double those for charcoal used with gasoline (40 mg compared to 17 mg).
Methanol and TBA concentrations contributed to the difference in total
28
-------
alcohols, while ethanol levels did not change. The difference in alcohol
emissions from blend relative to gasoline charcoals during the hot purge cycle
was less than that in the cold purge cycle.
C. Total Hydrocarbons
Average total hydrocarbon emissions were slightly higher from 50 g
samples of TV A blend charcoal than from 50 g samples of TV A gasoline
charcoal (11.9 g versus 9.7 g) as shown in Table 8. This difference was not
significant at a 90% confidence level. DOE total hydrocarbon emissions were
nearly equivalent from gasoline and blend canisters, with an average of 7.0 g
from gasoline charcoal and 6.5 g from blend charcoal. On a fleet-to-fleet basis,
total hydrocarbons from gasoline canisters were highest from TV A charcoal (9.7
g) and lowest from EPA charcoal (6.0 g). TV A blend charcoals emitted higher
levels of total hydrocarbons than DOE blend charcoal samples, 11.9 g versus 6.5
g, respectively. An insufficient number of EPA blend charcoal samples were
analyzed to make comparisons.
A comparison can be made between gasoline and blend charcoals by
vehicle class. Total hydrocarbon emissions from Chevy Chevette (TVA fleet)
blend canisters were, on average, higher than from gasoline canisters, 13.8 g
compared to 11.6 g, but this difference was not significant at a 90% confidence
level (see Table 9). Total hydrocarbon emissions from Ford Escort (DOE fleet)
gasoline and blend charcoal samples were nearly equivalent (7.0 g versus 6.5 g)
as mentioned earlier (Ford Escorts make up the entire DOE fleet). The Chevy
Chevette gasoline charcoal samples were highest in total hydrocarbon emissions
(11.6 g), followed by Ford Escort charcoal (7.0 g), 83 Ford EPA samples (about
6g), and the Ford Fairmont sample (3.71 g). Among the blend canisters, Chevy
Chevettes had highest total hydrocarbon emissions (13.8 g) followed by the Ford
Fairmont (7.1 g), the Ford EPA sample (6.8 g), and the Ford Escorts (6.5 g).
Hot purge cycle total hydrocarbon emissions exceeded cold purge cycle
total hydrocarbon levels for both gasoline and blend TV A canisters. Table 10
shows average total hydrocarbon values of 9.8 g and 1.3 g from the gasoline hot
and cold purge cycles, and 12.0 g and 2.1 g from the blend hot and cold purge
cycles, respectively. The difference between 9.8 g and 1.3 g from the gasoline
hot and cold purge cycles is significant at the 95 percent confidence level.
D. Comparison of Charcoal Weight Loss to the Sum of Water Content,
Alcohols, and Total Hydrocarbons
The weights of charcoal samples were measured before and after each
purge cycle to determine the mass of materials removed during purging. The
recovered weights of water, methanol, ethanol, TBA, and total hydrocarbons
were summed, and these values plus charcoal weight losses are reported in
Table 11. The percent differences between charcoal weight losses and total
recovered weights are also listed. Recovered weights were similar to or
exceeded actual weight loss (differences from -k to +114%) except for the hot
purge of charcoal TV A 8887, in which recovered weight was M percent lower
than charcoal weight loss. The best agreement between recovered weight and
charcoal weight loss occurred with DOE and EPA charcoals; the percent
differences were all 15 percent or less. Among the DOE charcoals, only one
29
-------
sample (DOE 205) did not agree within 8 percent (recovered mass was 15%
higher for DOE 205). This charcoal sample, which was tested after TV A
charcoal 17^7, may have been subject to hydrocarbon carry-over. TVA 17^7
produced the highest level of hydrocarbons of all charcoal samples (see Table
7).
Recovered weight was determined during six cold purge cycles and all hot
purge cycles of TVA charcoals. The agreement between charcoal and measured
recovered weight of TVA charcoals was not as good as with DOE and EPA
charcoals; only 44 percent (7 of 16) of the recovered weights agreed within 15
percent of the charcoal weight losses. For five of the hot purge charcoals,
recovered weight exceeded charcoal weight loss by more than 15 percent.
Actual weight losses and recovered weights for these charcoals were on the
high end of the range of weight losses, with charcoal weight losses exceeding
9 g and recovered weight exceeding 13 g. Three of the cold purge charcoal
samples also had recovered weights which were more than 15 percent higher
than charcoal weight losses.
The relatively large difference between charcoal weight losses and
recovered weights of some of the TVA charcoal samples may be due in part to
the higher fraction of unsaturated hydrocarbons in TVA effluent relative to
DOE and EPA charcoal effluents. A greater fraction of unsaturated compounds
affects the carbon-hydrogen ratio of the effluent, the calculated quantity of
hydrocarbons, and therefore, the recovered weight (which is composed of
hydrocarbons, water, and alcohols). A comparison of detailed hydrocarbon
emissions shows that, on average, a greater fraction of hydrocarbons from hot
purged TVA charcoals was unsaturated ( 60 percent) compared to the
hydrocarbons measured in hot purged DOE and EPA charcoal effluent ( 34-36
percent). Cold purged TVA hydrocarbons were composed of approximately 46
percent unsaturated compounds (this is discussed in more detail in Section F).
The higher fraction of unsaturated compounds in TVA charcoal effluent is also
consistent with the more intense odor produced by TVA charcoal samples
compared to DOE and EPA charcoal samples.
The fraction of unsaturated compounds in the purged effluent affects the
density of the hydrocarbon mixture, and thus, the calculated quantity of
hydrocarbons. The densities of the DOE and EPA charocal effluents may have
more closely approximated the Federal Register fuel density (16.33 g/ft^) which
was used to calculate the hydrocarbon concentrations (it was not practical for
this program to use individual hydrocarbon densities to calculate the
concentration of each of the 99 hydrocarbons). If the densities of DOE and EPA
charcoal effluents were similar to 16.33 g/ft3, the calculated hydrocarbon
values would be a good approximation of the hydrocarbons in the charcoal
effluent. This is a possible explanation for the relatively close agreement
between recovered weights and charcoal weight losses of DOE and EPA
charcoals compared to TVA charcoals. The TVA charcoal effluent, on the other
hand, was typically composed of a higher percentage of unsaturated
hydrocarbons (which would have a lower density than effluent from the DOE or
EPA charcoals). Thus, the calculated hydrocarbon concentrations for TVA
charcoals could be overstated. This could explain the relatively high recovered
weight compared to the charcoal weight loss of some TVA charcoals.
30
-------
Another factor which can influence the measurement of hydrocarbon
concentrations is the varying tendency of the hydrocarbons to remain in the
gaseous state for analysis. The recovery of compounds with boiling points
exceeding that of 4-methyloctane (U2°C) was not determined for this program.
It is possible that some losses could have occurred if higher boiling compounds
were emitted by the charcoal, but not recovered as gases for analysis.
Comparing cold and hot purge charcoal weight loss, the weight of effluent
removed during hot purging generally exceeded the amount purged during the
cold purge cycle. Charcoal weight loss of TV A charcoals from hot purging was
2 to 10 times greater than the weight loss from cold purging. DOE charcoal
weight loss from hot purging was also higher than cold purge weight loss (from 3
to 46 percent) for six of the eight charcoals. Of the two remaining charcoal
samples, one had equivalent cold and hot purge charcoal weight losses (DOE
206) and one had a hot purge weight loss which was 16 percent lower than the
cold purge weight loss (DOE 104). the EPA charcoal samples had hot purge
weight losses which were 13 to 81 percent greater than cold purge weight losses.
Higher charcoal weight losses from hot purging compared to cold purging is also
consistent with the higher total recovered weights which were measured from
hot purge cycles.
E. Working Capacity3
Average TVA working capacity was slightly higher from gasoline canisters
than from blend canisters, 2.1 g and 1.9 g, respectively, as shown in Table 8.
No significant difference between DOE gasoline and blend charcoal working
capacities was observed (average of 1.8 g each). The average working capacity
from the gasoline TVA fleet (2.1 g) was slightly higher than that from the DOE
fleet (1.8 g), which was in turn slightly higher than that from the EPA fleet (1.7
g). The average TVA blend working capacity was 0.1 g higher than the DOE
blend (1.9 g versus 1.8 g).
Working capacity of 50 g charcoal samples from gasoline Chevy Chevette
canisters was slightly higher than from the blend Chevy Chevette (2.3 g
compared to 2.2 g), while the Ford Escorts had equivalent working capacities
(1.8 g) for gasoline and blend canisters, as seen in Table 9. Among gasoline
canisters, Chevy Chevette charcoal samples had a higher average working
capacity (2.3 g) than Ford Escorts (1.8 g), which was higher than that of the 83
Fords with DFM3.3V1GXFX engines (1.6 g). With the blend fuel, Chevy
Chevette charcoals also had a higher average working capacity compared to the
Ford Escort charcoals, 2.2 g versus 1.8 g.
F. Detailed Selected Hydrocarbons
A detailed hydrocarbon analysis was performed on charcoal effluent from
several cold and all hot purges. A sample chromatogram is shown in Figure 4.
The calculated weight of each compound for each sample is listed in Appendices
aWorking capacities were measured and are reported as grams of HC per 50
gram charcoal sample. This measure may be slightly misleading since the "50
gram" samples were weighed prior to the first cold purge. Therefore, the 50
grams included the mass of whatever adsorbed compounds were present which
varied from approximately five to fifteen grams, depending on the sample.
31
-------
F
35 30
Retention Time, rain.
Figure U. Selected detailed hydrocarbon chromatogram for Canister Number
EPA A1480049 hot purge cycle, diluted ~1 to 10
-------
F-l through F-
-------
TABLE 12. COMPOUND NUMBERS FOR SELECTED DETAILED HYDROCARBONS
1.
Methyl Acetylene
51.
2.
Isobutane
52.
3.
Isobutene
53.
ft.
n-Butane
5ft.
5.
trans-2-butene
55.
6.
cis-2-butene
56.
7.
Isopentane
57.
8.
1-pentene
58.
9.
Pentane
59.
10.
2-M ethyl-1 -butene
60.
11.
Isoprene(2-Methyl-1,3-butadiene)
61.
12.
trans-2-pentene
62.
13.
cis-2-pentene
63.
1ft.
2-Methyl-2-butene
6ft.
15.
2,2-Dimethylbutane
65.
16.
Cyclopentene
66.
17.
Cyclopentane
67.
18.
3-Methyl-l-pentene
68.
19.
ft-Methyl-l-pentene
69.
20.
2,3-Dimethylbutane
70.
21.
2,3-Dimethyl-l-butene
71.
22.
2-Methylpentane
72.
23.
ft-Methyl-2-pentene
73.
2ft.
3-Methylpentane
7ft.
25.
2-Methyl-l-pentene
75
26.
1-Hexene
76.
27.
Hexane
77.
28.
2-Ethyl-l-butene
78.
29.
cis-3-Hexene
79.
30.
2-Methyl-2-pentene
80.
31.
cis-3-methyi-2-pentene
81.
32.
cis-2-hexene
82.
33.
1-Hexyne
83.
3ft.
trans-3-methyl-2-pentene
8ft.
35.
2,ft-Dimethylpentane
85.
36.
Methylcyclopentane
86.
37.
Benzene
87.
38.
Cyclohexane
88.
39.
Methylcyclopentene
89.
ftO.
3-Methyl-l ,3-pentadiene
90.
ftl.
2,3-Dimethylpentane
91.
ft2.
2-Methylhexane
92.
ft3.
Cyclohexene
93.
ftft.
5-methyl-2-hexene
9ft.
ft5.
3-Methylhexane
95.
ft6.
2,2,ft-Trimethylpentane
96.
ft7.
n-Heptane
97.
ft 8.
