&EPA
United States
Environmental Protection
Agency
Office of Mobile Source Air Pollution Control
Emission Control Technology Division
2565 Plymouth Road
Ann Arbor, Michigan 48105
Air
Additional Mini-Canister
Evaluation
EPA 460/3-85-010
December 1985
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EPA 460/3-85-010
Additional Mini-Canister Evaluation
by
Lawrence R. Smith
Southwest Research Institute
6220 Culebra Road
San Antonio, Texas 78284
Contract No. 68-03-3162
Work Assignment 29
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 fulfillment of
Work Assignment No. 29 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 or product names is not to be considered as an endorsement by the
Environmental Protection Agency.
Publication No. EPA-460/3-85-010
11
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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
program, authorized by Work Assignment 29 under Contract 68-03-3162, was
initiated March 11, 1985 and completed in August 1985. This program was
identified within Southwest Research Institute as Project 03-7338-029. The
EPA Project Officer for the program was Mr. Craig A. Harvey of the Emission
Control Technology Division, Ann Arbor, Michigan. The SwRI Project Leader
and principal researcher for the project was Dr. Lawrence R. Smith. Mr.
Charles T. Hare was Project Manager and was involved in the initial technical
and fiscal negotiations and subsequent major program decisions.
ill
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ABSTRACT
This program involved the continuation of testing on charcoal mini-
canisters that were developed and previously tested in Work Assignment 12 of
this Contract. The results of the previous study are reported in EPA Report
No. 460/3-84-014. In this study, additional testing was conducted both on mini-
canisters previously exposed to a hydrocarbon-only blend, and on mini-canisters
previously exposed to a hydrocarbon-methanol blend. Switching of exposure
blends (between the hydrocarbon-only and the hydrocarbon-methanol blend) on
the same set of mini-canisters was also undertaken to determine if any of the
effects of the previous blend exposure were reversible. Breakthrough times,
working capacities and canister weight gains were monitored for each of the
mini-canisters during all testing. Laboratory humidity, temperature, and
barometric pressure were also monitored to determine the effect of these
parameters on mini-canister working capacity and weight gain. Hydrocarbon
and methanol speciation were conducted on the vapors purged from eight of the
canisters (four from the hydrocarbon-methanol blend exposures and four from
the hydrocarbon-only blend exposures).
IV
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SUMMARY
Detailed testing was conducted on charcoal mini-canisters developed and
previously tested in Work Assignment 12 of this Contract. The charcoals used
in these studies had been obtained from new evaporative canisters ordered for
four vehicle types: a 1983 Chrysler Reliant K, 1984 Ford Escort, a 1983
Chevrolet Monte Carlo, and a 1983 Toyota Corolla. The testing was conducted
with a bench-scale apparatus designed to repeatedly load either a hydrocarbon-
only blend (butane, isobutylene, and toluene) or a hydrocarbon-methanol blend
(methanol, butane, isobutylene, and toluene) onto separate sets of twelve
reduced size mini-canisters, and to purge off the hydrocarbons (and methanol)
after each loading. The charcoals were evaluated by the measurements of
retained charcoal weight after purging, time to hydrocarbon breakthrough, and
charcoal working capacity.
The additional testing in this study was conducted in three tasks and
involved both the mini-canister charcoal samples previously exposed to the
hydrocarbon-only blend and those exposed to the hydrocarbon-methanol blend.
In the first task, loading and purging of the mini-canisters previously exposed to
the hydrocarbon-methanol blends in Work Assignment 12 were continued until
the cumulative loading (this study and Work Assignment 12) was approximately
equal to the cumulative loading of the mini-canisters exposed to the
hydrocarbon-only blend in Work Assignment 12. (This had not been done in that
work assignment due to time limitations.) In the second task, both sets of
mini-canister charcoals were subjected to changes in exposure blends (charcoal
previously exposed to the hydrocarbon-only blend was exposed to the
hydrocarbon-methanol blend, and vice versa). During this task, daily humidity,
temperature, and barometric pressure measurements were recorded. The third
task involved the speciation of vapors purged from eight of the mini-canisters
(four from the hydrocarbon-methanol blend exposures in the first task, and four
from the hydrocarbon-only blend exposures in the second task). The procedures
used to purge and analyze the vapors from the charcoal samples were developed
at Southwest Research Institute (SwRI) in Work Assignment 27 of this contract.
Both room temperature and elevated temperature purges were conducted on the
samples.
The most significant observations made from the data in this study (not
necessarily in order) are as follows:
In general, on a per gram of charcoal basis, the working capacities
were larger, the breakthrough times were shorter, and the weight
gains larger for the mini-canisters exposed to the hydrocarbon-only
blend as compared to the mini-canisters exposed to the
hydrocarbon-methanol blend. However, when the day-to-day
variations in the hydrocarbon-methanol blend values (this study) and
the variations in test conditions are taken into consideration, it is
difficult to quantify any meaningful difference between for the two
blends on a per gram of charcoal basis.
Ford and Toyota charcoal had longer breakthrough times and larger
working capacities than either the GM or Chrysler charcoal on a per
gram of charcoal basis for exposure to both blends.
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In general, the switch to the hydrocarbon-only blend after the Task
1 testing of the mini-canisters with the hydrocarbon-methanol blend
produced lower working capacities, shorter breakthrough times
(except for the Toyota charcoal), and less weight gain (except for
the Toyota charcoal). It should be noted that in addition to the
change in blend composition, the use of bypass valves was initiated
during this portion of the testing, and that some of the differences
in working capacity and weight gain may be related to the use of the
bypass valves. However, this does not explain the apparent
contradiction between the findings of lower working capacity and
less weight gain for HC-only versus the HC-methanol blends.
In comparing the three sets of average results for the switching of
the exposure blend from hydrocarbon-only to hydrocarbon-methanol
and back to hydrocarbon-only, there is in all cases an overlap of
standard deviations for working capacity, breakthrough time, and
weight gain values, which indicates that no significant difference
was found due to the presence of methanol.
In one segment of the testing, variations in laboratory humidity
were found to have a high correlation with variations in mini-
canister weight gain and working capacity. Linear regression plots
of daily working capacities and weight gains versus daily laboratory
humidity in grains of water per cubic foot of air gave r2 values from
0.74 to 0.82 for weight gain and 0.63 to 0.78 for working capacity
(excluding r2 of 0.18 and 0.28 for Toyota working capacities). This
observation indicates that variations in laboratory humidity must be
taken into consideration when evaluating charcoal samples in this
manner.
Butane and isobutylene are removed for the most part from mini-
canister charcoals during room temperature purging, however, only
a small fraction of toluene is removed from the mini-canister
charcoal during room temperature purging. This observation
indicates that toluene plays a more important role in mini-canister
weight gain than either butane or isobutylene.
While all four charcoal types show similar purge characteristics for
butane, isobutylene, and toluene, there are considerable differences
in relation to methanol. For the Chrysler and GM mini-canisters,
only one half of the detectable methanol can be purged from the
charcoal during room temperature purging, while 85 to 94 percent of
the methanol can be removed from the Ford and Toyota canisters,
respectively, during the room temperature purges. This observation
indicates that methanol may be more important in weight gain
increases and working capacity decreases for the Chrysler and GM
charcoals than for the Ford or Toyota charcoals. Excluding water,
methanol amounted to 15-18 percent of the total weight from the
Chrysler and GM mini-canisters and 4-5 percent of the weight from
the Ford and Toyota mini-canisters. However, when the water
weight was included, the methanol only amounted to 3-5 percent of
the total weight purged from any of the canisters. When comparing
VI
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the ratio of butane to methanol in the four types of charcoal, there
is an enrichment of methanol in the Chrysler and GM charcoals and
a slight depletion of methanol (small amount of methanol pass
through?) in the Ford and Toyota charcoals.
In the purging experiments, considerably more water was found in
the Chrysler and GM charcoals than in the Ford and Toyota
charcoals. This observation indicates a relation between the
affinity of the four charcoal types for water and methanol, with the
Chrysler and GM charcoals having a higher affinity for both
methanol and water than the Ford and Toyota charcoals. The levels
of water in the canisters do not appear to be a result of methanol,
however, as both the charcoals exposed to the hydrocarbon-only and
the hydrocarbon-methanol blends gave similar water levels for each
charcoal type.