2,ft,ft-Trimethyl-l-pentene
98.
ft 9.
2,2,ft-Trimethyl-l-pentene
99.
50.
Methylcyclohexane
2,ft,ft-Trimethyl-2-pentene
2,ft-Dimethylhexane
2,5-Dimethylhexane
2,3,ft-T rimethylpentane
2,3,3-T rimethylpentane
Toluene
2-Methyl-3-heptene
3,5,5-Trimethyl-l-hexene
2-Methylheptane
ft-Methylheptane
3-Methylheptane
2,5-Dimethyl-l,5-hexadiene
2,2,5-Trimethylhexane
2-Ethyl-l-hexene
1 -cis-ft-Dimethylcyclohexane
Octane
2,3,5-Trimethylhexane
2,ft-Dimethylheptane
2,5-Dimethylheptane
3,5-Dimethylheptane
Ethylbenzene
2,3-Dimethylheptane
p-Xylene
m-Xylene
2-Methyloctane
ft-Methyloctane
3-Methyloctane
o-Xylene
Nonane
trans-2-nonene
Propylbenzene
2,3-Dimethyloctane
0-Ethyltoluene
l,2,ft-Trimethylbenzene
Isobutylbenzene
Decane
p-Cymene
Indan(e)
ft-Phenyl-l-butene
m-Diethylbenzene
1-Methyl-3-propylbenzene
n-Butylbenzene
p-Diethylbenzene
o-Diethylbenzene
2-Methyldecane
Bicyclopentyl
Undecane
l,2f3,ft-Tetramethylbenzene
Pentylbenzene
34
-------
TABLE 13. PERCENTAGE OF EACH HYDROCARBON GROUP TO TOTAL DETAILED HYDROCARBONS®
Cold Purge Cycle
Gasoline Blend
Canister
Canister
Number
<40
41-55
56-72
73-84
85-99
Number
<40
41-55
56-72
73-84
85-99
TVA 2090
__b
TVA 1991
<1
16
33
43
9
TVA 2099
8
31
23
29
10
TVA 2067
3
23
14
39
9
TVA 8887
M
20
10
26
U_
TVA 8961
14
35
12
23
_8
Avg.
21
26
16
28
10
Avg.
6
25
22
42
9
S.D.C
e
e
e
e
e
S.D.c
7
10
10
18
1
C.V.(%)d
e
e
e
e
e
C.V.(%)d
123
38
45
43
6
Hot Purge
Cycle
Gasoline
Blend
Canister
Canister
Number
<40
41-55
56-72
73-84
85-99
Number
<40
41-55
56-72
73-84
85-99
TVA 2090
<1
<1
3
59
38
TVA 1991
< 1
<1
2
63
35
TVA 2099
2
2
12
60
25
TVA 2067
< 1
<1
3
63
34
TVA 8887
<1
15
23
52
9
TVA 8961
<1
13
27
53
8
TVA 1925
<1
<1
4
55
41
TVA 1725
< 1
4
14
54
26
TVA 1747
< 1
<1
6
65
29
TVA 8902
<1
16
24
56
_4
Avg.
0.5
4
11
57
28
Avg.
< 1
6
13
59
23
S.D.C
1.0
7
9
4
15
S.D.C
< 1
7
11
5
13
C.V.(%)d
200
175
93
7
52
C.V.(%)d
< 1
117
85
8
57
aThe percentages in Appendices F-5 to F-9 were summed by hydrocarbon group and in total. The group sum was then
divided by the total to obtain the data for this table.
b|Vlo data
CS.D. = standard deviation
dC.V. = coefficient of variation
insufficient data to calculate standard deviation and coefficient of variation.
-------
TABLE 13 (CONT'D). PERCENTAGE OF EACH HYDROCARBON GROUP TO TOTAL
DETAILED HYDROCARBONS*
Hot Purge Cycle
Canister
Gasoline
Blend
Canister
Number
4 0
41-55
56-72
73-84
85-99
Number
< 40
41-55
56-72
73-84
85-99
DOE 201
<1
25
44
31
<1
DOE 101
<1
24
36
39
1
DOE 202
<1
30
43
26
1
DOE 102
<1
26
41
27
6
DOE 205
1
14
23
47
14
DOE 104
<1
15
26
47
12
DOE 206
8
39
29
19
_4
DOE 106
__b
~
____
Avg.
2
27
35
31
5
Avg.
<1
22
34
38
6
S.D.c
4
10
10
12
6
S.D.c
<1
6
8
10
6
C.V.(%)d
200
37
29
39
120
C.V.(%)d
<1
27
24
26
100
EPA A1480008
4
57
22
16
<1
EPA A1480049
1
27
32
37
4
EPA A1480073
2
37
34
26
1
EPA A1480039
< 1
31
23
38
8
EPA A1480060
4
36
20
33
_j7
Avg.
2
38
26
30
4
S.D.c
2
12
6
9
4
C.V.(%)<1
100
32
23
30
100
EPA A1480096 <1 35 23 31 11
aThe percentages in Appendices were summed by hydrocarbon group and in total. The group sum was then
divided by the total to obtain the data for this table.
bNo Data
CS.D. = standard deviation
^C.V. = coefficient of variation
-------
DOli-blend
oOli-y.i 11 ne
EPA-blend
EPA-ydiaol ine
M-->5
7 3-84
41-55
85-99
Compound Number
56-72 73-84
Compound Number
85-99
Figure 5
Comparison of the distribution of detJ>M hy.li.,; ,irb.»n salons from hot
purge cycLes averaged by fl«et «iuii by Im-i typi;
-------
o 60%
TVA2090
Hot
01
Q
Cold
Hot
to
TVA2099
Cold
Hot
TVA206 7
Co Ld
Hot
Cold
00
Hot
56-7 >
85-99
Cold
Hot
56-72
85-99
Compound Number Compound Number
Figure 6. Comparison of the distribution of detailed hydrocarbon emissions sampled
from TVA charcoal samples during cold and hot purge cycles
-------
2067, and 8961. The peaks occurred in the C7 to Cg and the C9 category. It is
difficult to discern any meaningful difference between the hydrocarbon distri-
butions of the gasoline charcoals (2090, 2099, and 8887) and the blend charcoals
(1991, 2067, and 8961).
A comparison of detailed hydrocarbon emissions was also made for the
sum of cold and hot purge tests for TVA canisters. These results are reported
in Table 10. The percentage of each hydrocarbon group to total hydrocarbons
TABLE 10. PERCENTAGE OF EACH HYDROCARBON GROUP TO TOTAL
DETAILED HYDROCARBONS FROM COLD AND HOT PURGE
CYCLES OF TVA CHARCOALS*
Canister
Fuel Type
Number
40
41-55
56-72
73-80
85-99
Gasoline
2090
_b
—
—
—
—
2099
0
15
13
57
15
8887
15
12
18
05
9
Avg.
8
10
16
51
12
S.D.C
e
--
—
—
—
C.V.(%)d
__e
--
—
—
--
Blend
1991
0
0
5
63
32
2067
0
3
7
57
33
8961
6
21
26
00
7
Avg.
2
8
13
55
25
S.D.C
0
11
11
13
15
C.V.(%)d
173
102
87
23
61
aThe percentages in Appendices F-5 and F-6 were summed for cold and hot
purge by hydrocarbon group and in total. The group sum was then divided by
the total to obtain data for this table.
^No data
CS.D. = Standard deviation
^C.V. = Coefficient of variation
insufficient data to calculate standard deviation and coefficient of
variation
was summed for cold and hot purges. The group sum was then divided by the
total (of both cold and hot purges) to obtain data for this table. The resulting
group values for each canister typically fell between the individual cold and hot
purge values.
The hydrocarbon speciation data were subdivided into percent paraffins,
olefins, and aromatics for each charcoal sample. The data are given in
Appendix G and are summarized in Table 15. Peak areas which included a
mixture of paraffins, olefins, and/or aromatics, were omitted from the
calculations. Actual distribution of the compounds could differ as a result of
these unresolved peaks.
39
-------
TABLE 15. SUMMARY OF PERCENTAGES OF PARAFFINS, OLEFINS
AND AROMATICS IN PURGED CHARCOAL EFFLUENT FROM 50 g
SAMPLES FROM IN-USE EVAPORATIVE CANISTERS3
Canister Purge
Fleet Cycle
Paraffins
53
36
66
61
Olefins
7
Aromatics
39
63
34
35
TV A Cold
TV A Hot
DOE Hot
EPA Hot
0
The hot purged effluent of TVA charcoals was on average, composed of a
predominance of aromatics (63 percent) over paraffins (36 percent), while hot
purged DOE and EPA charcoals produced more paraffins (66 and 64 percent,
respectively) than aromatics (34 and 35 percent). The relatively large
difference in proportions of paraffins and aromatics between canister fleets
could be related to differences in the compositions of fuels used for each fleet.
The cold purge cycle of TVA charcoals produced, on average, higher fractions
of paraffins and olefins than hot purged TVA charcoal samples, but a lower
percentage of aromatics.
G. Summary of Results
The emissions data measured in this program have been analyzed to
determine relationships to several variables. The data have been compared by
fleet, fuel type, vehicle class, and type of purge cycle (cold or hot). Comparing
the data by groups was in most cases not statistically valid because overlap
occurred for most data groupings at the 95 percent confidence level. Relative
comparisons were made, however.
. The TVA fleet of canisters (gasoline and blend) produced higher levels of
water and total hydrocarbons and had higher working capacities than
canisters from the DOE or EPA fleets. The TVA canisters (gasoline and
blend) produced higher levels of total alcohols than the DOE canisters.
These higher values were apparently due to the Chevy Chevette canisters.
EPA gasoline canisters had average water content, total hydrocarbon
levels, and working capacities that were similar to but slightly lower than
those from the DOE canisters. It is difficult to interpret the differences
observed between fleets (TVA, DOE, EPA) due to vehicle operation
characteristics which likely varied between fleets. The length of time a
vehicle sits between trips, the speed at which a vehicle is operated, the
vapor pressure of the fuel, and ambient temperature are a few of the
variables that will affect the type of vapors to which an evaporative
canister is exposed.
• Only small differences in water content, total hydrocarbon levels, and
working capacities were discerned between gasoline and blend canisters.
40
-------
• Alcohols were produced by both gasoline and blend fueled vehicle
canisters. Roughly equivalent levels of total alcohols were produced by
TV A gasoline and blend charcoals, however, DOE blend charcoals
produced approximately four times the quantity of alcohols emitted by
DOE gasoline charcoals. Total alcohol content did not appear to correlate
with water content, total hydrocarbons, or working capacity.
• Hot purge water, total hydrocarbon, and total alcohol emissions were
generally higher than cold purge emissions for TV A gasoline and blend
charcoal samples.
• TV A canisters produced a higher proportion of heavier hot purge detailed
hydrocarbons than DOE or EPA canisters. DOE hot purge hydrocarbons
were evenly distributed between light and heavy ends. The hydrocarbon
distribution from hot purged EPA charcoal was identified by an "M"
shaped distribution curve which was proportionally higher in C7 and Cg
compounds and in C9 compounds.
• TV A canisters contained more unsaturated hydrocarbons than DOE and
EPA canisters.
• There was no observable difference in the hydrocarbon distribution from
gasoline and blend canisters.
• Cold purge detailed hydrocarbons were predominantly in the C3 to Cg
range and hot purge hydrocarbons in the C9 to Cjj range.
• Total recovered weight (sum of weights of water, alcohols, and total
hydrocarbons) typically exceeded charcoal weight loss (determined by
weighing before and after purging). Total recovered and charcoal weight
loss agreed within 15% for all DOE and EPA canisters, but for less than
half of the TV A canisters. The disparity between TV A weight losses could
be due to a greater proportion of unsaturated compounds in the TVA
charcoal effluent.