vii
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TABLE OF CONTENTS
FOREWORD iii
ABSTRACT iv
SUMMARY v
LIST OF TABLES xi
LIST OF FIGURES xii
I. INTRODUCTION I
A. Project Objective 1
B. Approach and Scope 1
II. PROCEDURES 3
A. Equipment and Procedures Used in Task 1 and 2 Testing 3
1. Mini-Canisters 3
2. Charcoal 6
3. Hydrocarbon and Methanol Blend Compositions 7
4. Hydrocarbon Breakthrough 7
5. Breakthrough Time, Mini-Canister Weight Gain, and
Working Capacity Measurements 7
B. Equipment and Procedures Used in Task 3 Testing 8
1. Sampling System 8
2. Analytical Procedures 12
a. The Measurement of Methanol 12
b. The Measurement of Water Content 12
c. The Measurement of Detailed Individual
Hydrocarbons 13
III. MINI-CANISTER TESTING 15
A. Task 1 - Continuation of Hydrocarbon-Methanol Blend
Charcoal Testing 15
B. Task 2 - Switching of Exposure Blends 17
C. Task 3 - Purge/Speciation of Mini-Canister Charcoal 19
IX
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TABLE OF CONTENTS (CONPD)
Page
IV. RESULTS 21
A. Task 1 - Continuation of Hydrocarbon-Methanol Blend
Charcoal Testing 21
B. Task 2 - Switching of Exposure Blends 25
1. Switching of HC-Methanol Blend to HC-Only Blend
(Using Task 1 Mini-Canister Charcoals 25
2. Switching of Exposure Blends (Using Charcoal Exposed to
the HC-Only Blend in Work Assignment 12) 25
C. Task 3 - Purge/Speciation of Mini-Canister Charcoal 31
V. QUALITY ASSURANCE 33
REFERENCES 35
APPENDICES
A - Exposure Summaries for Tasks 1 and 2
B - Daily Working Capacities, Breakthrough Times and Weight Gains
for Task 1 Testing
C - Daily Working Capacities, Breakthrough Times and Weight Gains
for Task 2 Testing (HC-Methanol Mini-Canisters Exposed to HC-Only
Blend)
D - Daily Working Capacities, Breakthrough Times, and Weight Gains
for Task 2 Testing (Continuation of HC-Only Blend Exposure for
HC-Only Mini-Canisters)
E - Daily Working Capacities, Breakthrough Times, and Weight Gains
for Task 2 Testing (HC-Only Mini-Canisters Exposed to HC-Methanol
Blend)
F - Daily Working Capacities, Breakthrough Times, and Weight Gains for
Task 2 Testing (Re-exposure of HC-Only Mini-Canisters to HC-Only
Blend)
G - Mini-Canister Daily Environment
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LIST OF TABLES
Table Page
1 Charcoal Weights (HC-Methanol Exposures) 16
2 Charcoal Weights (HC-Only Exposures) 18
3 Charcoal Weights for Samples Undergoing Task 3 Speciation 20
4 Comparison of Working Capacities for Canisters Exposed
to a HC-Methanol Blend and to a HC-Only Blend 22
5 Comparison of Breakthrough Times for Canisters Exposed
to a HC-Methanol Blend and to a HC-Only blend 23
6 Summary of Weight Gain for Mini-Canisters Exposed to the
HC-Methanol Blend 24
7 Comparison of Weight Gain for Canisters Exposed to a
HC-Methanol Blend and to a HC-Only Blend 24
8 Comparison of Working Capacities, Breakthrough Times, and
Weight Gain for Seven Mini-Canisters with the HC-Methanol
Blend and with the HC-Only Blend 26
9 Comparison of Working Capacities, Breakthrough Times, and
Weight Gains for Twelve Mini-Canisters Exposed to a HC-Only
Blend in Work Assignment 12 and this Work Assignment 28
10 Comparison of Average Working Capacity, Breakthrough Time,
and Weight Gain for Eight Mini-Canisters Exposed to Both
HC-Only, then HC-Methanol, and then to HC-Only Blends 29
11 Linear Regression Plots of Humidity Versus Working Capacity
and Weight Gain for the Eight Mini-Canisters Exposed to the
HC-Methanol Blend 30
12 Results Purge/Speciations 31
13 Precision, Accuracy, and Completeness Objectives for Break-
through Time, Weight Gain, and Working Capacity Analyses 33
14 Precision, Accuracy, and Completeness Objectives for
Methanol, Water, and Selected HC Speciation Analyses 34
XI
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LIST OF FIGURES
Figure
1 Several views of the charcoal evaluation apparatus 4
2 Flow schematic of charcoal evaluation apparatus 5
3 Weighing metal charcoal holder 9
k Schematic of charcoal purge and sampling system 10
5 Charocal purge and sampling system 11
XII
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I. INTRODUCTION
Southwest Research Institute (SwRI) has been involved in a number of
projects for the Environmental Protection Agency (EPA) to determine the
effects of alcohol fuels on vehicular fuel evaporative emission control
systems.(l»2»3»4)* One of these programs (Work Assignment 12 of EPA contract
68-03-3162, EPA Publication 460/3-81-029) led to the development of miniature
evaporative charcoal canisters and a prototype system for simulating
evaporative charcoal canister operation/D In this previous study, the charcoals
from four types of unused evaporative charcoal canisters were subjected to
repeated loading and purging of either a hydrocarbon vapor blend containing
methanol, or a hydrocarbon-only blend. The charcoals were evaluated by the
measurement of retained weight, time to hydrocarbon breakthrough, and
working capacity. This report describes further detailed testing of the charcoal
mini-canisters developed and tested in Work Assignment 12.
A. Project Objective
The objective of this study was to continue Work Assignment 12
evaluations in order to provide additional information as to the effects of
methanol on evaporative canister charcoal. Testing was carried out in order to
investigate the effects of equivalent exposures of either hydrocarbon-only or
hydrocarbon-methanol blends on two sets of mini-canisters, and to determine
the effects of switching exposure blends (from hydrocarbon-only to
hydrocarbon-methanol and vice versa) on the mini-canisters. Time to
hydrocarbon breakthrough, retained weight gain, and charcoal working capacity
were monitored daily during testing. Although not included in the original
Scope of Work for the program, daily laboratory humidity, temperature, and
barometric pressure were recorded during a portion of the testing to evaluate
the effects of these parameters on the breakthrough time, weight gain, and
working capacity measurements. In another phase of the program, mini-
canister charcoal samples were subjected to room temperature and elevated
temperature purges using equipment and procedures developed and qualified in
another work assignment for this contract (Work Assignment 27)^), which
involved the evaluation of in-use evaporative charcoal canisters. The effluent
purged from the canisters in this phase of the study was analyzed for methanol,
individual hydrocarbons, and water to permit further evaluations as to the
effect of methanol on evaporative canister charcoal.
B. Approach and Scope
To effectively accomplish the project objectives, the project was carried
out in three tasks. In the first task, the eleven mini-canisters previously
exposed to a hydrocarbon-methanol blend in Work Assignment 12 were
subjected to additional blend loading and purging until approximately the same
cumulative loading as that for mini-canisters exposed to the hydrocarbon-only
blend in Work Assignment 12 was accomplished, and until stable breakthrough
* Numbers in parenthesis designate references at the end of this report.
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times, weight gains, and working capacities were achieved over a 3 to 4 day
period. Breakthrough times were recorded for each mini-canister during each
load cycle. Weight gain and working capacity were recorded daily for each
mini-canister. At the completion of Task 1, the eleven mini-canisters were
exposed to the hydrocarbon-methanol blend one more time to breakthrough;
then the charcoal was removed from four of the mini-canisters and stored for
subsequent speciation in Task 3.
Task 2 investigated the effect of switching exposure blends and consisted
of two parts. In the first part the remaining seven Task 1 mini-canisters were
subjected to additional exposures with a hydrocarbon-only blend. The second
part of Task 2 involved the continued testing of charcoal previously exposed to
a hydrocarbon-only blend in Work Assignment 12, and the subsequent switching
of the exposure blends. Breakthrough times, weight gains, and working
capacities were also monitored during Task 2 testing. In addition, laboratory
humidity, temperature, and barometric pressure were recorded daily during
Task 2. An additional four rnini-canisters were stored for Task 3 speciation in
Task 2.
In the third task, the eight charcoal samples saved from Tasks 1 and 2
were subjected to room temperature and high temperature purges with a stream
of dry nitrogen, using procedures and apparatus developed in Work Assignment
27 of this contract. The effluent vapors from both the room temperature and
high temperature purges of the charcoal samples were analyzed for butane,
isobutylene, toluene, methanol, and water using analytical techniques also
developed and/or applied in Work Assignment 27.
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II. PROCEDURES AND INSTRUMENTATION
This section describes the procedures and instrumentation utilized in this
project. The charcoal mini-canisters, the apparatus developed to allow
repeated loading and purging of hydrocarbons from the mini-canisters, and the
procedures used to measure hydrocarbon breakthrough times, weight gain
retained on the mini-canisters, and the mini-canister working capacity, were all
developed in Work Assignment 12 of this contract^) and have been applied to
the Task 1 and Task 2 testing conducted in this program. The apparatus and
procedures used for the room temperature and high temperature purging of the
mini-canister charcoal and the subsequent speciation of the effluent were
developed in Work Assignment 27 of this contract^) and have been used in Task
3 testing. The procedures and equipment as used in this study are described
briefly in the following sections. A more in-depth description may be found in
the cited references.
A. Equipment and Procedures used in Task 1 and 2 Testing
The bench scale apparatus for evaluating evaporative canister charcoal is
shown in several views in Figure 1. The mini-canister system is composed of a
hydrocarbon source (liquids and compressed gases); a series of valves,
flowmeters, and tubing to direct equal flows to the mini-canisters; a vacuum
pump for purging with room air; and a hydrocarbon analyzer and recorder. The
flow schematic of the apparatus is shown in Figure 2. The fuel and delivery
gases were set to 20 psig at the cylinder regulator and were individually
controlled with needle valves to achieve the desired proportion of butane,
isobutylene, toluene, and methanol (as needed). Load and purge cycles were
controlled by a timer which automatically switched the purge pump and the fuel
solenoid valves on and off. Total hydrocarbon concentrations could be
monitored at the exit to individual canisters or in the purge manifold before the
pump. A sample line to the HC analyzer allowed sequential hydrocarbon
analyses to determine break-through time for each mini-canister. A second
vacuum pump, which was manually operated, was used to remove hydrocarbons
which broke through the mini-canisters. The apparatus was modified for Task
2 testing by the installation of bypass valves to allow the hydrocarbon vapor
flow to bypass each canister as it reached breakthrough.
1. Mini-Canisters
The mini-canisters that were used during experimentation were
made of an acrylic tube (5 3/4 in. long, 1 in. diameter) with a threaded
aluminum cap. The volume of each mini-canister was approximately 7k
milliliters. The bottom of each canister was capped by a polypropylene cap
with a large hole cut from the center. A metal screen was inserted into the cap
to retain the charcoal while allowing vapors or air to pass freely. A large hole
(5/8 in) was drilled into the canister top for a purge outlet, and a smaller hole
(1/16 in) was drilled in the side of the canister top for fuel delivery. A screen
was placed in the purge opening to prevent charcoal from being pulled off while
under vacuum. In addition, glass wool was used at the purge opening and at the
bottom cap to prevent the loss of charcoal dust.
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Charcoal Evaluation Apparatus
Measuring Hydrocarbon Breakthrough
Toluene and Methanol Delivery System
Figure 1. Several Views of the Charcoal Evaluation Apparatus
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To
Fume
Hood
Purge
Manifold
Fuel Manifold
Total of 12
Mini-Canisters
To
Fume
Hood
Figure 2. Flow schematic of charcoal evaluation apparatus
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2. Charcoal
All charcoal used in this program had been previously tested in Work
Assignment 12. The Work Assignment 12 charcoal consisted of four types of
activated charcoal obtained from new evaporative canisters ordered for four
vehicle types. Charcoal weights and volumes contained in the canisters are
listed as follows:
Typical Standard Approximate Approximate
Size Canister Volume of Density3
Charcoal Weight, g Charcoal, ml %/ml
1983 Chrysler Reliant K 344 1270 0.27
1983 Ford Escort 407 1030 0.40
1983 Chevrolet Monte Carlo 438 1500 0.29
1983 Toyota Corolla 362 870 0.42
a According to information from a charcoal supplier, Chrysler and GM charcoal are
believed to be wood based, while Ford and Toyota charcoal are coal based.