• Hot purge charcoal weight loss typically exceeded cold purge charcoal
weight loss for each fleet.
41
-------
V. QUALITY ASSURANCE
The Quality Assurance (QA) guidelines addressed in the QA Project Plan
were followed in performing the work for this program. Calibrations were
performed on the analytical instruments and daily sampling system leak checks
were conducted. The data is available for inspection if desired. Precision,
accuracy,and completeness figures determined for this program are summarized
in Table 16.
TABLE 16. PRECISION, ACCURACY, AND COMPLETENESS
Analytical
Measurement Procedure
Methanol Gas Chromatograph
(FID)
Ethanol Gas Chromatograph
(FID)
TBA Gas Chromatograph
(FID)
Water Gravimetric
Content
THC Gas Chromatograph
(FID)
Selected Gas Chromatograph
HC Speciation (FID)
a Standard deviation except where indicated
b Coefficient of variation
c Based on recovery experiments conducted on the sampling system
d Recovery is the same as that for the THC, however the recoveries of
individual HC species will vary. It was not within the scope of this program
to determine the recovery of each component in the gasoline spike.
Precision
Std. Dev.a Accuracy, % Completeness, %
2b 91c >95
4b 94c >95
2b 85c >95
0.00 105c >95
0.04 70c >95
10b 70d >93
43
-------
REFERENCES
1. Code of Federal Regulations, Title 40, Chapter 1, Part 85, Subpart H,
Sections application to Light-Duty Vehicles.
2. Unpublished data from EPA-RTP report.
3. Procedures provided to EPA by Ford and ARCO.
4. Warner-Selph, Mary Ann, "The Effect of Methanol on Evaporative
Canister Charcoal Capacity," Final Report to the Environmental
Protection Agency prepared under Contract No. 68-03-3162, Work
Assignment 12, Report No. EPA 460/3-84-014, January 1985.
45
-------
APPENDIX A
BUTANE WORKING CAPACITY PROCEDURE
-------
APPENDIX A
BUTANE WORKING CAPACITY PROCEDURE
Following the "room temperature" purge to a stable weight, conduct a butane
working capacity test on the canister as follows:
1. Record the initial canister weight.
2. Load the canister with butane until breakthrough occurs (1000
ppmC), and record the time to breakthrough.
3. Record the loaded canister weight.
Purge the canister with room temperature aira at the same flow
rate as the previous purge until the weight stabilizes to within one
gram over an hour, and record the elapsed time and final weight.
The loaded weight minus the final weight is the working capacity.
5. Repeat steps I to 4.
6. If the difference between the two working capacities as measured
above is greater than 10% of the higher value, repeat steps 1 to 4
again.
On the cansiters that underwent speciation of their initial room temperature
purge, speciation shall also be done on the vapors from the butane working
capacity purge to see what other compounds, if any, are desorbed along with
the butane. Then the high temperature purge and speciation would be
conducted as planned on all the canisters being tested.
aDry nitrogen was used instead of room air to minimize the possibility of
adding water to the charcoal. Per what was found in the mini-canister work,
the use of dry nitrogen probably yielded greater working capacities than would
have been found with room air.W
A-2
-------
APPENDIX B
THE MEASUREMENT OF METHANOL,ETHANOL, AND TERTIARY
BUTYL ALCOHOL IN EXHAUST
The measurement of methanol, ethanol, and tertiary butyl alcohol (TBA)
in exhaust is accomplished by bubbling the exhaust through glass impingers
containing deionized water. The exhaust sample is collected continuously
during the test cycle. For analysis, a portion of the aqueous solution is
injected into a gas chromatograph equipped with a flame ionization detector
(FID). External methanol, ethanol, and TBA standards in deionized water are
used to quantify the results. Detection limits for this procedure are on
the order of 0.06 ppm in dilute exhaust for both methanol and ethanol.
SAMPLING SYSTEM
Two glass impingers in series, with each containing 25 mil of deionized
water are used to collect exhaust sanqples for the analysis of methanol,
ethanol, and TBA. A flow schematic of the sample collection system is
shown in Fiaure 1. The two glass impinqers collect 99+ percent each of methanol
and ethanol, and ggpercent of TBA in exhaust. The temperature of the impingers
are maintained at 0-5°C by an ice water bath, and the flow rate through the
impinger is maintained at 4 i/mmute by a sample pump. A dry gas meter is
used to determine the total flow through the impinger during a given sampling
period. The temperature of the gas stream is monitored by a thermocouple
immediately prior to the dry gas meter. A drier is included in the system
to prevent condensation in the pump, flowmeter, dry gas meter, etc. The
flowmeter in the system allows continuous monitoring of the sample flow
to insure proper flow rates during the sampling. The Teflon line connecting
the CVS and the solenoid valve is heated to M.75°F in order to prevent
water from condensing in the sample line. Several views of the sampling
system are shown in Figure 2.
ANALYTICAL PROCEDURE
The analysis of methanol, ethanol, and TBA is accomplished by collecting
the alcohols in deionized water and analyzing the sample with a gas chroma-
tograph equipped with an FID. The analysis flow schematic for methanol,
ethanol, and TBA is shown in Figure 3. A detailed description of the
procedure follows.
For the analysis of the three alcohols, dilute exhaust is bubbled
through two glass impingers each containing 25 mJl of deionized water. Upon
completion of each driving cycle, the impinger is removed and the contents
are transferred to a 30 m£ polyethylene bottle, and capped.
A Perkin-Elmer 3920B gas chromatograph equipped with a flame
ionization detector is used to analyze the sample. A 5 yJi portion of
the sample is injected into the gas chromatograph (GC). The analytical
B-2
-------
Gas Temperature
Digital Readout
Heated Line
On-Off Solenoid
^ Valve
Sample
Pump
Drying
Tube
Sample
Probe
Impingers
Regulating
Valve
Ice Bath
Cas Volume
Dilut e
Iilal3|g|sl
Dry
Gas
Meter
Dilut e
Exhaust
Ice Bath
Temperature Readout
Cas Volume
Digital Readout
Figure 1. Methanol, ethanol, and TBA sample collection flow schematic
-------
Front View
Regulating
Valve
Close-up of Upper Front
Figure 2. Methanol, ethanol, and TBA sampling system
B-4
-------
Close-up of Impingers (Side View)
I
Solenoid
Ice Bath
Drier
Dry Gas Meter
Pump
View
Methanol, ethanol, and TBA sampling system
B-5
-------
Unused Sample
saved as needed
Sample analysis
in gas chromatograph
with FID
A/D Converter
Hewlett-Packard
3353
Computer System
Figure 3. Methanol, ethanol, and TBA analysis flow schematic
B-6
-------
column is a 3' x 1/8" Teflon column containing 120/150 mesh Porapak Q.
The carrier gas which is helium, flows through the column at a rate of
20 m£/minute. The column temperature is maintained at approximately 105°C
for methanol, 140°C for ethanol, and 150°C for TBA analyses. A 79.1 ppm
methanol standard is shown in Figure 4, a 78.9 ppm ethanol standard is shown
in Figure 5, and a 78.9 ppm TBA standard is shown in Figure 6.
To quantify the results, the sample peak areas are compared to the
peak areas of standard solutions. Figure 7 shows tne analytical system
with gas chromatograph, detector, A/D converter, and recorder.
CALCULATIONS
The procedure has been developed to provide the user with the con-
centrationof methanol, ethanol, and TBA in exhaust. The results will be
expressed in yg/m'3 of exhaust and ppm. The equations for determining the
concentrations in pg/m3 and ppm are derived in the following manner.
The first step is to correct the volume of exhaust sampled to a
standard temperature, 68UF, and pressure, 29.92"Hg, by use of the
equation
P xv p xv
exp exp = corr corr
T T
exp corr
vexp = experimental volume of gas sampled in ft3
vcorr = volume of gas sampled m ft3 corrected to 68°F and
29.92"Hg
pexp = experimental barometric pressure
pcorr = 29.92"Hg
Texp = experimental temperature in °F + 460
Tcorr = 68°F + 460 = 528°R
Solving for vcorr gives:
V pexp^"H9' x Vexp ^ x ^28 R
vcorr =
T ( R) x 29.92"Hg
exp
The next step converts the volume from cubic feet to cubic meters
by use of the conversion factor: 1 cubic meter is equal to 35.31
cubic feet.
„ p ("Hg) x V (ft3) x 528°R
corr (m3) = -522 .
T x 29.92"Hg * 35.31
exp
(Equation 1)
B- 7
-------
•
1
i
* -
,
t
i
-
I
.
i
i
i
i
'
1
t
1
1
i
i
i
r--
i
i
;
.
1
i
;
79° 1 W
i
,
.
i
,
•
m-
. —
>
—
ro
P i
r i
I
—
<\j-
——..
— —
i
— _
j—
— —
— —
/—
—
—1—
w/ -
—
—" —
La-
z
—_ _
o ~
—
i
¦
1— -
l
l -
o l
6 5 4 3 2 1 0
Retention time, min.
Figure 4. Chromatogram of methanol standard
B-8
-------
1
'
1
1
J
.
1
¦
1 '
;
1
" - - "1
1' ' ' ¦
i
1
1
'
'
'
,
J-ppm—-
to •
— —eth
anol- —
—
.
-
r
.
—
— _
—
_ ,
"
i
I
—
— — —
i
i
f
—
1...
—
/
/
— —- —
z — .
y
1
-
- 7
U
—
~'1~~t
o 1
5 4 3 2 1 0
Retention time, rain.
Figure 5. Chromotogram of ethanol standard
B-9
-------
XP
78". y ppp'
TBA i
c£>
V-
x>
4
6
5
3
2
0
1
Retention Time, min.
Figure 6. Chromatogram of TBA standard
B-10
-------
AtMftM
Mr***"
Cokiwm
Cmmmh
CMotmm
Cobolt
Curium
Dyiptauwm
Erbium
lw«tiu«
Hum
fro*
God
Goll
G •»•».
Gold
M 56 13734
u t; (MJJ
It 4 Mill
r (i w «*o
I S 10.111
Ir 35 ntt*
C* 41 11140
Co 70 400t
a ft (25ij
C * II01115
Co SI 14011
Ci iS 131*05
a 17 35 453
Cr 14 51996
Co 17 519331
Co 1* 63 54
C» 96 [147]
0y 66 16150
' ~« BS4]
1*716
*» 151.96
Iron
Krypton
Kr
lood
34
57
Iw 103
fb M
li 3
lu 71
Mg II
Monaonoto Mn IS
Moodolovium Md 101
Morcury Hg (0
Molybdenum Mo 41
h
Et
lu
Noon
Noplunivm
Nickol
Niobium
Nilrogon
Nobolium
Osmium
O > vain
Recorder
'» 196.967
No 10
Np 93
Ni II
Nb 41
N 7
No 102
Ot 76
n •
46
IS
71
94
.-—•"urn k 'J
13.(0
I3«.9I
(2S7J
207.19
6939
174.97
24.312
54.9310
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200 59
95.94
144.24
20.113
037J
51.71
92 906
, 14.0067
[154 J
1902
15.9994
1064
riSSM
BSj
'«!$
iomaf.
Scondiw
Seleniun
Silicon
Silver
Sodium
Sfronliun
S ulfur
Tantalum
Technetio
Tellurium
Terbium
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten Wolf
Uranium
Vanadium
Xenon
Ytterbium
Yttrium
Zinc
Zirconium
-------
The next step is to find the concentration of methanol, ethanol, or
TBA in \ig/ml. Since the gas chromatograph FID has a linear response in
the concentration of concern, then the following equation holds.
Csam (Vg/n*> C3td (yg/mI)
A A
sam std
Csam = concentration of the sample in \iq/ml
Asam = ^ PeaJc area of sample in relative units
cstd = concentration of the standard in pg/m£
Agt(j = GC peiak area of standard in relative units
Solving for C gives:
sam
C (Mg/ml) x A
C . y 0 \ std SdiQ
sam (pg/mJt) =
std
This Csatt (yg/m£) in solution is corrected for any necessary
dilution by multiplying by the dilution factor, D.F.
, . 0. C _ (Ug/mA) x A x D.F.
C (Mg/mJt) std sam
sam = .
std
To obtain the total amount in yg of methanol, ethanol, or TBA in the
aqueous absorbing solution, the absorbing reagent volume is multiplied by
the concentration to give:
yg sample = Cgam (yg/mJl) x Abs. Vol. (ml)
_ C (yg/mJL) x a x d.f. x Abs. Vol. (ml)
5lq sam
Astd
(Equation 2)
To obtain yg sample/m3, Equation 2 is divided by Equation 1 to give:
c(yg/mI) x A x d.F. x Abs. Vol. (ml)
/ ^ stu sam
w
X Texp X 29-92"H
-------
To find the concentration of methanol, ethanol, or TBA in ppm, the
density of each alcohol is needed. At 29.92"Hg and 32°F, one mole of
gas occupies 22.4 liters. This volume is corrected to 68°F from the
equation
Ti = 32°F + 460 = 492°R
V = VL
T T]_
VL = 22.4JI
P1
V = volume at 68 F
T = 68°F + 460 = 528°R
Solving for V gives:
V
1 x t = 22.4 x 528
V = x m = 24.042,
Tj_ 492
Since one mole of gas occupies 24.04)1 at 68°F, the density can be found
in g/Ji by dividing the molecular weight in g/mole by 24.04 H/mole
. , mol. wt. g/mole
den
-------
At this point, the concentration can be expressed in Ug/m3 (Equation 3)
and ppm (Equation 5) at 68°F and 29.92"Hg from the raw data.
Hewlett-Packard Calculations
In order to insure maximum turnaround in a minimum time period, a
Hewlett-Packard 67 program was developed to calculate the methanol, ethanol,
and TBA concentrations in Ug/m3 and ppm from the raw data. This program
is presented in Figure 8.
Sample Calculation
Assume exhaust samples were collected in glass impingers for cold
and hot UDDS segments of a four*-bag FTP. Raw data for these tests are
presented in Figure 9. Calculations were performed using the HP-67
program and manual calculations.
Manual calculations for the cold start UDDS segment of the FTP
For Bubbler #1 - Methanol
C , (Ug/mJl) * A * D.F. x Abs. Vol. (mi)
, 3 „ std sam
pg/m CH3OH = a «P ("Hg]
std exp
T x 29.92"Hg * 35.31 ft3/m3
v exp _
528°R x V(ft3)
exp
= (79.1 uq/ml) x 10,000 * 1 * 25
20,000 x 29.80"Hg
(460 + 75) x 29.92"Hg x 35.31 ft3/m3
X 528°R x 3.196 ftJ
= 1.11x 104 ng/m3
The concentration of methanol in Bubbler #2 is calculated in
the same manner using the appropriate dilution factor, standard
concentration, standard area, and sample area:
For Bubbler #2:
. 3 7.91 uq/mJt * 10,000 * 1 x 25
U9/m = 25,000 x' 29.80
x H60 + 75) x 29.92"Hq x 35.31 ft3/m3
528UR x 3.196 ftJ
= 8.89 x io2 yg/m3
B-14
-------
Figure 8. HP-67
User Instructions
STEP
INSTRUCTIONS
INPUT
DATA/UNITS
KEYS
OUTPUT
DATA/UNITS
Oi
Switch to on; switch to run
" 1
0?
Feed side 1 of card in from right to left
1
£
0-1
Set decimal place
g
Sci
1
Input Sample Volume
ft3
1 A II 1
2
Input Barometric Pressure
"Hg
R/S
3
Input Sample Temperature
°F
1 R/S11
4
Input Absorbing Reaqent Volume
mi.
tr/sI r
5
Input Dilution Factor, Bubbler #1
1 R/si r
6
Input Methanol Standard Cone. Bubbler #1
yg/mJI
R/S
7
Input Methanol Standard Area, Bubbler #1
counts
1
R/S 1
1
8
Input Methanol Sample Area, Bubbler #1
counts
1
R/S 1
1
9
Output Methanol Sample Cone., Bubbler #1
1
1
1
yg/m
10
Input Dilution Factor, Bubble*: #2
R/S
11
Input Methanol Standard Cone., Bubbler #2
yg/mJ.
R/S 1
1
12
Input Methanol Standard Area, Bubbler #2
counts
R/S
13
Input Methanol Sample Area, Bubbler #2
counts
R/S
14
Output Methanol Sample Cone., Bubbler #2
R/S
yg/m
J
15
Output Methanol Sample Cone., Bubbler #1 & #2
R/S
1
yg/m
16
Output Methanol Sample Cone.
ppm
17
Input Ethanol Standard Cone., Bubbler #1
yg/mJl
R/S
18
Input Ethanol Standard Area, Bubbler #1
counts
R/S 1
1
19
Input Ethanol Sample Area, Bubbler #1
counts
R/S
20
Output Ethanol Sample Cone., Bubbler #1
yg/m3
21
Input Ethanol Standard Cone., Bubbler #2
yg/m£
R/S
22
Input Ethanol Standard Area, Bubbler #2
counts
R/S
23
Input Ethanol Sample Area, Bubbler #2
counts
I R/sJ
1
24
Output Ethanol Sample Cone., Bubbler #2
R/S
yg/m3
^
25
Output Ethanol Sample Cone., Bubbler #1 S #2
R/S
yg/m
26
Output Ethanol Sample Cone.
1
1
ppm
27
Input TBA Standard Cone., Bubbler #1
yg/m£
1 R/sl 1 1
28
Input TBA Standard Area, Bubbler #1
counts
1 R/s
29
Input TBA Sample Area, Bubbler 41
counts
R/S
30
Output TBA Sample Cone., Bubbler ffl
yg/m3
31
Input TBA Standard Cone., Bubbler if2
yg/m£
1 R/S
32
Input TBA Standard Area, Bubbler #3
counts
R/S
33
Input TBA Sample Area, Bubbler 42
counts
1 R/s
34
Output TBA Sample Cone., Buboler #2
1 R/Sl1 1
yg/m3
35
• Output TBA Sample Conc», Bubbler #1 & #2
1 R/S
yg/m3
36
Output TBA Sample Cone.
1
T
PPm
-------
Figure 8 (cont'd). HP-67 Program Form
STEP KEY ENTRY
KEY CODE
COMMENTS
STEP KEY ENTRY KEY CODE
COMMENTS
001
f LBL A
31 25 11
In sample Vol, ftJ
In Barometric Pres.
"Hg
In Sample Temp, F°
In Sol.Vol., mil
In Dilution Factor
In Std Methanol
Cone, Mg/mi
In Std Methanol Area
In Methanol Sample
Area, Bub#l
Out Methanol Sample
Cone, Bub#l Ug/m
In Dilution Factor
In Std. Methanol
Cone, Mg/mi.
In Std. Methanol
Area
In Methanol Sam.
Area, Bub#2
Out Methanol Sam.
Cone, Bub#2, Mg/ni*
Out Methanol Cone,
Ug/m
Out ppm Methanol
In Std Ethanol
Cone, ug/m&
In Std. Ethanol Area
R/S
84
2
02
RCL 5
34 05
81
X
71
R/S
84
060
R/S
84
X
71
81
STO 1
33 01
R/S
84
R/S
84
X
71
4
04
R/S
84
6
06
Rn. fi
34 Dfi
010
n
on
+
fil
+
61
R/S
84
RCL 1
34 01
1
oi
81
nq
R/S
84
070
1
m
y
71
fi
ne.
STT> 9
n m
81
RCL 2
34 02
R/S
84
R/S
84
RCL 3
34 03
X
71
X
71
020
STO 3
33 03
R/S
84
RCL 3
34 03
f
81
R/S
84
R/S
84
X
71
X
71
R/S
- 84.
080
STO 7
33 07
L.
81
R/S
84
R/S
84
RCL 5
34 05
x
71
X
71
STO 4
33 f>4
R/S
84
R/S
fld
T
81
030
RPT. ?
34 n?
R/S
84
X
71
X
71
STO 5
33 05
R/S
84
RCL 5
34 05
RCL 7
34 07
R/S
84
090
+
61
X
71
R/S
84
R/S
84
3
03
81
0
00
R/S
84
R
08
X
71
3
03
040
R/S
84
R1
RCL 4
34 04
R/S
84
+
61
h RTN
35 ??
R/S
84
1
01
100
3
03
3
03
3
03
-
81
R/S
84
050
HPT. 3
34 03
y
71
n/s
Q4
81
In Ethanol Sam. Area
R/S
84
110
X
71
Bub#l
STO 6
33 Dfi
Out Ethanol Sample
nSSi: _
Cone, Ug/
In Std. Ethanol Ar>
In Ethanol Sample
Area, Bub#2
Out Ethanol Cone.<
Bub.#2,ug/m
Out Ethanol Cone.'
Ug/m
Out Etnanol Cone.,
ppm
In Std TBA Cone.,
Mg/mX,
In Std TBA Area
In TBA Sample
Area, Bub //I
Out TBA Sample
Cone, Bub #1,
Ug/m-5
In Std TBA Cone.
Ug/mJt
In Std TBA Area
In TBA Sample
Area, Bub #2
Out TBA Cone.,
Ug/m3
Out TBA Cone.,
ppm
REGISTERS
0
1
2
3
4
5
6
7
8
9
SO
S1
S2
S3
S4
S5
S6
S7
S8
S9
A
B
C B-16
0
E
I
-------
SWRI PROJECT NO. TEST NO. TEST DATE:
FUEL: CVS NO. TUNNEL SIZE: DRIVER:
SAMPLE COLLECTION BY: CHEMICAL ANALYSIS BY:
GENERAL COMMENTS:
Test No. 1 2 3 4 5
Driving Cycle
CS-FTP
HS-FTP
HFET
SET-7
30 mph
Bekgrnd.
Volume, Ft.3
3.196
3.207
2.010
3.730
1.625
8.241
B.P., "Hg
29.80
29.50
29.02
29.25
30.02
29.95
Temp. °F
75
85
96
85
80
83
Absor. Rea. Vol., mi
25
75
50
50
25
75
Dilution Factor, Bubbler #1
1
1
10
2
5
1
Std. Cone. Ug CH-jOH/m£ Bub.#l
79.1
0.791
791.
7.91
79.1
7.91
Std. Area - Bubbler #1
20000
1000
10000
1000
5000
5000
SamDle Area - Biibbler #1
10000
3000
1000
3000
1000
15000
Sam. Cone, pg CH30H/m3, Bub#l
1.1JX104
2.05X103
7.54X105
2.37X105
2.37X104
7.83X103
Dilution Factor, Bubbler #2
1
1
5
1
2
1
Std. Conc.ua CH-»OH/m£ Bub.#2
7.91
0.791
7.91
0.791
7.91
0.791
Std. Area - Bubbler #2
25000
5000
5000
1000
1500
6000
Sample Area - Bubbler
10000
15000
6000
100
300
1000
Sam. Cone. pgCI^OH/m3,Bub#2
8.89X102
2.05X103
4.52X104
3.95X101
1.75X103
4.35X101
Total Cone. UgCH-}OH/m3
1.20X104
4.1QX103
7.99X105
P.37X104
4.55X104
7.87X103
PPM Methanol
9.00
3.08
" 600
17.8
34.2
5.91
Std. ("!nnr- UaCH^OH/mP, Bub. SI
^r
00
0.784
784
7.84
78.4
7.84
Std. Area - Buhhler #1
10.000
500
20000
3000
15000
20000
SamDle Area - Bubbler ^1
2000
1500
2000
1000
3000
15000
Sam. Cone. uaC-jHsOH/mVh#!