Different charcoal mesh sizes could also affect the density.
The clean charcoal weights (from Work Assignment 12) used in the mini-
canisters are listed below:
Charcoal Weight, g
Charcoal HC Blend HC-Methanol Blend
Chrysler 1 18.9a 18.9
Chrysler 2 17.6a 17.2
Ford 1 27.9 28.4
Ford 2 27.5 31.1
Ford 3 27.9 26.5
Ford 4 27.9
GM 1 19.5 22.3
GM 2 18.5 20.5
GM 3 19.5 21.1
Toyota 1 29.1 34.1
Toyota 2 29.0 31.8
Toyota 3 28.8 29.1
aAs a result of variations in the mini-canister volumes, only 96%
of Chrysler 1 and 89.5% of Chrysler 2 charcoal (by weight) used
in Work Assignment 12 could be placed in the mini-canisters used
in this Work Assignment. To permit comparisons between the
two work assignments, the actual Work Assignment 12 values
have been multiplied by 0.960 (Chrysler 1) and 0.895 (Chrysler 2).
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3. Hydrocarbon and Methanol Blend Compositions
The compositon of the hydrocarbon and hydrocarbon-methanol
blends as used in this study, and for comparison those used in Work Assignment
12, are presented below:
This Work Assignment
Mini-Canister Flow, mg/min
Hydrocarbon Component
Butane
Isobutylene
Toluene
Methanol
Total
HC
29.4
7.0
2.0
0.0
38.4
HC-Methanol
27.0
6.4
2.0
2.9
38.3
Work
Assignment 12
Mini-Canister Flow, mg/min
HC
31
7
2
_0_
40
HC-Methanol
29
7
2
2
40
The HC-methanol blend composition is based on calculated mass flow rates
(butane and isobutylene), individual hydrocarbon speciation (butane, isobutylene,
and toluene)* and wet chemistry collection with GC analysis (methanol).
4. Hydrocarbon Breakthrough
Hydrocarbon vapors were delivered to the canisters at the above
flowrates to establish hydrocarbon breakthrough times. In Task 1, the length of
the load cycle was based on the longest breakthrough time of the twelve
mini-canisters. With the use of bypass valves in Task 2, the length of the load
cycle varied with the length of the breakthrough time because the hydrocarbon
flow was diverted at breakthrough. The purge cycle for all Task 1 and Task 2
testing was 110 minutes. Hydrocarbon breakthrough was determined to occur
when the hydrocarbons passing through the mini-canisters reached a 1000 ppmC
concentration. The hydrocarbons were monitored continuously during the load
cycle to determine breakthrough, and during the purge cycle to monitor the
hydrocarbon levels, by the use of a Beckman 402 Hydrocarbon Analyzer.
Working
5. Breakthrough Time, Mini-Canister Weight Gain, and
Capacity Measurements
Breakthrough time is the time lapse between the initiation of the
mini-canister hydrocarbon loading and breakthrough, and is measured with a
pre-programmed electronic timer. The hydrocarbon level emitted by the
mini-canister is monitored continuously to breakthrough (defined as 1000
ppmC), at which point the timer reading is recorded. The hydrocarbon
concentration is read from a strip chart recorder connected to a Beckman 402
Hydrocarbon Analyzer.
* This method was developed in Work Assignment 27, and was not available for
use in the Work Assignment 12 flow rate determinations.
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Mini-canister weight gain is the gain in weight by the mini-canister
after a designated purge cycle as compared to a predetermined cansister weight
(clean weight, weight at the end of Work Assignment 12, etc.) For these
determinations, the mini-canisters were weighed after designated purge cycles
using a top-loading balance.
Working capacity is defined as the difference between the weight of
the mini-canister after hydrocarbon loading to breakthrough and the weight of
the mini-canister after the 110 minute purge cycle. The weight difference is
the amount of fuel vapor that is adsorbed by the charcoal during the load cycle
and removed by the purge cycle.
B. Equipment and Procedures Used in Task 3 Testing
The procedures and instrumentation required to sample and analyze
alcohols, water, and hydrocarbons purged from mini-canister charcoal samples
at room temperature and at high temperature (355-375°F, 180-190°C) are
described in this section. The sampling system was designed to remove
compounds retained on charcoal in a stream of nitrogen. Impingers were used
to sample methanol, Drierite to sample water, and Tedlar bags for hydrocarbons
(butane, isobutylene, and toluene). Gas chromatography was used to analyze
methanol and hydrocarbons, and water content was measured by Drierite weight
gain.
1. Sampling System
The charcoal from each mini-canister 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. A view of the canister is shown in Figure 3. 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
canister, consisted of two chambers: one for room-temperature and one for
heated purging. A schematic of the sampling system is shown in Figure 4, and
views of the system are shown in Figure 5. 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 precaution reduced
the possibility of room air being drawn into the purge system.
A Thomas dual-head pump, operating at approximately 42 £/rnin (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 methanol, water content, bag
hydrocarbon, and continuous hydrocarbon analyses. Methanol was sampled in
impingers, and water in a Drierite tube at sample flowrates of about 4 £/min;
and bag hydrocarbons were collected at approximately 1 £ /min. A continuous
hydrocarbon analyzer, Beckman Model 400, was operated according to the
manufacturer's specifications to monitor the sample stream for hydrocarbons.
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Figure 3. Weighing metal charcoal holder
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Cold Purge Unit
To Vent Hood
To HC Analyzer
Regulating
Valve
/) Magnehelic
V
Charcoal
Container
Drierite
Dryer
3-Way Valve
Heated Sample Line
To Vent Hood
Charcoal
Container
Impingers
in Ice Bath
Hot Purge Unit
Figure 4. Schematic of charcoal purge and sampling system
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Cold and Hot Purge Units
Sampling Cart
Figure 5. Charcoal purge and sampling system
I i
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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).
2. Analytical Procedures
Charcoal effluent samples were analyzed by several procedures.
Impinger samples were analyzed for methanol, a Drierite tube was weighed
before and after testing to determine water content, and bag samples were
analyzed for detailed individual hydrocarbons. The procedures are described in
this section.
a. The Measurement of Methanol
Methanol was sampled by bubbling the charcoal effluent during
a cold or hot purge cycle through two glass impingers in series, each containing
25 mfof deionized water. The temperature of the impingers was maintained at
0 to 5°C by an ice bath, and the flow rate through the impingers was
maintained at 4 £/min by a sample pump. The samples were transferred to
polyethylene containers after completion of a cold or hot purge cycle.
The methanol samples were analyzed on a Perkin-Elmer 3920B
gas chromatograph (GC) equipped with a flame ionization detector. A 5 M£
portion of the sample was injected into the GC and analyzed isothermally at
105°C. Sample peak areas were compared to external standards to obtain
alcohol concentrations in /ug/m3. These values were converted to g of methanol
using the following equation:
grams methanol = (concentration, /ug/m3) x (purge flowrate, ft3/min)
x (purge time, min) x (0.028317 m3/ft3) x (10-6g/ng)
b. The Measurement of Water Content
Water is sampled from the charcoal effluent during the cold or
hot purge cycle using a preweighed 4 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 as follows:
water content, grams = (Drierite wt. gain, g) x (purge flowrate, ft^/min)
x (purge time, min) x
flow through Drierite tube, ft
Y 29.92 in Hg (temperature. °F + 460) °R
X
barometer, in Hg 528°R
12
-------
c. The Measurement of Detailed Individual Hydrocarbons
Butane, isobutylene, and toluene were collected in Tedlar bags
at approximately 1 £/min during the cold or hot purge cycle and analyzed using
a gas chromatographic (GC) system. The GC system permits the quantitative
determination of more than 80 hydrocarbons with carbon numbers 4 to 10. The
capillary column used to separate the compounds is a Perkin-Elmer F-50
versilube, 150 ft x 0.020 inch WCOT stainless steel column. The column is
initially cooled to -95°C for sample injection. Upon injection, the
temperature is programmed at a 4°C increase per minute to 85°C. The column
temperature is held at 85°C for approximately 15 minutes to permit complete
column flushing. A flow controller is used to maintain a 1.5 ml/min carrier
flow rate. The 10 m£ sample volume for C^-C^o permits accurate determi-
nation of 0.1 ppmC 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, and the relative FID response factors for benzene, toluene,
butane, and isobutylene.
13
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MINI-CANISTER TESTING
Additional detailed testing was conducted on the charcoal mini-canisters
developed and previously tested in Work Assignment 12 of this contract. This
additional testing was conducted both on the mini-canister charcoal samples
previously exposed to a hydrocarbon-only blend and on the mini-canister
charcoal samples previously exposed to a hydrocarbon-methanol blend. In Task
1, loading and purging of the eleven mini-canisters that were previously exposed
to the hydrocarbon-methanol blend in Work Assignment 12 was continued with
the hydrocarbon-methanol blend. This loading and purging was continued until
the cumulative loading (this study and Work Assignment 12) was approximately
equal to the cumulative loading of the mini-canisters exposed to the
hydrocarbon-only blend in Work Assignment 12, and until stable breakthrough
times, working capacities, and weight gains were achieved. In Task 2, both sets
of mini-canister charcoals were subjected to changes in exposure blends
(charcoal previously exposed to the hydrocarbon-only blend was exposed to the
hydrocarbon-methanol blend, and vice versa) to determine the resulting effects
on the mini-canister breakthrough times, working capacities, and weight gains.
During Task 2 testing, daily humidity, temperature, and barometric pressure
measurements were initiated. Task 3 testing involved the hydrocarbon and
methanol speciation of vapors purged from eight of the mini-canisters (four
from the hydrocarbon-methanol blend exposures in Task 1 and four from
hydrocarbon-only blend exposures in Task 2). The procedure used to purge and
analyze the vapors from the charcoal samples was developed by SwRI in Work
Assignment 27 of this contract. Both room temperature and elevated
temperature purges were conducted on the samples. The remainder of this
section describes in detail the testing conducted in these three tasks.
A. Task 1 - Continuation of Hydrocarbon-Methanol Blend Charcoal Testing
Each mini-canister previously exposed to the HC-methanol blend in Work
Assignnment 12 was weighed (on 4/29/85) before testing was initiated in Task 1.