4.40X103
2.03X103
7.47X105
2.6X103
4.34X104
1.*94X103
Std. Cone. UoCoHqOH/mJl Bubfr2
7.84
0.784
7.8*
0.784
7.84
0.784
Std. Area - Bubbler #2
15000
10000
5000
1000
2000
20000
SamDle Area - Bubbler #2
5000
5000
4000
800
3000
1000
Sam. Cone. ugC?H^OH/m3Bub#2
7.23X102
3.39X102
2.99X104
3.13X102
1.30X104
1.24X101
Total Cone. UaC-^HcOH/m3
5.14X103
2.37X103
7.77X105
2.92X103
5.64X104
1.95X103
PPM Kthannl
2.68
1.24
406
1.53
29.4
1.02
VEHICLE:
MILES:
CALCULATIONS BY:
Figure 9. Methanol and ethanol sample collection sheet
B-17
-------
The concentration from the two bubblers can be added for a
total methanol concentration:
Total yg methanol/m^ = conc.(Bubbler #1) + conc.(Bubbler #2)
= 1.11 x 104 yg/m3 + 8.89 x 102 yg/m3
= 1.20 x io4 yg/m3
PPM CH^OH = yg/m^ t density yg/mi
. ^ , „ iiol. Wt. (CH-?OH) x 1000
density yg/m£ = ^041
Mol. Wt. CH3OH = 32.04 g/mole
32.04 x 1000
density = = 1333 yg/mJl
24.04&
4 3
ppm methanol = 1.20 x 10 r 1333 yg/m£. = 9.00 ml/m = 9.00 ppm
The calculations for ethanol are carried out in the same manner by
substituting the appropriate standard concentrations, peak areas and
molecular weight into the above formulas. The calculations give the
following concentrations.
Bubbler #1, 4.40 * 10^ yg ethanol/iru
Bubbler #2, 7.34 x 10 yg ethanol/m
Bubbler #1 and #2, 5.13 * 10 yg ethanol/m
ppm, 2.68 ethanol
Note: The values used in these calculations are picked from a range of
temperatures, standards, dilution factors, etc., to validate the calcula-
tions and may not be representative of expected raw data. These
calculations are presented to confirm that the manual and HP-67
calculations give the same results. This was confirmed on six sets of
calculations.
LIST OF EQUIPMENT AND REAGENTS
The equipment and reagents for the analysis of the methanol and
ethanol is divided into two groups. The first involves the sample
acquisition and the second the instrumental analysis of the sample once
it has been obtained. Manufacturer, stock number and any pertinent
descriptive information are listed. The preparation of standards is
also discussed.
B-18
-------
Sampling
1. Glass impingers, Ace Glass Products, Catalog #7530-11, plain tapered
tap stoppers with 18/7 arm joints and 29/42 bottle joints.
2. Flowmeter, Brooks Instrument Division, Model 1555, tube size R-2-15-C,
graduated 0-15, sapphire float, 0-5 k/m±n range.
3. Sample pump, Thomas Model 106 CA18, capable of free flow capacity of
4 £/min.
4. Dry gas meter, American Singer Corporation, Type AL-120, 60 CFH
capacity.
5. Regulating valve, Nupro 4MG, stainless steel.
6. Teflon tubing, United States Plastics Corporation, 1/4" OD x 1/8" ID
and 5/16" OD x 1/8" ID.
7. Teflon solenoid valve, the Fluorocarbon Company, Model DV2-144NCA1.
8. Drying tube, Analabs Inc., Catalog #HGC-146, 6" long, 1/4" brass
fittings.
9. Miscellaneous Teflon nuts, ferrules, unions, tees, clamps, connectors,
etc.
10. Digital readout for dry gas meter.
11. Miscellaneous electrical switches, lights, wirings, etc.
12. Six channel digital thermometer, Analog Devices, Model #2036/J/l.
13. Iron/Constantan type J single thermocouple with 1/4" OD stainless
steel metal sheath, Thermo Sensors Corporation.
14. 30 mJl polypropylene sample storage bottles, Nalgene Labware, Catalog
#2006-0001.
15. Deionized or distilled water.
16. Class A, 10 mil volumetric pipet.
17. Class A, 1000 m& volumetric flask.
Instrumental Analysis
1. 5 pi syringe, Hamilton Co., Reno, Nevada.
2. Perkin-Elmer Model 3920B gas chromatograph equipped with flame
ionization detector.
B-19
-------
3. Soltec Model B-281 1 mv recorder.
4. Hewlett-Packard Model 3353 gas chromatograph computer system with
remote printer.
Preparation of Primary Standards
The primary standards for methanol, ethanol, and TBA are prepared
by diluting a known volume of methanol, ethanol, or TBA with deionized
(or distilled) water. Standards less than ^500 ppm are prepared by
diluting higher concentration standards with deionized water.
B-20
-------
APPENDIX C
CALCULATION OF HYDROCARBON RECOVERY (IN GRAMS)
FROM BAG PPMC
-------
APPENDIX C
CALCULATION OF HYDROCARBON RECOVERY (In Grams) FROM BAG ppmC
Bag ppmC/10^ x Purge flowrate, ft^/min x Purge time, min,
x B«P«i in Hg x __5282F_ x 16.33 g = Weight gasoline, g
29.92 in Hg °F + 460 ft3 HC
Example:
Bag concentration = 1520 ppmC
Purge flowrate = 1.53 ft^/min
Purge time = 71.00 minutes
B.P. = 29.04 in Hg
Temp. = 82.4°F
1520/106 x 1.53 x 71.00 x 29.04/29.92 x 528/(82.4 + 460) x 16.33 = 2.6 g HC
If hydrocarbons are unleaded gasoline with density of 0.737 g/ml:
2.6 g x 1 ml/0.737 g = 3.5 ml gasoline
C-2
-------
APPENDIX D
CHARCOAL WEIGHT LOSS AND CONTINUOUS HC LEVELS DURING THE
THE PURGE CYCLE (OF DELCO IN-USE CHARCOAL) OF THE
BUTANE WORKING CAPACITY PROCEDURE
-------
APPENDIX D
CHARCOAL WEIGHT LOSS AND CONTINUOUS HC LEVELS DURING THE
PURGE CYCLE (OF DELCO IN-USE CHARCOAL) OF THE
BUTANE WORKING CAPACITY PROCEDURE
Cycle
Time, min
Continuous
Weight Loss,
HC, DDmC
R/hr
1
6.2
4500
„a
12.1
2000
5.0
22.8
810
2.4
32.4
400
1.1
34.5
300
__b
2
8.0
4400
45.8
16.5
1400
3.9
24.0
640
1.5
32.0
320
0.7
35.4
280
__b
3
7.0
3600
40.5
14.0
1100
2.7
21.0
640
1.2
28.0
410
0.9
31.2
300
__b
4
7.0
5000
36.2
14.0
1900
5.1
21.0
900
2.4
28.0
460
1.0
37.8
300
0.7
5
7.0
4900
46.4
14.3
1600
4.5
21.0
600
1.3
28.0
390
0.8
^Canister not weighed before purge
Canister gained weight slightly, probably due to water
absorption during the weighing process.
D-2
-------
APPENDIX E
WORKING CAPACITY FOR INDIVIDUAL WORKING
CAPACITY CYCLES
-------
APPENDIX E
WORKING CAPACITY FOR INDIVIDUAL WORKING
CAPACITY CYCLES
Source
Canister
Number
Working Capacity, g/50 g charcoala
Cycle 1
Cycle 2
Cycle 3
Average
TVA
2090a
2.57
2.23
2.43
2.41
2099a
1.96
2.09
2.70
2.79
1925
1.95
2.43
2.19
2.19
8887a
1.80
1.45
1.40
1.55
1991a
2.24
2.29
2.02
2.18
2067a
2.38
2.76
2.31
2.48
1725
2.94
2.52
1.76
2.41
1747
1.62
1.78
1.58
1.66
8961a
1.46
1.23
1.42
1.37
8902
1.34
1.85
1.46
1.55
SwRI
201
1.72
2.35
2.15
2.07
(from DOE
202
2.02
1.55
2.15
1.91
fleet)
205
2.34
1.65
2.03
2.01
206
0.90
2.10
1.01
1.34
101
-J)
1.70
1.16
1.43
102
1.65
1.81
1.86
1.77
104
2.37
1.57
2.39
2.11
106
1.97
2.25
1.48
1.90
EPA
A1480008
__b
1.28
1.01
1.15
A1480049
1.80
1.33
1.48
1.54
A1480073
1.62
1.82
1.82
1.75
A1480039
1.81
1.37
2.29
1.82
A1480060
1.51
2.58
2.58
2.22
A1480096
1.16
1.97
2.06
1.73
aWorking capacity = charcoal weight (when loaded to 1000 ppmC
with butane) - charcoal weight (after cold purging to 600 ppmC
hydrocarbons)
^No Data
E-2
-------
APPENDIX F
SELECTED DETAILED HYDROCARBONS
-------
APPENDIX F-i. SELECTED DETAILED HYDROCARBONS EMITTED DURING COLD AND HOT
PURGING OF 50 g SAMPLES OF CHARCOAL FROM 1N-USE TVA
EVAPORATIVE CANISTERS, g
Compound
Number
1
2
3
0
5
6
7
8
9
10
11
12
13
10
15
16
17
IS
19
20
21
22
23
20
25
26
27
28
29
30
31
32
33
30
35
36
37
38
39
00
01
02
aNo data
^Not detected
Canister Number
2090
Cold3 Hot
2099
8887
1991
2067
<0.01
J°.
8961
Cold Hot Cold Hot Cold Hot Cold Hot Cold Hot
0.33
<0.01
<0.01
0.01
<0.01
0.02
<0.01
<0.01
<0.01
0.01
0.02
0.01
0.02
01 0.09 0.01
0.02
<0.01 0.29
0.05
<0.01 <0.01
0.03
0.62
<0.01
0.03
0.01
0.01
0.02
<0.01
<0.01
<0.01
• 0.12
0.06 J<0.01
0.03 <0.01
0.01 ~
0.03 |<0.01 }<0.01
0.01
Jo.(
01
<0.01
0.02 )<0.01 "
0.02 0.01 <0.01
0.01 <0.01
<0.01
<0.01
0.02
0.01
0.01
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01 <0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
F-2
-------
APPENDIX F-l (CONT'D). SELECTED DETAILED HYDROCARBONS EMITTED DURING COLD AND
HOT PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE TVA
EVAPORATIVE CANISTERS, g
Canister Number
2090
2099
Number Cold3
Hot
Cold
Hot
43
_b
44
—
—
—
45
0.01
0.04
—
46
0.03
0.08
0.01
47
48
49
0.02
0.04
>
0.02
0.01 !