These weights, along with the clean charcoal weights (Work Assignment 12) and
the weights at the end of the 7th day of loading and purging with the HC-
methanol blend in Work Assignment 12 are presented in Table 1. As can be seen
in the table, all eleven of the mini-canisters lost a significant amount of the
weight gained in Work Assignment 12. The HC-methanol blend composition
used in this study, along with the composition of the blend as used in Work
Assignment 12, was presented in Section II. A. 3.
The eleven mini-canisters were exposed to a 3-hour continuous loading of
HC-methanol blend followed by a 110-minute purge (to 230 ppm) on April 30, and
a 3-hour continuous loading of HC-methanol blend followed by a 25-minute
purge (to 2800 ppm) on May 1. Breakthrough times were not recorded for these
cycles, but weight gain and working capacities were recorded. The three-hour
load followed by a 25-minute purge was carried out to expose the charcoal to a
load-purge sequence of HC-methanol similar to that which occurred on Day 8
with the HC-only blend in Work Assignment 12.
15
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TABLE 1. CHARCOAL WEIGHTS (HC-METHANOL EXPOSURES)
Type of
Charcoal
Chrylser 1
Chrysler 2
Ford 1
Ford 2
Ford 3
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
Clean
Charcoal Weight a,g
18.9
17.2
28.4
31.1
26.5
22.3
20.5
21.1
34.1
31.8
29.1
Charcoal Weight, g,
End of Work Assign. 12b
22.4
30.1
32.9
28.0
28.7
26.4
27.0
34.8
32.6
30.0
Charcoal Weight, g,
4/29/85
22.4
20.5
29.3
31.8
27.2
26.7
24.3
25.1
34.2
32.0
29.6
aWeights from Work Assignment 12, page 8 of EPA Report 460-3-84-014
bdean charcoal weights plus weight gain for day 7, page A-9 of EPA report 460/3-84-014
The routine load/purge sequence as conducted in Work Assignment 12 was
initiated on 5/1/85 using the 1000 ppmC breakthrough level. After discussions
with the Project Officer, it was decided that the bypass valves installed at the
initiation of this Work Assignment would not be used in Task 1 in order to more
closely duplicate load/purge conditions used in Work Assignment 12. The
valves, which were installed to allow diverting of the flow once breakthrough
was observed, were used only in Task 2. For the remainder of the Task 1
testing, the load cycles were terminated after breakthrough had occurred for
all eleven canisters, with the following purge cycle 110 minutes in duration.
The working capacity and retained weight gain were recorded daily, while
breakthrough times were measured during each cycle for each mini-canister.
Task 1 testing was terminated after 19 load/purge cycles (summarized in
Appendix A-l). This number of cycles gave a cumulative loading of 129 grams
per mini-canister in this Work Assignment and an overall cumulative loading of
197 grams when including the loading in Work Assignment 12. This compares to
155 grams of cumulative loading for the mini-canisters exposed to the HC-only
blend in Work Assignment 12. The cumulative loading with the HC-methanol
blend was allowed to exceed the cumulative loading with the HC-only blend in
an attempt to 1) obtain stable breakthrough times, weight gains, and working
capacities for the mini-canisters, and 2) attempt to compensate for some of the
loss in weight gain between Work Assignment 12 and this Work Assignment.
At the completion of Task 1, the eleven canisters were exposed to the
HC-methanol blend one more time to breakthrough (173 minutes, or 6.63 grams
of blend per canister) and weighed. The charcoal was then removed from four
16
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of the mini-canisters (one representing each manufacturer), sealed in glass
containers, and stored at 6°F for subsequent speciation in Task 3. The
remaining seven mini-canisters were purged for 110 minutes (purge manifold
concentration of 240 ppmC), weighed, and made ready for testing in Task 2.
B. Task 2 - Switching of Exposure Blends
In Task 2, the seven remaining mini-canisters from Task 1 were exposed
to a HC-only blend to determine if any change in working capacity would result.
The composition for the HC-only blend used for this additional exposure was
given in Section II. A. 3. Butane and isobutylene rates were increased in the
blend to give a total exposure rate similar to the rate with methanol present
(38.3 mg/min). The use of the bypass valves was also initiated during this
portion of the testing. The valves permit the vapor to be diverted once
breakthrough has occurred thus limiting any additional loading or change in the
proportions of adsorbed species following breakthrough. As a result, these
mini-canisters were now exposed to varying amounts of HC-only blend
depending on the breakthrough times. The purge time for each load/purge cycle
was maintained at 110 minutes. The mini-canisters were exposed to a total of
14 load/purge cycles (summarized in Appendix A-2) after which the charcoal
was removed from the mini-canisters and stored in sealed polyethylene bottles
at room temperature.
During the next phase of Task 2 the mini-canisters were refilled with the
charcoal that had previously been exposed to the HC-only blend in Work
Assignment 12. These refilled mini-canisters were then subjected first to
additional HC-only blend exposures, second to HC-methanol blend exposures,
and finally to additional exposures with the HC-only blend. The compositions of
the exposure blends were the same as used in Task 1 and in the initial phase of
Task 2. All testing was conducted with the use of the bypass valves to divert
the flow of the exposure vapor once breakthrough had occurred. Moisture
content, barometric pressure, and room temperature were recorded daily during
testing to determine what effect these parameters might have on variability in
mini-canister working capacity, breakthrough time, and weight gain.
For this phase of Task 2, the weight of the charcoal in each of the twelve
mini-canisters was recorded before testing was initiated. These charcoal
weights, along with the clean charcoal weights (Work Assignment 12) and the
weights at the end of the final day of loading and purging with the HC-only
blend in Work Assignment 12 are presented in Table 2. As was the case with
the charcoal samples exposed to the HC-methanol blend in Work Assignment 12,
these charcoal samples had lost a significant amount of the weight that had
been gained in Work Assignment 12. The discrepancy between the clean
charcoal weight and the 5/24/85 charcoal weight for Toyota 3 can not be
readily explained.
The exposure of the twelve mini-canisters to the HC-only blend was
initiated on May 24 and continued until a total of 24 load/purge cycles
(summarized in Appendix A-3) were completed on June 11. On June 12 the
twelve canisters were exposed to the HC-only blend one more time to
breakthrough and weighed. The charcoal was then removed from four of the
17
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TABLE 2. CHARCOAL WEIGHTS (HC-ONLY EXPOSURES)
Clean Charcoal Charcoal Weight, g, Charcoal Weight, g,
Type of Charcoal Weight, g* End of Work Assign. 12b 5/24/85
Chrysler 1 18.9C 26./C 23.8
Chrysler 2 17.6C 24.5C 22.1
Ford 1 27.9 32.9 29.7
Ford 2 27.5 32.4 29.1
Ford 3 27.9 32.8 29.7
Ford 4 27.9 32.8 29.7
GM 1 19.5 26.8 23.5
GM 2 18.5 25.3 21.5
GM 3 19.5 26.6 23.6
Toyota 1 29.1 33.5 30.1
Toyota 2 29.0 33.3 29.9
Toyota 3 28.8 33.2 28.6
aWeights from Work Assignment 12, page 8 of EPA Report
bClean charcoal weights plus weight gain for day 19, page A-6 of EPA Report 460/3-84-014
cAs a result of variations in the mini-canister volumes, only 96.0% of Chrysler 1 and 89.5%
of Chrysler 2 charcoal (by weight) used in Work Assignments 12 could be placed in the
mini-canisters used in this Work Assignment. To permit comparisons between the two Work
Assignments, the actual Work Assignment 12 values have been multiplied by 0.960 (Chrysler 1)
and 0.895 (Chrysler 2)
mini-canisters (one representing each manufacturer), sealed in glass containers
and stored at 6°F for subsequent speciation in Task 3. The remaining eight
mini-canisters were purged for 110 minutes (purge manifold concentration of 115
ppmC), weighed, and made ready for HC-methanol blend exposure. On June 13
the HC-only blend was altered to include methanol, and HC-methanol blend
testing on the remaining eight mini-canisters was initiated. The HC-methanol
blend testing was terminated on June 28 after a total of 20 load/purge cycles
(summarized in Appendix A-4). At this time the blend was changed once again
to exclude methanol, and the eight mini-canisters were made ready for
additional exposure to the HC-only blend.
The additional HC-only exposures were initiated on July 1 and terminated
on July 15 after 10 load/purge cycles (Appendix A-5). On the last cycle of the
last day of testing with the HC-only blend, zero air from a compressed gas
cylinder was used instead of room air for the 110 minute purge cycle for two of
the mini-canisters. This experiment was carried out to investigate the effect
of purging with air containing little or no water on the mini-canister working
capacity and weight gain.
18
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C. Task 3 - Purge/Speciation of Mini-Canister Charcoal
The eight charcoal samples saved from Tasks 1 and 2 were subjected to
both cold (room temperature) and hot (180 to 190°C) purges with a stream of
dry nitrogen using procedures and apparatus developed in Work Assignment 27
of this contract. The effluent vapors from both the cold and hot purges of the
charcoal samples were analyzed for butane, isobutylene, toluene, methanol,
and water using analytical techniques also developed and/or applied in Work
Assignment 27. Humidity was found to be an important variable in Task 2
testing, therefore water was added to the list of compounds analyzed.
The clean charcoal weights, the weight of the charcoal after the last load
cycle (in Task 1 or Task 2), the weight of the charcoal before cold
purge/speciation, and the weight of the charcoal after the not purge speciation
are listed for each of the eight samples in Table 3. In general the weight of the
charcoal after the last load cycle (in Task 1 or Task 2) agreed with the weight
of the charcoal at the time of the Task 3 speciation (within 0.1 to 0.2 grams).
There was, however, a 1.0 to 1.3 gram variation between the Ford charcoal
weights after loading and at the time of the Task 3 speciation. For both Ford
samples, condensation was noted on the sides of the mini-canisters after the
last load cycle and on the walls of the glass storage bottle when the charcoal
samples were transferred for speciation. The condensation remaining on the
mini-canisters and on the glass storage bottles during sample transfer likely
accounted for these weight variations. The 0.7 gram variation in the Toyota
charcoal sample exposed to the HC-only blend can not be explained.