<0.01
50
—
0.03
—
51
—
0.01
\
<0.01
52
53
jo.03
0.03
0.04
54
0.03
0.03
0.07
55
0.02
0.03
V
0.04
56
57
I 0.09
} 0* 15
0.21
58
59
0.04
0.03
1 0.09
60
61
62
0.04
| 0.03
0.08
63
0.02
0.01
0.04
64
—
<0.01
<0.01
65
—
0.01
0.03
66
0.03
0.01
0.06
67
0.01
<0.01
0.01
68
0.01
<0.01
0.02
69 |
70
0.04
jo.01
| 0.06
71
0.10
0.02
0.17
72
M A \
~
<0.01
--
73
74 J
0.62
0.09
0.79
75
76
~
0.01
0.12
77
0.11
0.01
0.13
78
0.35
0.04
0.48
79
0.14
0.01
0.12
80
0.04
<0.01
0.04
81
0.27
0.02
0.21
82
1.19
0.07
0.86
83
0.67
0.02
0.43
8887
1991
2067
8961
Cold Hot Cold Hot Cold Hot Cold
0.02
0.06
0.02
0.02
0.11
0.02
0.01
0.04
0.02
0.01
0.03
0.01
0.10
0.19
0.10
Hot
0.03
0.15
0.06
<0.01 <0.01 <0.01
0.01
<0.01
0.01
<0.01
0.01
<0.01
J 0.(
01 0.05 0.03 0.02
<0.01
.02
jo.01 J
0.01
0.06
0.01
0.02
<0.01
0.02
0.01
0.06
0.05
0.03
0.03
0.01
0.01
0.04 0.10 0.20 0.04
.09
0.01 \ 0.08 I 0.04 10.01 10.02
0.08 0.01 0.07 0.04
0.03
0.04
0.02
0.12
0.06
0.06 0.09
0.07
0.07
0.12
0.10
0.24 0.40
0.01
<0.01
<0.01
0.01
<0.01
<0.01
0.05
0.01
0.02
0.06
<0.01
0.02
0.01
<0.01
0.01
0.03
<0.01
0.01
0.08
0.17
J<0.01 J 0.06 j
0.01
<0.01
0.01
0.01
0.02
0.01
<0.01
0.01
0.05
0.02
0.06
0.03
0.27
0.11
0.11
0.15
0.08
0.02
0.05
0.21
0.09
0.01
0.05
0.01
0.19
0.02
0.08
0.01
<0.01
0.02
0.08
0.03
I 0.01
lo.Ol
0.04
0.07
0.14
0.01
0.01
0.02
0.03
0.08
0.01
<0.01
0.01
0.01
0.02
0.01
<0.01
0.01
0.01
0.05
0.02
0.01
0.04
0.04
0.13
<0.01
<0.01
0.01
0.01
0.03
0.01
<0.01
0.01
0.01
0.03
0.03
<0.01
0.05
0.02
0.11
0.10
0.01
0.12
0.03
0.15
0.02
<0.01
0.03
0.01
0.05
0.52
0.06
0.68
0.12
0.64
0.07
0.01
0.16
0.02
0.19
0.08
0.01
0.16
0.03
0.20
0.39
0.03
0.47
0.05
0.31
0.10
0.01
0.22
0.02
0.16
0.03
<0.01
0.05
<0.01
0.03
0.23
0.02
0.38
0.02
0.11
1.06
0.08
1.63
0.10
0.52
0.55
0.04
0.86
0.03
0.17
aNo data
^Not detected
F-3
-------
APPENDIX F-l (CONPD). SELECTED DETAILED HYDROCARBONS EMITTED DURING COLD AND
HOT PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE TV A
EVAPORATIVE CANISTERS, g
Canister Number
Compound 2090 2099 8887 1991 2067 8961
Number Colda Hot Cold Hot Cold Hot Cold Hot Cold Hot Cold Hot
98
99
J 0.38 Jo.01 jo.21 j 0.01 J 0.03 J 0.01 J 0.27 _jj J 0.45 j 0.01 J 0.06
85
86
87 0.42 0.02 0.28 0.02 0.04 0.02 ' 0.43 0.03 0.54 0.03 0.07
88 0.18 0.01 0.13 0.01 0.02 0.01 0.26 0.01 0.34 0.01 0.03
89 0.17 <0.01 0.10 <0.01 0.01 <0.01 0.14 0.01 0.17 <0.01 0.01
90 0.22 0.008 0.13 0.01 0.02 0.01 0.16 0.02 0.23 0.01 0.02
91 0.30 0.013 0.18 0.01 0.03 0.01 0.24 0.02 0.34 0.02 0.04
92
93
94 ' 0.47 0.018 0.28 0.02 0.04 0.01 0.33 0.04 0.49 0.03 0.06
95 0.20 <0.01 0.12 <0.01 0.01 <0.01 0.11 0.01 0.17 0.01 0.01
96 0.41 0.02 0.27 0.02 0.03 0.01 0.31 0.03 0.43 0.03 0.05
97 0.13 -- -- <0.01 0.01 <0.01 0.08 <0.01 0.11 0.01 0.01
v « ^ v w • v v « * v v * v 4 w • v • w « v • m > w • v •• v • ^ r v • w«> w • v T
J 0.27 J 0.011 Jo.16 Jo.01 Jo.02 J 0.01 J 0.21 J 0.02 jo.31 j 0.06 J 0.04
0.01 <0.01 " 0.04 " 0.03 <0.01 0.01
J 0.03 )<
Total 7.41 1.14 6.14 0.93 2.58 2.02 6.60 0.85 9.06 2.53
aNo data
^Not detected
4.80
F-4
-------
APPENDIX F-2. SELECTED DETAILED HYDROCARBONS EMITTED DURING HOT
PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE TV A
EVAPORATIVE CANISTERS, g
Compound
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
Canister Number
2090
„a
2099
0.33
J<0.
01
/
^ 0.01 j
1925
0.01
0.16
} 0.13
0.12
<0.01
0.01
0.02
0.01
}o.
}o.
8887
0.29
<0.01
<0.01
^ <0.01
<0.01
Jo.03 ^
<0.01
0.01
.03
<0.01
0.01
<0.01
1991
2067
0.62
<0.01 <0.01
0.03
<0.01
0.03
0.11
<0.01
0.03
01
J 0.01 J <0.01 J<0.
j°.04 " jo.
0.03
01
01
1725
0.02
0.05
0.02
0.02
0.05
0.02
0.03
<0.01
01
0.02
0.04
1747
0.03
0.02
0.01
0.01
0.03
S961
}°.
03
0.01
0.01
0.01
^0.03 |
0.04
0.01
>0.02
0.02
}°-
}o.
8902
0.02
<0.01
<0.01
<0.01
<0.01
0.01
).
<0.01
0.01
<0.01
<0.01.
0.01
02
06
}
}
0.01
a~ Not detected
F-5
-------
APPENDIX F-2 (CONPD). SELECTED DETAILED HYDROCARBONS EMITTED DURING HOT
PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE TVA
EVAPORATIVE CANISTERS, g
Compound Canister Number
Number 2090 2099 1925 8887 1991 2067 1725 1747 8961 8902
43 ..a
45 0.01 -- <0.01 0.02 -- 0.01 - -- 0.03 0.04
46 0.03 0.01 0.03 0. 11 -- 0.03 - 0.03 0.15 0.21
47 0.02 0.02 0.04 0.02 - 0.01 0.04 0.01 0.06 0.05
18
19
}<0-01 II ><0.01 ~~ ~I II " \ 0.01 \ <0.01
0.01 -- - - - ' 0.02
<0.01 -- <0.01 -- -- -- <0.01
\ 0.03 jo.01 >0.01 >0.05 >0.02 \ 0.03 \ 0.01 >0.04. >0.09 >0.10
' A rtl f\ A7 ' r\ ftl r\ r\t ' n t ' a a*. S n r\-r * a ao ' « . ' n « ^
50 -- - - 0.01 -- - - - 7 0.02 0.01
51 -- <0.01 s -- <0.01 v -- -- -- -- <0.01 <0.01
52
53
51 ' 0.03 ' 0.07 ' 0.03 ' 0.06 '<0.01 ' 0.01 ' 0.07 " 0.08 ' 0.12 ' 0.10
55 0.02 0.01 0.02 0.05 0.01 0.02 0.05 0.09 0.10 0.08
37 | 0.09 j 0.21 °_'_09 V 0.10 ^0.04 ^ 0-12 | 0.21 }o.20 J 0.10
58
59 J 0.01 j 0.09 | 0.03 J 0.08 j 0.01 j 0.06 J 0.07 J 0.06 j 0.17 J 0.18
^0.04 | 0.08 | 0.02 10.07 ^ 0.01 ^0.04 J 0.06 | 0.05 ^0.14 ^
1725
1747
—
0.03
0.04
0.01
0.04
> 0.04.
0.07
0.08
0.05
0.09
0.21
f 0.20
0.07
| 0.06
0.06
> 0.05
60
61
62
63 0.02 0.01 0.02 0.05 0.01 ' 0.02 0.05 0.10 ' 0.08 ' 0.14
64 -- <0.01 <0.01 0.01 0.01 0.01 0.01 <0.01 0.02 0.01
65 -- 0.03 0.02 0.02 0.01 0.01 0.03 0.01 0.05 0.03
66 0.03 0.06 0.03 0.06 0.02 0.04 0.06 0.07 0.13 0.17
67 0.01 0.01 <0.01 0.01 <0.01 0.01 0.01 0.03 0.03 0.05
68 0.01 0.02 0.01 0.02 0.01 0.01 0.01 0.02 0.03 0.05
7Q 0.04 jo.06 } 0.02 ^0.06 ^0.03 j 0.05 j0.01 ^0.07 ^0.11 ^ 0.15
71 0.10 0.17 0.09 0.06 0.10 0.12 0.14 0.30 0.15 0.09
72 -- — 0.01 0.03 0.02 0.03 0.02 0.04 0.05 0.07
^ 0.62 | 0.79 | 0.41 j 0.27 | 0.52 j 0.68 ^ 0.61 1 Jo.64 j
0.40
73
71 . , , , , , , ^ ^
H II } 0.12 j 0.05 ^ 0.11 ^ 0.07 jo.16 ^0.08 J ' ^0.19 \ 0.32
77 0.11 0.13 0.05 0.11 0.08 0.16 0.08 0.18 0.20 0.25
78 0.35 0.48 0.26 0.15 0.39 0.47 0.35 0.90 0.31 0.26
79 0.14 0.12 0.05 0.08 0.10 0.22 0.08 0.21 0.16 0.18
80 0.04 0.04 0.02 0.02 0.03 0.05 0.02 0.04 0.03 0.03
81 0.27 0.21 0.13 0.05 0.23 0.38 0.14 0.39 0.11 0.11
82 1.19 0.86 0.55 0.21 1.06 1.63 0.60 1.77 0.52 0.40
83 0.67 0.43 0.30 0.09 0.55 0.86 0.30 0.84 0.17 0.19
84 1.57 1.05 0.97 0.22 1.65 2.11 0.83 2.45 0.34 0.35
a~ Not detected
F-6
-------
APPENDIX F-2 (CONT'D). SELECTED DETAILED HYDROCARBONS EMITTED DURING HOT
PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE TV A
EVAPORATIVE CANISTERS, g
Compound Canister Number
Number ~2090 2099 1925 ~8887~ 1991" 2067 1725 W ~896l" "890T
j 0.38 ^ 0.21 ^ 0.17 ^ 0.03 ^0.27 | 0.45 ^0.16 ^0.41 | 0.06 ^0.07
85
86
87 ' 0.42 ' 0.28 0.29 0.04 0.43 0.54 0.21 0.56 0.07 0.07
88 0.18 0.13 0.11 0.02 0.26 0.34 0.08 0.33 0.03 0.01
89 0.17 0.10 0.08 0.01 0.14 0.17 0.07 —a 0.01 0.01
90 0.22 0.13 0.12 0.02 0.16 0.23 0.09 0.21 0.02 0.02
91 0.30 0.18 0.20 0.03 0.24 0.34 0.13 0.34 0.04 0.03
H 10.27 ^ 0.16 | 0.19 ^ 0.02 ^ 0.21 ^ 0.31 ^ 0.12 | 0.30 ^0.04 ~
94 0.47 0.28 0.31 0.04 0.33 0.49 0.20 0.48 0.06
95 0.20 0.12 0.12 0.01 0.11 0.17 0.08 0.16 0.01
96 0.41 0.27 0.33 0.03 0.31 0.43 0.19 0.45 0.05
97 0.13 - 0.14 0.01 0.08 0.11 0.06 0.13 0.01
^ j 0.01 " | 0.17 | <0.01 | 0.04 | 0.03 | 0.02 ^0.12 ^ <0.01 ^
Total 8.99 7.22 5.92 2.92 8.30 11.18 5.76 13.30 5.15 4.78
a— Not detected
F-7
-------
APPENDIX F-3. SELECTED DETAILED HYDROCARBONS EMITTED DURING
HOT PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE
SWRI EVAPORATIVE CANI5TERS (DOE FLEET),g
Compound Canister Number
Number 201 202 205 206 101 102 104 106a
1 -b
2
3
4 0.03
5
6
7 <0.01
8
9 <0.01
10
11
12
13
14 <0.01
15 <0.01
17
18
19
20 <0.01 <0.01 0.01 0.01 <0.01 <0.01
21
22
23
24 <0.01 0.02 0.02 0.04 '<0.01 0.01 <0.01
25
26
27
28
29
30
31
32
33
34
35 0.01 ' 0.02 0.03 0.04 0.01 0.02 0.01
202
205
206
101
102
104
0.03
0.04
0.02
0.03
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
—
<0.01
<0.01
—
<0.01
<0.01
>0.01
<0.01
<0.01
<0.01
<0.01
—
<0.01
—
—
—
—
<0.01
—
—
—
—
—
<0.01
—
—
—
—
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
|<0.01 j 0.02 ^0.03 j 0.05 j 0.01 ^0.11 j <0.