19
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TABLE 3. CHARCOAL WEIGHTS FOR SAMPLES UNDERGOING TASK 3 SPECIATION
ho
o
Type of Charcoal
Chrysler
Chrysler
Ford
Ford
GM
GM
Toyota
Toyota
Exposure
Gas
HC-Methanol
HC-Only
HC-Methanol
HC-Only
HC-Methanol
HC-Only
HC-Methanol
HC-Only
Initial Sample
Weight. R
18.9
17.6a
28.4
27.9
20.5
19.5
34.1
29.1
Sample Weight
After Last Load, R
26 A
25.7
36.6
35.7
28.7
27.3
35.5
Sample Weight
Before Speciation, R
26.0
25.5
35.6
28.5
27.1
41.2
34.8
Sample Weight
After Speciation,
17.7
16.7
26.8
26.0
18.6
17.6
33.3
28.4
aAs a result of variations in the mini-canister volumes, only 89.5% of the charcoal (by weight) used in
Work Assignment 12 could be placed in the mini-canister used in this Work Assignment. To permit
comparisons between the two work Assignments, the actual Work assignment 12 value has been multiplied by 0.895
-------
IV. RESULTS
This section describes the results for each of the three tasks conducted in
this program. Task 1 includes breakthrough times, working capacity, and weight
gain results for additional HC-methanol exposures of the mini-canisters
previously exposed to a HC-methanol blend in Work Assignment 12.
Breakthrough times and working capacities on a per gram of charcoal basis have
been compared to Work Assignment 12 results for the HC-only blend exposures.
Task 2 includes working capacity, breakthrough time and weight gain results
related to switching between exposure blends for the two sets of charcoal.
Daily laboratory humidity, temperature, and barometric pressure were recorded
during Task 2. A discussion relating laboratory humidity to mini-canister
working capacity and weight gain is presented. Task 3 includes analytical
results for room temperature and elevated temperature purging of the charcoal
from eight of the mini-canisters (four from hydrocarbon-methanol blend
exposures in Task 1 and four from hydrocarbon-only blend exposures in Task 2).
Discussions related to charcoal type, exposure blend, and type of purge (room or
elevated temperature) are presented.
A. Task 1 - Continuation of Hydrocarbon-Methanol Blend Charcoal Testing
Working capacities, breakthrough times, and canister weight gains
(relative to 4/29/85 canister weights) for the Task 1 testing are presented in
Appendix B. In general, the working capacities (Appendix Table B-l) for the
eleven canisters increased through May 3 (after 7 cycles), followed by a gradual
decrease in working capacities (with the exception of the May 9 working
capacities) with each subsequent load/purge cycle. Since the mini-canister
working capacity is dependent on the weight of the charcoal in the mini-
canister, and the weight of the charcoal in each of the mini-canisters varies
from canister to canister, it is necessary to divide the working capacity for
each mini-canister by its clean charcoal weight before manufacturer or blend
comparisons can be made. The working capacities for the canisters exposed to
the HC-methanol blend in this study have been averaged (Appendix Table B-l)
and divided by their respective clean charcoal weights (Table 1 Section III). The
resulting values are presented in Table 4. For comparison, the 18th day
exposure working capacities for the twelve canisters exposed to the HC-only
blend in Work Assignment 12 have also been divided by their respective clean
charcoal weights with the resulting values also listed in Table 4. The
load/purge cycle conditions on the 18th day of loading with the HC-only blend
in Work Assignment 12 were found to more closely resemble the conditions used
in this Work Assignment; therefore, working capacities from the 18th day were
selected over working capacities determined on the 16th and 17th days of
loading and over an average working capacity for the three days. The working
capacity values determined on a per gram of charcoal basis were found to be
slightly higher with the HC-only blend than with the HC-methanol blend for all
four manufacturers (3 to 13 percent); however, when the day-to-day variability
for the HC-methanol blend working capacity (this Work Assignment) and the
variations in test conditions are taken into consideration, it is difficult to
quantify any meaningful difference in the working capacity for the two blends
on a per gram of charcoal basis. For both the HC-methanol and the HC-only
blends, the Ford and Toyota charcoals had higher per gram of charcoal working
capacities than either the Chrysler or the GM charcoal.
21
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TABLE 4. COMPARISON OF WORKING CAPACITIES FOR CANISTERS
EXPOSED TO A HC-METHANOL BLEND AND TO A HC-ONLY BLEND
Working Capacity Working Capacity
mg HC-Methanol Blend/g Charcoal mg HC-Only Blend/g Charcoal
Chrysler 1 147 + 22 196
Chrysler 2 153 + 23 168
Ford 1 188+8 197
Ford 2 187 + 8 201
Ford 3 193+8 197
Ford 4 195
GM 1 127 + 24 136
GM 2 127 +24 137
GM 3 129 + 24 137
Toyota 1 184+7 193
Toyota 2 188+3 190
Toyota 3 188 + 4 194
Breakthrough times for Task 1 testing are tabulated in Appendix B-2.
General trends in breakthrough times were difficult to determine from the
data, therefore average values for the 17 load/purge cycles were calculated and
have also been tabulated in Appendix Table B-2. Breakthrough times were
calculated on a per gram of charcoal basis in an attempt to compare the results
generated in this Work Assignment to those obtained in Work Assignment 12 for
the HC-only blend. Average breakthrough times for the eleven mini-canisters
divided by their respective clean charcoal weights are presented in Table 5.
For comparison, average breakthrough times (days 17 to 19) for the mini-
canisters exposed to the HC-only blend in Work Assignment 12 have also been
divided by their clean charcoal weights and are presented in Table 5. The Work
Assignment 12 values have also been multiplied by the ratio of the exposure
rates (40/38.3) for the two sets of canisters to compensate for the differences
in the exposure rates. This process is necessary since the breakthrough times
are inversely related to the exposure rates.
Except for the two Chrysler samples, the breakthrough times for the
mini-canisters exposed to the HC-methanol blend were slightly longer on a per
gram basis than the breakthrough times for the mini-canisters exposed to the
HC-only blend. However, as was the case with the working capacities,
variations in the data make rigid comparisons difficult. Ford and Toyota
charcoal had longer breakthrough times than either GM or Chrysler charcoal on
a per gram basis for exposure to both blends.
Task 1 daily canister weight gains relative to charcoal weights at the
start of this Work Assignment (4/29/85) are listed in Appendix Table B-3.
Before the Task 1 testing was initiated, all eleven of the mini-canisters had lost
a significant portion of the weight gain previously accumulated in Work
22
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TABLE 5. COMPARISON OF BREAKTHROUGH TIMES FOR CANISTERS EXPOSED
TO A HC-METHANOL BLEND AND TO A HC-ONLY BLEND
HC-Methanol HC-Only
Breakthrough Times,3 Breakthrough Times,*3
Minutes/g Charcoal Minutes/g Charcoal
Chrysler 1 2.8 + 0.4 3.6 + 0.4
Chrysler 2 3.4 + 0.5 3.6 + 0.5
Ford 1 4.7 + 0.2 4.5 + 0.4
Ford 2 4.7 + 0.2 4.3 + 0.4
Ford 3 4.7 + 0.2 4.2 + 0.5
Ford 4 - 4.2 + 0.4
GM 1 2.8 + 0.4 2.7 + 0.2
GM 2 2.8 + 0.4 2.7 + 0.2
GM 3 2.9 + 0.4 2.8 + 0.3
Toyota 1 5.2 + 0.2 4.5 + 0.5
Toyota 2 4.8+0.2 4.5+0.4
Toyota 3 4.9+0.1 4.6 + 0.4
aAverage breakthrough times from Table B-2 divided by respective clean
charcoal weight in grams
bAverage breakthrough times from Page A-4 of EPA Report 460/3-84-014
divided by respective clean charcoal weight in grams and then multiplied by a
ratio of the exposure rates (40/38.3)
Assignment 12 testing. In the case of the GM, Toyota, and Ford charcoals, the
mini-canisters regained this lost weight during the Task 1 testing (additional
weight was gained by the Ford canisters). The Chrysler charcoal, however, did
not regain the weight lost between the end of Work Assignment 12 and the start
of Task 1. The weight gain in relation to the clean charcoal weights for the
eleven mini-canisters is summarized in Table 6.
Table 7 presents the net charcoal weight gains for the mini-canisters
exposed to both the HC-methanol blend and the HC-only blends divided by their
respective clean charcoal weights. The weight gained per gram of charcoal is
higher for the canisters exposed to the HC-only blend than for those exposed to
the HC-methanol blend for all four types of charcoal. These differences can
not be readily explained. Variations in daily laboratory humidity may have
contributed in part to these differences. The relationship of laboratory
humidity to mini-canister working capacity and weight gain is discussed in the
next section of this report.
23
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TABLE 6. SUMMARY OF WEIGHT GAIN FOR MINI-CANISTERS
EXPOSED TO THE HC-METHANOL BLEND
Weight Gain, ga
At the End of Retained from Work Weight Gain
Canister Contents Work Assignment 12 Assignment 12 on 4/29/83 at the end of Task 1
Chrysler 1 5.5 3.5 4.9
Chrysler 2 5.2 3.3 4.5
Ford 1 1.7 0.9 3.1
Ford 2 1.8 0.7 3.0
Ford 3 1.5 0.7 2.6
GM 1 6.4 4.4 6.6
GM 2 5.9 3.8 6.0
GM 3 5.9 4.0 6.1
Toyota 1 0.7 0.1 0.7
Toyota 2 0.8 0.2 0.7
Toyota 3 0.9 0.5 0.6
aRelative to the clean charcoal weights
TABLE 7. COMPARISON OF WEIGHT GAIN FOR CANISTERS EXPOSED TO A
HC-METHANOL BLEND AND TO A HC-ONLY BLEND
Weight Gain Weight Gain
mg HC-Methanol Blend/g Charcoal mg HC-Only Blend/g Charcoal
Chrysler 1 260 410
Chrysler 2 260 390
Ford 1 110 180
Ford 2 96 180
Ford 3 98 180
Ford 4 — 180
GM 1 300 370
GM 2 290 370
GM 3 290 360
Toyota 1 21 150
Toyota 2 22 150
Toyota 3 21 150
24
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B. Task 2 - Switching of Exposure Blends
The results for this section are divided into two parts. The first part
reports the results of testing the seven remaining Task 1 HC-methanol mini-
canisters with a HC-only blend, and the second part reports results for
continued testing of the charcoal previously exposed to the HC-only blend to
establish a new baseline, followed by testing with the HC-methanol blend and
once more with the HC-only blend.