<0.01 0.02 0.02 0.04 <0.01 0.01 <0.
} <0'01 ~ I- I- " I" ~
| 0.02 | 0.05 j 0.04 ^0.09 j 0.01 j 0.04 j <0.
01
01
^ <0.01 j 0.01 10.02 ^ 0.02 } 0.01 ^0.01 | <0.
01
36 - - -- -- <0.01 <0.01
38 j 0.01 J 0.03 j 0.02 ^0.04^0.01 | 0.02
HQ
^2 j 0.14 | 0.24 | 0.14 | 0.35 ^ 0.15 ^0.19
aHole in sample bag, no data
b-- Not detected
F-8
-------
APPENDIX F-3 (CONT'D). SELECTED DETAILED HYDROCARBONS EMITTED
DURING HOT PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE
SWRI EVAPORATIVE CANISTERS (DOE FLEET), g
Compound
Number
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
Canister Number
201
-b
0.12
0.25
0.21
0.13
0.05
0.75
0.17
0.24
0.09
0.01
0.07
0.30
0.08
202
0.22
0.33
0.28
205
0.12
0.19
0.1*
206
0.29
0.42,
0.34
101
0.14
0.25
0.23
102
0.17
0.24
0.23
^ <0.01 | 0.01 | <0.01 ^ 0-01 ^ <0.01 ^ 0.01 j
0.02
0.01
<0.01
0.02
0.01
0.03
0.01
0.01
<0.01
0.02
<0.01
104
0.09
0.12
0.14
<0.01
0.01
<0.01
jo.28 j 0.30 jo.14 j 0.29 jo.ll ^0.23 ^ 0.12
0.19
0.19
0.19
0.19
0.09
0.09
0.19
0.19
0.18
0.20
0.18
0.21
| 0.53 j 0.68 j 0.39 j 0.51 j 0.55 j 0.59 j
J 0.52 J 0.52 ^ 0.24 J 0.35 J 0.36 J 0.40 J
J 0.42 j 0.42 j 0.20 j 0.30 J 0.30 j 0.36 j
0.26
0.03
0.03
0.33
0.05
0.06
0.30
0.67
0.05
0.17
0.03
0.05
0.16
0.02
0.02
0.22
0 .On
0.04
0.10
0.02
0.42
0.13
0.12
0.15
0.06
0.01
0.04
0.21
0.06
}
0.07
0.05
0.29
> 0.26
0.19
0.16
0.14
0.01
0.12
0.62
0.21
0.07
0.01
0.31
0.04
0.05
0.13
0.03
<0.01
0.03
0.17
0.06
0.14
0.02
j 0.68 j
jo.io j
0.13
0.27
0.08
0.01
0.09
0.38
0.10
0.11
0.05
0.47
0.15
0.16
0.19
0.09
0.01
0.07
0.34
0.09
0.10
0.12
0.54
0.28
0.05
0.06
0.21
0.19
0.09
jo.15 ^0.12 j 0.12 j 0.05 jo.09 j 0.13 j
0.14
0.02
0.03
0.06
0.13
0.02
> 0.72
0.09
0.31
0.06
<0.01
0.08
0.44
0.14
106a
aHole in sample bag, no data
b-- Not detected
F-9
-------
APPENDIX F-3 (CONT'D). SELECTED DETAILED HYDROCARBONS EMITTED
DURING HOT PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE
SWRI EVAPORATIVE CANISTERS (DOE FLEET), g
Compound
Number
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
Total
Canister Number
201
202
205
206
101
102
104
0.20
0.19
0.80
0.20
0.25
—b
0.54
\ 0.02
0.02
0.07
0.03
0.03
0.29
0.04
0.03
0.01
0.16
0.06
0.04
0.04
0.12
0.01
0.02
0.06
0.02
0.02
0.02
0.05
<0.01
<0.01
0.01
0.01
0.01
<0.01
0.01
0.01
0.02
0.08
0.02
0.02
0.03
0.04
0.01
0.03
0.10
0.03
0.02
0.02
0.06
>0.01
0.02
0.10
0.03
0.02
0.02
0.06
0.03
0.03
0.15
0.05
0.03
0.05
0.09
0.01
0.01
0.01
0.01
0.01
0.02
0.02
0.03
0.14
0.05
0.03
0.03
0.09
—
0.01
<0.01
0.01
—
<0.01
0.01
—
—
0.02
<0.01
0.02
6.19
6.74
6.39
5.51
5.70
6.11
5.25
106a
aHole in sample bag, no data
b-- Not detected
F-10
-------
APPENDIX F-4. SELECTED DETAILED HYDROCARBONS EMITTED DURING
HOT PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE
EPA EVAPORATIVE CANISTERS, g
Compound
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
0008
__a
0.03
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
03
0.02
<0.01
0.10
<0.01
0.50
Canister Number (A148- )
0049
0073
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
> 0.02
<0.01
0.01
jo. 04 jo.
<0.01
jo.01 "
<0.(
j OA
0.02
0.02
<0.01
01
}o.
01
<
j <0.<
<0.(
^0.(
0.04
<0.01
.01
<0.01
.01
0.03
<0.01
0.08
<0.01
0039
2.33
j 0.03 j 0.01 j 0.02 j 0.
" 0.01
.01
<0.01
0.01
0.02
0060
> 0.02
0.01
)o.
0.
j <0.
03
0.02
01
0.04
0.18
0.39
0.19
0.31
0096
0.01
0.02
<0.01
<0.01
<0.01
K
01
<0.01
0.01
j 0.01 j <0.
0.07
01
jo.04 j 0.01 jo.01 ^ 0.02 j 0.03 J
0.03
<0.01
0.02
0.15
a~ Not detected
F-ll
-------
APPENDIX F-4 (CONT'D). SELECTED DETAILED HYDROCARBONS EMITTED
DURING HOT PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE
EPA EVAPORATIVE CANISTERS, g
Compound
Number
0008
Canister Number (A148- )
0049
0073
0039
0060
0096
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
--a
0.23
1.14
0.23
0.03
0.01
0.28
0.19
0.19
0.05
0.01
0.01
0.09
0.01
0.01
0.12
0.26
0.13
| 0.01 | 0.01 |
0.02
0.01
0.26
0.54
0.22
0.01
0.05
0.02
0.08
0.17
0.12
0.01
0.01
0.17
0.68
0.18
^0.01 ^
0.02
0.01
| 0.25 ^0.17 ^ 0.24 ^ 0.08 ^ 0.17 ^
0.17
0.20
0.22
0.22
0.09
0.07
0.16
0.14
^0.40 ^0.62 ^ 0.76 | 0.20 | 0.34 }
| 0.22 ^0.24 ^ 0.32 J 0.09 J 0.18 |
}0.03 }
0.08
0.01
}0.27
^ 0.03 [
0.04
0.11
0.02
<0.01
0.02
0.11
0.04
0.11
^0.22
j 0.29
0.08
0.08
0.03
0.04
<0.01
0.03
0.13
0.14
0.02
0.02
0.02
0.03
> 0.06
^ 0.07
0.16
0.15
0.02
0.02
0.72
0.08
0.28
0.04
0.01
0.05
0.24
0.07
0.24
0.07
0.03
0.02
0.01
0.01
0.16
0.06
0.02
0.02
0.10
0.01
0.02
0.04
0.02
0.10
0.02
0.62
0.07
0.21
0.03
0.01
0.04
0.12
0.08
0.17
0.03
0.09
0.02
<0.01
0.17
0.19
0.13
0.09
0.20
0.06
0.01
0.06
0.30
0.10
0.35
0.08
0.82
0.15
0.01
0.02
0.01
0.20
0.24
0.24
0.49
0.19
^ 0.06 ^ 0.05 }
0.15
0.12
0.01
0.01
0.10
0.02
0.02
0.06
0.08
0.02
^0.18 ^ 0.44 ^ 0.36
| 0.03 ^ 0.08 ^
0.09
0.09
0.18
0.07
0.01
0.07
0.32
0.14
0.44
3-- Not detected
F-12
-------
APPENDIX F-4 (CONPD). SELECTED DETAILED HYDROCARBONS EMITTED
DURING HOT PURGING OF 50 g SAMPLES OF CHARCOAL FROM IN-USE
EPA EVAPORATIVE CANISTERS, g
Compound
Number
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
Total
Canister Number (A148- )
0008
0049
0073
0039
0060
0096
>0.02
0.02
0.01
0.02
0.04
0.07
0.02
0.05
0.03
0.02
0.08
0.11
0.01
0.02
0.01
0.01
0.03
0.05
<0.01
<0.01
<0.01
—a
0.01
0.02
<0.01
0.01
0.01
0.05
0.02
0.04
0.02
\
0.02
0.02
0.02
0.05
0.07
> 0.01
0.02
0.01
0.04
0.04
0.06
0.02
0.03
0.02
--
0.07
0.10
<0.01
<0.01
<0.01
—
0.02
0.03
0.02
0.04
0.06
0.09
<0.01
<0.01
—
0.01
0.02
"
— ~
0.01
0.02
5.28
5.00
5.89
4.82
5.28
5.79
aNot detected
F-13
-------
APPENDIX F-5. PERCENTAGE OF DETAILED HYDROCARBONS PURGED FROM 50 g CHARCOAL
SAMPLES FROM IN-USE TVA GASOLINE EVAPORATIVE CANISTERS*
Canister Number
2090
2099
8887
Compound
Number
4
7
10
12
13
14
20
21
22,23
24
25,26
27,28
29
30,31
33,34
35
36
37,38,39,40
41,42
45
46
47
50
52,53
54
55
56,57
58,59,60
Working
Cold Capacity
Purge^ Purge
98
Hot
Purge
__c
Working
Capacity Hot
Purge Purge
Cold
Purge
2
6
3
6
3
2
2
2
2
10
2
98
9d
2
1
Cold
Purge
4
2
1
1
1
1
5
3
1
2
1
1
2
1
1
1
4
2
5
1
1
1
1
1
3
1
Working
Capacity
Purge
94
Hot
Purge
8d
1
1
3
1
1
2
1
3
2
Percentages were calculated based on the peak area of individual (or groups of inseparable)
compounds as a fraction of total area.
^No data
c~ is less than 1
^Butane peak not added into totals, probably a residue from the previous working capacity analysis.