1. Switching of HC-Methanol Blend to HC-only Blend - (Using Task 1
Mini-Canister Charcoals)
Working capacities, breakthrough times, and canister weight gains
(relative to 4/29/85 canister weights) for the Task 2 testing of the seven
remaining Task 1 HC-methanol mini-canisters with the HC-only blend are
presented in Appendix C. In general, the switch to the HC-only blend produced
lower working capacities, shorter breakthrough times (except for the Toyota
charcoal), and less weight gain (except for the Toyota charcoal) for the mini-
canisters. Table 8 presents a comparison of these properties for the seven
mini-canisters. The decrease in working capacity and shorter breakthrough
times seem inconsistent with the decrease in weight gain with additional
exposure.
It should be noted that in addition to the change in blend
composition, the use of the bypass valves was initiated during this portion of
the testing, so some of the differences in working capacity and weight gain may
be related to the use of the bypass valves. Additional exposure after
breakthrough (as in Work Assignment 12 and Task 1 of this work assignment
where no bypass valves were used) could result in preferential displacement of
one type of hydrocarbon retained on the charcoal initially with another (i.e.
butane displaced by toluene, resulting in an enrichment of toluene on the
charcoal). If this enriched hydrocarbon species were more difficult to purge
from the charcoal than the nominal blend mix, then an increase in weight gain
and a corresponding decrease in working capacity would result with the
additional exposure after breakthrough.
2. Switching of Exposure Blends - (Using Charcoal Exposed to the HC-
Only Blend in Work Assignment 12")
Working capacities, breakthrough times, and canister weight gains
(relative to 5/24/85 mini-canister weights) for the HC-only blend testing of
charcoal previously exposed to the HC-only blend in Work Assignment 12 are
presented in Appendix D. Despite some continued variability, working
capacities, breakthrough times, and weight gains were found to stabilize after
the third load/purge cycle; therefore average, values for the working capacities
and breakthrough times were calculated to include all data after the first three
cycles. An attempt was made to correlate the daily working capacities and
weight gain with the laboratory humidity level, but little or no correlation was
observed (all mini-canisters gave linear regression r^ values < 0.05). However,
the laboratory humidity did not vary greatly from day to day during this portion
of the testing. Daily measurements of laboratory air specific humidity
25
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TABLE 8. COMPARISON OF WORKING CAPACITIES, BREAKTHROUGH TIMES, AND WEIGHT GAIN
FOR SEVEN MINIX:ANISTERS WITH THE HC-METHANOL BLEND AND WITH THE HC-ONLY BLEND
HC-Methanol Blend
HC-Only Blend
Canister
Chrysler 2
Ford 2
Ford 3
GM 1
GM 3
Toyota 2
Toyota 3
Average working
Capacity, grams
2.63 + 0.39
5.82 + 0.25
5.12 + 0.22
2.84 + 0.53
2.72 + 0.52
5.98 + 0.11
5.47 + 0.12
Average Breakthrough
Times, Minutes
58.8 + 7.9
146.8 + 7.0
125.8 + 5.1
61.5 + 9.7
60.2 + 8.5
151.9 + 7.0
141.7 + 4.2
Weight Gain,
grams3
1.2
2.3
1.9
2.2
2.1
0.5
0.1
Average Working
Capacity, grams
1.88 + 0.35
5.10 + 0.33
4.38 + 0.32
1.95 + 0.44
1.87 + 0.43
5.52 + 0.10
5.03 + 0.14
Average Breakthrough
Times, Minutes
55.5 + 7.0
139.5 + 9.1
123.5+ 12.2
54.1 + 7.9
53.0 + 7.5
154.0 + 6.5
143.8 + 4.9
Weight Gain,
grams3
0.8
1.9
1.6
1.8
1.7
0.5
0.4
3Relative to 4/29/85 canister weights
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(grains/ft^), room temperature, and barometric pressure for Task 2 testing from
May 27 to 3uly 13 are reported in Appendix G. Much higher correlations
between working capacities and weight gain with laboratory humidity were
noted when the blend was switched to include methanol (r^ from 0.18 to 0.82),
however, day-to-day variations in humidity were more pronounced in this
portion of the study. These correlations will be discussed in more detail in the
following paragraphs.
Table 9 presents a comparison of the working capacities,
breakthrough times, and weight gains on a per gram of charcoal basis for the
twelve mini-canisters exposed to the HC-only blend in this Work Assignment
and in Work Assignment 12. In general, the working capacities were larger, the
breakthrough times longer, and the weight gains larger per gram of charcoal in
the Work Assignment 12 exposures as compared to the exposures in this Work
Assignment. The differences between these parameters for the two Work
Assignments, however, does vary with charcoal type. The differences in
parameters between the two Work Assignments may be a result of the
additional HC-only blend exposure in this Work Assignment, and/or the use of
the bypass valve to divert the vapor flow after breakthrough in this Work
Assignment and not in Work Assignment 12. As previously explained, additional
exposure after breakthrough (as in Work Assignment 12 with no bypass valve)
could have resulted in preferential displacement of one type of hydrocarbon
retained on the charcoal initially with another.
After removal of the four HC-only mini-canisters for Task 3
speciation, the remaining 8 mini-canisters were exposed first to the HC-
methanol blend (20 load-purge cycles) and then once again to the HC-only blend
(13 load-purge cycles). The working capacities, breakthrough times, and
canister weight gains (relative to 5/2^/85 canister weights) are presented in
Appendix E for the HC-methanol blend testing and in Appendix F for the
additional HC-only blend testing.
The switch first to the HC-methanol blend and then back to the HC-
only blend gave similar working capacities, breakthrough times, and weight
gains for each of the eight mini-canisters exposed to the two blends. Table 10
presents a comparison of the averages and standard deviations of these
properties for the eight mini-canisters.
In comparing the three sets of average results, there is in all cases
an overlap of standard deviations for working capacity, breakthrough time, and
weight gain values. However, there were differences among the charcoal types.
GM and Chrysler mini-canisters in general gave higher working capacities for
the HC-methanol blend, compared with the HC-only blend, increasing
breakthrough times with additional exposures (HC-only or HC-methanol), and
decreasing weight gain with additional exposures. The Ford and Toyota mini-
canisters in general gave similar average working capacities for the three
exposures (largest difference between average values for a mini-canister, 0.22g)
and decreasing breakthrough times with additional exposures. However, Ford
mini-canister weight gains did decrease with additional exposures. Some of the
differences between GM/Chrysler and Ford/Toyota trends may be related to the
use of the bypass valves in this Work Assignment. In Work Assignment 12 the
27
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TABLE 9. COMPARISON OF WORKING CAPACITIES, BREAKTHROUGH TIMES,
AND WEIGHT GAINS FOR TWELVE MINI-CANISTERS EXPOSED TO
A HC-ONLY BLEND IN WORK ASSIGNMENT 12 AND THIS WORK ASSIGNMENT
Working Capacity,
mg/g Charcoal
Chrysler
Chrysler
Ford 1
Ford 2
Ford 3
Ford 4
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
This Work
Assign.3
76 +11
75+11
153 + 9
147 + 9
143 + 9
146 + 9
56+11
54 + 10
58+11
169 + 5
164 + 6
165 + 6
Work
Assign. 12b
196
168
197
201
197
195
136
137
137
193
190
194
Breakthrough Times,
Min/g Charcoal
This Work
Assign.0
2.4 + 0.2
1.9 + 0.4
4.4 + 0.2
4.1 + 0.2
4.1 + 0.3
4.1 + 0.2
1.7 + 0.2
1.6 + 0.2
1.9 +0.2
4.8 + 0.1
4.7 +0.2
4.8 + 0.3
Work
Assign. 12d
3.6 + 0.4
3.6 + 0.6
4.5 + 0.4
4.3 + 0.4
4.2 + 0.5
4.2 + 0.4
2.6 + 0.2
2.7 + 0.2
2.8 +0.3
4.5 + 0.5
4.5 + 0.4
4.6 + 0.4
Weight gain,
mg/g Charcoal
This Work
Assign.6
370
390
150
150
Work
Assign. 12f
150
350
290
340
55
50
25
390
180
180
180
180
370
370
360
150
150
150
aAverage working capacity values from Appendix Table A-l divided by respective clean charcoal
weight in grams
k Working capacity values from 18th day of exposure in Work Assignment 12, page A-10
EPA Report 460/3-84-014 divided by respective clean charcoal weight in grams
cAverage breakthrough times from Appendix Table D-2 divided by respective clean charcoal
weight in grams
dAverage breakthrough times from page A-4 of EPA report 460/3-84-014 divided by clean charcoal
weight in grams and then multiplied by a ratio of the exposure rates (40/38.4)
eMini-canister weight on June 11 minus the clean charcoal weights and divided by the clean
charcoal weights
* Mini-canister weights at completion of Work Assignment 12 minus the clean charcoal weights
and divided by the clean charcoal weights
28
-------
TABLE 10. COMPARISON OF AVERAGE WORKING CAPACITY, BREAKTHROUGH TIME,
AND WEIGHT GAIN FOR EIGHT MINI-CANISTERS EXPOSED TO HC-ONLY,
THEN HC-METHANOL, AND THEN TO HC-ONLY BLENDS
Average Working Capacity +_ 1 Standard Deviation, grams
HC-onJy Blend (May/June) HC-methanol Blend HC-only Blend (July)
Chrysler 1
Ford 1
Ford 2
Ford 4
GM 2
GM 3
Toyota 2
Toyota 3
Chrysler 1
Ford 1
Ford 2
Ford 4
GM 2
GM 3
Toyota 2
Toyota 3
Chrysler 1
Ford 1
Ford 2
Ford 4
GM 2
GM 3
Toyota 2
Toyota 3
1.44 + 0.20
4.27 + 0.25
4.04 + 0.25
4.07 + 0.25
1.00 + 0.18
1.13 + 0.21
4.75 + 0.17
4.76 + 0.18
Average Breakthrough Time
44.8 + 4.1
123.8 + 5.5
112.9 + 5.7
114.6 + 6.5
30.1 + 3.5
36.4 ±3.8
135.2 + 4.4
137.7 + 7.4
Average Weight Gain +_
1.95 + 0.43
1.77 + 0.55
1.92 + 0.50
1.77 + 0.53
2.20 + 0.37
2.37 + 0.39
0.51 + 0.20
0.78 + 0.22
1.86 + 0.54
4.28 + 0.47
4.02 + 0.43
4.16 + 0.50
1.26 + 0.45
1.50 + 0.46
4.55 + 0.10
4.64 + 0.18
+ 1 Standard Deviation, Minutes
50.0 + S.7
119.2 + 6.6
108.7 +" 7.2
115.6 + 5.5
32.6 + 6.7
41.0 + 6.2
130.3 + 4.4
137.0 + 4.3
1 Standard Deviation, grams
1.38 + 0.96
1.74 + 0.88
1.84 + 0.79
1.63 + 0.85
1.76 + 0.73
1.85 + 0.77
0.72 + 0.18
0.967 0.25
1.66 + 0.29
4.06 + 0.30
3.85 + 0.28
4.05 + 0.30
1.09 + 0.25
1.37 + 0.26
4.60 + 0.12
4.70 + 0.10
49.6 + 5.9
115.9 + 8.1
107.2 + 7.7
116.1 + 7.0
33.2 + 3.5
42.8 + 4.8
128.1 + 6.7
135.7 + 3.5
1.36 + 0.55
1.66 + 0.56
1.73 + 0.46
1.56 + 0.58
1.68 + 0.44
1.68 + 0.45
0.70 + 0.07
1.03 + 0.09
Average Mass of Water Vapor in air 4- 1 Standard Deviation, grains/ft^
6.17 + 0.35 5.90 + 0.85 5.96 + 0.29
29
-------
Chrysler and GM mini-canisters were exposed to considerably longer additional
exposure times after breakthrough (no bypass valve) than either the Ford or
Toyota mini-canisters. This additional exposure could have resulted in the
preferential displacement of one type of hydrocarbon retained on the charcoal
initially with another. Additional exposures in this Work Assignment (either
with HC-only or HC-methanol) with the bypass valve in use may have slowly
reversed this effect in the GM/Chrysler case resulting in different trends as
compared to the Ford/Toyota mini-canisters.
The daily laboratory humidity also seems to play an important role
in influencing the measured mini-canister parameters, especially working
capacity and weight gain. A discussion of this relationship follows.
As can be seen in Table 10 and in Appendices D, E, and F, the day-
to-day variations in the recorded parameters for the HC-methanol blend were
much larger than those recorded for the HC-only blend exposures. It was also
observed that the laboratory humidity in this portion of the testing showed
more day-to-day variation than in either of the HC-only exposures. To
determine the relationship of the laboratory humidity to the mini-canister
weight gain and working capacities during the HC-methanol exposures, linear
regressions of working capacities and weight gains versus humidity (y = a+bx,
where y = weight gain or working capacity and x = moisture content in grains of
water per cubic foot of air) were computed for each of the eight mini-canisters.
The results of these regressions are presented in Table 11. The r2 values
represent the fraction of weight gain or working capacity variability than can
TABLE 11. LINEAR REGRESSION PLOTS OF HUMIDITY VERSUS WORKING
CAPACITY AND WEIGHT GAIN FOR THE EIGHT MINI-CANISTERS EXPOSED TO
THE HC-METHANOL BLEND
Working Capacity Weight Gain
-_ __»_
Chrysler 1 0.78 5.06 -0.55 0.74 -4.17 0.96
Ford 1 0.75 6.99 -0.47 0.74 -3.39 0.89
Ford 2 0.64 6.63 -0.45 0.76 -2.79 0.80
Ford 4 0.64 6.83 -0.46 0.74 -3.28 0.85
GM 2 0.63 3.67 -0.42 0.79 -2.61 0.76
GM 3 0.66 3.99 -0.43 0.79 -2.67 0.78
Toyota 2 0.28 4.92 -0.06 0.79 -0.33 0.18
Toyota 3 0.18 5.15 -0.09 0.82 -0.56 0.28
be explained by changes in the laboratory humidity. The "a" values (y
intercepts) represent the weight gains (relative to 5/24 canister weights) and
working capacities at zero humidity, while the "b" values represent the slope of
plotted lines or "regression coefficients" (change in working capacity or weight
30
-------
gain in relation to change in moisture content). As can be seen in the table, all
four canister types give relatively high correlations of weight gain with
laboratory humidity (r2 = 0.74 to 0.82). Three of the four canister types
(Chrysler, Ford, GM) also give relatively high correlations of working capacity
with humidity (r2 = 0.63 to 0.78), while the Toyota canisters give a much lower
correlation (r2 = 0.18 to 0.28). The negative "a" values for the weight gain
regressions indicate that a significant amount of the weight previously gained in
Work Assignment 12 could be due to moisture content. The negative working
capacity "b" values in the table indicate a decrease in working capacity with
increasing humidity, and the positive weight gain "b" values indicate an increase
in weight gain with increasing humidity. The low "b" values for the Toyota
canisters indicate that humidity influences the weight gain and working
capacity of the Toyota canisters to a much lesser extent than the other three
canister types.
C. Task 3 Purge/Speciation of Mini-Canister Charcoal
The results for the cold (room temperature) and hot (180 to 190°C) purges
of the eight mini-canisters from Tasks 1 and 2 of this study are reported in
Table 12. Several observations can be made from the data in the table. Butane
and isobutylene for the most part are removed from the mini-canister charcoal
during the cold purge cycle. From 86 to 99-plus percent of the butane and
isobutylene purged from the mini-canisters is removed during the cold purge.
The ratio of butane to isobutylene found in the charcoal (4.3 to 5.4 parts butane
to 1 part isobutylene ) was similar to the ratio of butane to isobutylene in the
exposure blends (4.1 to 1).
TABLE 12. RESULTS PURGE/SPECIATIONS
Weight of Compound Purged, grams
Charcoal
Chrysler
Chrysler
Ford
Ford
GM
GM
Toyota
Toyota
Exposure Blend
HC-methanol
HC-only
HC-methanol
HC-only
HC-methanol
HC-only
HC-methanol
HC-only
Butane
Cold Hot
0.80
0.72
3.62
3.40
0.48
0.51
4.38
2.82
0.06
0.10
0.29
0.15
0.04
0.03
0.72
0.01
Isobutylene
Cold Hot
0.18
0.16
0.67
0.73
0.11
0.11
0.88
0.60
0.01
0.01
0.05
0.03
0.01
0.01
0.14
0.00
Toluene
Cold Hot
0.02
0.05
0.12
0.15
0.05
0.02
0.19
0.48
0.63
0.26
1.53
1.77
1.00
0.24
1.18
1.92
Methanol
Cold Hot
0.19
NDa
0.28
ND
0.15
ND
0.29
ND
0.19
ND
0.05
0.01
0.17
ND
0.02
0.01
Water
Cold Hot
2.53
2.04
2.33
1.71
3.09
1.93
0.58
0.69
3.00
4.50
0.20
0.20
4.62
6.02
0.68
0.51
a ND = not detectable
Unlike butane and isobutylene, only a small fraction of the toluene was
removed from the mini-canisters during the cold purge (values ranged from 3 to
20 percent of the toluene). There was also a considerable enrichment of
31
-------
toluene in the mini-canisters as compared to the exposure blend compositions
with the ratio of butane to toluene dropping from ~14 to 1 in the exposure
blends down to 0.5 - 3.7 to 1 in the mini-canisters. This observation indicates
that toluene (and probably any other heavy hydrocarbons that reach the
canister) play an important role in increasing weight gain and decreasing
working capacity with increasing exposures. However, in extrapolating these
results to "real world" applications, it is uncertain how much difference there
would be between the effects of actual gasoline vapor and the simulated
(butane, isobutylene, toluene) vapor used in this study.
While all four charcoal types show similar purge characteristics for
hydrocarbons, there are considerable differences in relation to methanol. For
the Chrysler and GM mini-canisters, only half the detectable methanol can be
purged from the charcoal during the cold purge, while 85 to 94 percent of the
methanol can be removed from the Ford and Toyota canisters, respectively,
during the cold purge. This observation indicates that methanol may be more
important in weight gain increase and working capacity decrease for the
Chrysler and GM charcoals than for the Ford and Toyota charcoals. The
enrichment of methanol in the GM and Chrysler mini-canisters substantiates
this observation. The ratio of butane to methanol drops from 9.3 to 1 in the
exposure blend to 2.3 to 1 and 1.6 to 1 in the Chrysler and GM charcoals
respectively. The Ford and Toyota charcoals do not show this enrichment, and
even indicate there may be a small amount of methanol pass-through for these
two charcoals. The ratio of butane to methanol is higher in the Ford (11.5 to 1)
and Toyota (16.5 to 1) charcoals than in the exposure blend (9.3 to 1). Excluding
water weight, methanol amounts to 15-18 percent of the total purged weight
from the Chrysler and GM mini-canisters and 4-5 percent of the total weight
purged from the Ford and Toyota mini-canisters. However, when the weight of
the water is included, the methanol only amounts to 3-5 percent of the total
weight purged from any of the mini-canisters.
While water measurements were not originally included in the project
scope of work, the observation of a relationship between day-to-day laboratory
humidity levels and mini-canister weight gain and working capacity indicated
the need for these measurements. Considerably more water was found in the
Chrysler and GM charcoals (5.5 to 8.0 grams) than in the Ford and Toyota
charcoals (1.2 to 2.9 grams). Ford charcoal was found to differ from the other
three charcoal types in that more than 90 percent of the water could be
reinoved during the cold purge, while the remaining three charcoal types had
only 24 to 58 percent of the water removed during the cold purge. The affinity
of the four types of charcoal for water appears to be related to that for
methanol, with Chrysler and GM charcoals having a higher affinity for both
methanol and water than do the Ford and Toyota charcoals. The levels of water
in the canisters do not appear to be a result of the methanol, however, because
both the charcoals exposed to the HC-only and the HC-methanol blends gave
similar water levels for each charcoal type.
32
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V. QUALITY ASSURANCE
The Quality Assurance (QA) guidelines addressed in the QA report for this
Work Assignment and for Work Assignment 27 were followed in performing the
work for this program. Calibrations were performed on the analytical
instruments, balances and timers, and daily sampling system leak checks were
conducted on the charcoal purge and sampling system used in Task 3. The data
are available for inspection if desired.