-------
APPENDIX F-5 (CONT'D). PERCENTAGE OF DETAILED HYDROCARBONS PURGED FROM 50 g
CHARCOAL SAMPLES FROM IN-USE TV A GASOLINE EVAPORATIVE CANISTERS®
Canister Number
2090 2099 8887
Working Working Working
Compound Cold Capacity Hot Cold Capacity Hot Cold Capacity Hot
Number Purge** Purge Purge Purge Purge Purge Purge Purge Purge
61,62 —c 2 -- 1 1 — 2
63 -- -- 1 — — 1 — 1
65 — -- 1
66 1 — II — 2
69,70 — — -- — 1 2
71 1 2 — 1 1 -- 2
72 — - - — - - - 1
73,74 —46 — 73 — 7
75,76 — — 1 — 1 1 — 3
77 1 1 — 1 1 -- 3
78 2 3 — 4 2 -- 4
79 11 — 11 — 2
81 2 1 — 2 1 -- 1
82 8 4 — 7 4 -- 6
83 — 5 2 — 12 — 2
84 — 11 5 — 9 6 — 6
85,86 — 3 1 — 2 — — 1
87 3 1 — 2 1 — 1
88 II — 11
89 - 1 1
90 2 1 — 1 1
91 2 1 -- 2 1 -- 1
92,93 2 1 — 1 1 -- 1
94 — 3 1 — 2 2 — 1
95 - 1 1
96 3 1 — 2 2 — 1
97 - 1
Percentages were calculated based on the peak area of individual (or groups of inseparable)
compounds as a fraction of total area.
^No data
c— is less than 1
dButane peak not added into totals, probably a residue from the previous working capacity analysis.
-------
APPENDIX F-6. PERCENTAGE OF DETAILED HYDROCARBONS PURGED FROM 50 g CHARCOAL
SAMPLES FROM IN-USE TV A BLEND EVAPORATIVE CANISTERS®
Canister Number
1991
2067
8961
Compound
Number
4
7
14
24
27,28
33,34
35
36
37,38,39,40
41,42
45
46
47
50
52,53
54
55
56,57
58,59,60
61,62
63
65
66
Cold
Purge
b
1
1
3
1
1
2
2
2
14
3
2
1
1
2
Working
Capacity
Purge
97
Hot
Purge
5C
Cold
Purge
1
4
2
4
2
1
1
1
1
6
1
1
Working
Capacity
Purge
99
Hot
Purge
Cold
Purge
1
1
1
2
1
1
1
3
7
3
6
3
2
2
2
2
7
2
2
1
Working
Capacity
Purge
86
Hot
Purge
2
1
1
2
1
5
2
2
1
1
2
aPercentages were calculated based on the peak area of individual (or groups of inseparable)
compounds as a fraction of total area,
b— is less than 1
cButane peak not added into totals, probably a residue from the previous working capacity analysis.
-------
APPENDIX F-6 (CONT'D). PERCENTAGE OF DETAILED HYDROCARBONS PURGED FROM 50 g
CHARCOAL SAMPLES FROM IN-USE TVA BLEND EVAPORATIVE CANISTERS3
Canister Number
Compound
Number
1991
2067
8961
Cold
Purge
Working
Capacity
Purge
Hot
Purge
Cold
Purge
Working
Capacity
Purge
Hot
Purge
Cold
Purge
Working
Capacity
Purge
Hot
Purge
69,70
1
b
„
„
„
1
1
71
72
73,74
3
—
i
1
i
1
—
2
1
1 1
4
4
4
4
1
1
8
75,76
I J
i
1
1
1
—
3
77
1
i
1
1
1
—
3
78
5
3
2
3
2
—
4
79
1
1
1
1
1
—
2
81
1
—
2
1
2
1
—
1
82
6
9
6
10
3
—
7
83
2
5
3
5
1
—
2
84
6
14
8
13
4
—
4
85,86
1
2
—
3
—
—
1
87
1
4
2
3
1
—
1
88
1
2
1
2
—
--
—
89
—
1
1
1
—
—
--
90
—
1
1
—
1
—
—
--
91
1
2
2
2
1
—
1
92,93
1
2
2
2
2
—
—
94
1
3
3
3
1
—
1
95
—
1
1
1
—
—
—
96
1
3
2
3
1
—
1
97
—
1
—
1
—
—
--
Percentages were calculated based on the peak area of individual (or groups of inseparable)
compounds as a fraction of total area,
b-- is less than 1
cButane peak not added into totals, probably a residue from the previous working capacity analysis.
-------
APPENDIX F-7. PERCENTAGE OF DETAILED HYDROCARBONS HOT
PURGED FROM 50 g CHARCOAL SAMPLES FROM IN-USE
TVA EVAPORATIVE CANISTERS3
Compound Canister Number
Number
1925
1725
1747
890;
4
2b
lb
__c
—
13
—
1
--
—
41,42
—
—
—
1
45
—
—
—
1
46
—
—
—
3
47
—
—
—
1
52,53
—
1
«
2
54
—
1
—
2
55
—
1
—
1
56,57
1
3
1
1
58,59,60
—
1
—
3
61,62
—
1
—
2
63
—
1
1
2
66
—
1
—
3
67
—
—
—
1
68
—
—
—
1
69,70
—
1
—
2
71
1
2
2
1
72
—
—
—
1
73,74
4
7
Q
6
75,76
1
1
7
5
77
1
1
1
4
78
3
4
5
4
79
1
1
1
3
80
—
—
—
1
81
1
2
2
2
82
6
7
9
6
83
3
4
4
3
84
11
10
13
5
85,86
2
2
2
1
87
3
3
3
1
88
1
1
2
1
89
1
1
--
—
90
1
1
1
—
91
2
2
2
1
92,93
2
2
2
—
94
3
2
3
—
95
1
1
1
—
96
4
2
2
—
97
1
1
1
--
98,99
2
—
1
—
Percentages were calculated based on the peak area of
individual (or groups of inseparable) compounds as a
fraction of total area.
^Butane peak not added into totals, probably a residue
from the previous working capacity analysis.
c— is less than 1
F-18
-------
APPENDIX F-8 PERCENTAGE OF DETAILED HYDROCARBONS IN HOT
PURGED CHARCOAL EFFLUENT FROM 50 g SAMPLES FROM
IN-USE SWRI EVAPORATIVE CANISTERS (DOE FLEET)3
Compound
Canister Number
Number
201
202
205
206
101
102
104
106
20
__b
1
_ _
__ _
NDC
22,23
—
1
—
—
—
ND
24
—
1
—
—
—
ND
27,28
—
—
1
2
—
—
—
ND
35
—
—
—
1
—
—
—
ND
37,38,39
—
—
—
1
—
—
—
ND
41,42
2
3
2
6
2
3
—
ND
45
2
3
1
5
2
2
2
ND
4 6
4
5
2
8
4
4
2
ND
47
3
4
2
5
3
3
2
ND
52,53
4
4
2
5
2
3
2
ND
54
3
3
1
3
3
3
2
ND
55
3
3
1
3
3
3
2
ND
56,57
8
10
5
8
8
9
9
ND
58,59,60
7
7
3
6
5
6
3
ND
61,62
6
6
3
5
5
5
3
ND
63
4
3
2
2
3
3
1
ND
66
5
4
2
3
3
4
2
ND
67
1
1
—
—
1
1
—
ND
68
1
1
—
—
1
1
—
ND
69,70
2
2
1
1
1
2
1
ND
71
2
1
1
1
2
2
2
ND
72
1
—
1
—
—
1
—
ND
73,74
1 1
6
4
5
10
7
i *)
ND
75,76
1 1
2
3
1
1
1
ND
77
2
2
2
1
2
2
1
ND
78
3
2
2
2
4
3
5
ND
79
1
1
2
—
1
1
1
ND
81
1
1
2
1
1
1
1
ND
82
4
3
8
3
6
5
7
ND
83
1
1
3
1
2
1
2
ND
84
3
3
10
3
4
—
9
ND
85,86
—
—
1
1
—
4
1
ND
87
—
—
2
1
1
1
2
ND
88
—
—
1
—
—
—
1
ND
90
—
—
1
—
—
—
1
ND
91
—
—
1
—
—
—
1
ND
92,93
—
—
1
—
—
—
1
ND
94
—
1
2
1
—
—
2
ND
96
—
—
2
1
—
—
1
ND
Percentages were calculated based on the peak area of individual (or groups
of inseparable) compounds as a fraction of total area,
b-- is less than 1
CND - No Data r 1 a
-------
APPENDIX F-9. PERCENTAGE OF DETAILED HYDROCARBONS IN
PURGED CHARCOAL EFFLUENT FROM 50 g SAMPLES FROM
IN-USE EPA EVAPORATIVE CANISTERS3
Compound
Canister Number (A148- )
Number
0008
0049 0073
0039 0060
0096
22,23
__b
_ _
27,28
1
—
1
as 1
35
2
i
1
37,38,39
1
—
— ——
40,41,42
9
3
6
3 5
2
45
4
2
4
1 3
1
46
21
5
8
3 11
12
47
4
2
3
2 3
2
50
—
—
1
-- --
52,53
5
3
4
1 3
3
54
5
3
3
1 3
4
55
3
4
3
1 2
4
56,57
7
11
12
3 5
7
58,59,60
4
4
5
2 3
3
61,62
3
4
4
1 3
2
63
1
1
1
1 1
2
64
--
—
1
—
65
—
—
1
— —
„
66
2
2
2
2
2
69,70
1
1
1
i i
1
71
2
3
2
1 2
1
73,74
5
13
10
3 7
75,76
1
1 1
1
77
1
1
1
1 1
1
78
2
5
3
2 3
79
—
1
1
1
1
81
—
1
1
3 1
1
82
2
4
2
1 5
5
83
1
1
1
3 2
2
84
2
4
3
2 6
6
85,86
—
—
—
.. 1
1
87
—
1
1
.. 1
2
88
—
—
__
1
90
—
—
—
1
1
91
—
—
__
__ t
1
92,93
—
1 1
1
94
—
1
1
96
—
1
—
1
1
Percentages were calculated based on the peak area of individual
(or groups of inseparable) compounds as a fraction of total area.
b— is less than 1
F-20
-------
f
APPENDIX G
PERCENTAGE OF PARAFFINS, OLEFINS, AND AROMATICS
-------
APPENDIX G-l. PERCENTAGE OF PARAFFINS, OLEFINS, AND AROMATICS
IN PURGED CHARCOAL EFFLUENT FROM 50 g SAMPLES FROM
IN-USE EVAPORATIVE CANISTERS*
Canister
Identification
Purge
Cycle
Paraffins
Olefins
Aromatics
TVA 2090
cold
__b
2099
cold
55
6
39
8887
cold
48
17
35
1991
cold
60
3
37
2067
cold
44
2
54
8961
cold
61
8
31
Avg .
53
7
39
TVA 2090
hot
22
0
78
2099
hot
36
2
62
1925
hot
24
0
76
8887
hot
58
0
42
1991
hot
29
0
71
2067
hot
25
0
75
1725
hot
30
2
68
1747
hot
25
0
75
8961
hot
52
2
46
8902
hot
61
2
38
Avg .
36
1
63
DOE 201
hot
81
0
19
202
hot
75
0
25
205
hot
50
0
50
206
hot
75
0
25
101
hot
61
0
39
102
hot
74
0
26
104
hot
47
0
53
106
hot
--
--
--
Avg .
66
0
34
i
OO
¦a-
<
<
a,
UJ
19
0008
hot
81
0
0049
hot
65
0
35
0073
hot
71
6
23
0039
hot
47
0
53
0060
hot
60
0
40
0096
hot
61
0
39
Avg .
64
1
35
aPercentages were calculated based on peak areas of paraffins, olefins,
and aromatics as a fraction of the sum of the group area.
^No data
G-2
------- |