The program objectives for precision, accuracy, and completeness for the
measurement of breakthrough time, weight gain, and working capacity are
listed in Table 13. The objective of > 95 percent completeness was obtained
TABLE 13. PRECISION, ACCURACY, AND COMPLETENESS OBJECTIVES
FOR BREAKTHROUGH TIME, WEIGHT GAIN, AND WORKING CAPACITY ANALYSIS
Precision
Analytical Procedure Std. Dev. Accuracy, % Completeness, %
Breakthrough Time 9 ±10 >95
Weight Gain 0.00 ±0.01 >95
Working Capacity 0.04 ±0.02 >95
with 99+ percent of the breakthrough times, 100 percent of the weight gains,
and 97+ percent of the working capacities successfully recorded during the
course of the program. An eight ounce standard weight (226.80 grams), weighed
daily along with the mini-canisters, gave an average wieght of 226.82 ± 0.04
grams. This average value is accurate to within 0.01 percent of the actual
weight and can be assumed to be the accuracy of the weight gain and working
capacity values during the course of the program. It should be noted, however,
that initial weight gain values were recorded to one tenth of a gram, while the
remainder of the weight gain values were recorded to one hundredth of a gram.
The timers used to record the breakthrough times were checked periodically
during the program and found to agree within 5 percent with a precision
stopwatch.
Test to test variations in weight gain and working capacity were found to
exceed the objectives for precision, 0.00 grams for weight gain and 0.04 grams
for working capacity (i.e., the standard deviations for working capacity values
ranged from 0.10 to 0.54 grams over the range of mini-canisters and test
conditions). However, during the course of the program, it was found that day
to day variations in laboratory humidity produced corresponding variations in
rnini-canister weight gain and working capacity (refer to Section IV. B. 2.).
This relationship had not been determined previously and the effect on the
weight gain and working capacity measurements was not anticipated. The
standard deviations for the mini-canister breakthrough times fell below the 9
minute objective in most instances (96%) despite the variations in laboratory
humidity.
33
-------
The objectives for precision, accuracy, and completeness for methanol,
water content and selected HC speciation (from Work Assignment 27) are
presented in Table 14. All scheduled analyses were conducted in the study with
100 percent completeness. Accuracy and precision values in Table 14 were
determined in Work Assignment 27 validation experiments.
TABLE 1*. PRECISION, ACCURACY, AND COMPLETENESS OBJECTIVES FOR
METHANOL, WATER, AND SELECTED HC SPECIATION ANALYSIS
Analytical Precision
Measurement Procedure Std. Dev.a Accuracy, % Completeness
Methanol Gas Chromatograph 2b 91C >95
(FID)
Water Gravimetric 0.00 105C >95
Content
Selected Gas Chromatograph 10b 70d >95
HC Speciation (FID)
a Standard deviation except where indicated
b Coefficient of variation
c Based on recovery experiments conducted on the sampling system
d Based on the recovery of gasoline as THC. Recoveries of individual HC species
will vary.
34
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REFERENCES
1. Warner-Selph, M.A., "The Effect of Methanol on Evaporative Canister
Charcoal Capacity", Final Report EPA 460/3-84-
2. Warner-Selph, M.A., "In-Use Evaporative Canister Evaluation", Draft
Report Work Assignment 27, EPA Contract 68-03-3162.
3. Smith, L.R., "Blend Vapor Analysis", Program in Progress, Work
Assignment 12, EPA Contract 68-03-3192.
4. Dietzmann, H.E., "Gasoline Volatility Analysis", Letter Reports to EPA,
Work Assignments 4 and 7, EPA Contract 68-03-3192.
35
-------
APPENDIX A
Exposure Summaries for Tasks 1 and 2
-------
TABLE A-l. TASK I CONTINUATION OF METHANOL BLEND CHARCOAL TESTING
HC-Methanol
Blend Exposure for
Purge Manifold
Concentration
>
Date
4/30
5/1
5/2
5/3
5/6
5/7
5/8
5/9
5/10
5/13
Totals
Cycle
1
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
19
Load Time, min.
180
180
171
184
183
178
170
180
163
182
180
179
175
177
168
178
176
182
184
3370
Each Canister, g
6.89
6.89
6.55
7.05
7.01
6.82
6.51
6.89
6.24
6.97
6.89
6.86
6.70
6.78
6.43
6.82
6.74
6.97
7.05
129.06
Purge Time, min.
110
25
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
2005
at 1 10 Min., ppmC
230
2800
330
350
360
370
380
340
370
340
350
340
360
320
320
360
310
300
300
„
-------
TABLE A-2. TASK 2 TESTING, SWITCHING OF HC-METHANOL BLEND
TO HC-ONLY BLENDa
HC Blend Purge Manifold
Date Cycle Load Time Range*3, min. Exposure Rangec,g Purge Time, min Concentration, ppmC
5/15
5/16
5/17
5/20
5/21
5/22
5/23
1
2
1
2
1
2
1
2
1
2
1
2
1
2
54.8 to 154.8
63.0 to 149.0
64.3 to 161.5
68.0 to 161.0
56.5 to 168.5
53.0 to 153.3
50.7 to 151.8
47.7 to 151.0
44.4 to 153.4
45.7 to 152.0
49.4 to 157.5
47.2 to 153.0
49.9 to 146.3
46.0 to 143.2
2.10 to 5.94
2.42 to 5.72
2.47 to 6.20
2.61 to 6.18
2.17 to 6.47
2.04 to 5.89
1.95 to 5.83
1.83 to 5.80
1.70 to 5.89
1.75 to 5.84
1.90 to 6.05
1.81 to 5.88
1.88 to 5.62
1.77 to 5.50
110
110
110
110
110
110
110
110
110
110
110
110
110
110
200
200
220
190
190
160
170
150
160
160
170
180
150
160
aCharcoal previously exposed to HC-Methanol blend in Work Assignment 12 and Task 1 of
this Work Assignment
"Load time for each canister is the same as the breakthrough time, refer to Appendix Table C-2
cHC-only Blend Exposure in grams can be calculated for each canister by multiplying the
exposure rate, 38.4 mg/min., times the breakthrough time (Appendix Table C-2) and dividing by 1000
-------
TABLE A-3. TASK 2 SUMMARY OF TESTING, CONTINUATION OF HYDROCARBON-ONLY BLEND
CHARCOAL TESTING3
HC-Blend Purge Manifold
Date Cycle Load Time Range^1, min. Exposure Rangec,g Purge Time, min. Concentration, ppmC
5/24
5/27
5/28
5/29
5/30
5/31
6/3
6/4
6/5
6/6
6/7
6/10
6/11
6/12d
1
1
2
1
2
1
2
1
2
1
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
46.8 to 148.0
51.6 to 150.3
45.8 to 152.8
35.8 to 147.0
30.0 to 146.0
31.9 to 149.0
32.2 to 148.0
29.9 to 140.1
32.7 to 141.9
34.1 to 146.2
33.2 to 139.0
27. 9 to 137.3
32.9 to 141.7
33.5 to 135.0
31.9 to 135.2
29.1 to 140.7
30.5 to 144.0
26.5 to 137.8
22.1 to 141.0
24.6 to 138.1
26.3 to 141.6
27.3 to 140.2
25.7 to 145.5
23.6 to 142.2
31.3 to 141.1
1.80 to 5.68
1.98 to 5.77
1.76 to 5.88
1.37 to 5.64
1.15 to 5.61
1.22 to 5.72
1.24 to 5.68
1.15 to 5.38
1.26 to 5.45
1.31 to 5.61
1.27 to 5.34
1.07 to 5.27
1.26 to 5.44
1.29 to 5.18
1.22 to 5.19
1.12 to 5.40
1.17 to 5.53
1.02 to 5.29
0.85 to 5.41
0.94 to 5.30
1.01 to 5.44
1.05 to 5.38
0.99 to 5.59
0.91 to 5.46
1.20 to 5.42
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
130
200
190
210
220
200
180
200
210
190
160
170
180
100
100
110
100
100
100
110
110
100
100
115
aCharcoal previously exposed to HC-Only blend in Work Assignment 12
bLoad time for each canister is the same as the breakthrough time, refer to Appendix Table D-2
cHC-only blend exposure in grams can be calculated for each canister by multiplying the
exposure rate, 38.4 mg/min., times the breakthrough time (Appendix Table D-2)and dividing by 1000
^After HC-blend loading, the charcoal was removed from four of the mini-canisters (one
from each manufacturer) for subsequent speciation in Task 3
A-4
-------
TABLE A-4. TASK 2 TESTING, SWITCHING OF HC-ONLY BLEND TO HC-METHANOL BLEND3
Date Cycle Load Time^, min
HC-Methanol
Blend Exposure
g
Purge Time, min.
Purge Manifold
Concentration, ppmC
6/13
6/14
6/17
6/18
6/20
6/21
6/24
6/25
6/26
6/27
6/28
1
2
1
2
1
2
1
1
2
1
2
1
2
1
1
2
1
2
1
2
33.9 to 148.0
45.1 to 137.3
46.6 to 137.7
43.0 to 135.1
42.0 to 135.4
30.7 to 128.8
32.2 to 139.7
32.9 to 139.0
33.2 to 141.4
33.6 to 139.7
30.0 to 141.6
29.1 to 138.0
25.1 to 135.0
24.6 to 129.8
29.1 to 134.5
27.6 to 134.7
27.1 to 137.5
26.4 to 138.2
28.5 to 133.0
30.2 to 135.0
1.30 to 5.67
1.77 to 5.26
1.78 to 5.27
1.65 to 5. 17
1.61 to 5.19
1.18 to 4.93
1.23 to 5.35
1.26 to 5.32
1.27 to 5.42
1.29 to 5.35
1.15 to 5.42
1.11 to 5.29
0.96 to 5.17
0.94 to 4.97
1.11 to 5.15
1.06 to 5.16
1.04 to 5.27
1.01 to 5.29
1.09 to 5.09
1.16 to 5.17
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
150
165
200
185
160
155
145
140
140
145
130
120
130
110
115
140
120
130
125
155
aCharcoal previously exposed to HC-only blend in Work Assignment 12
^Load time for each canister is the same as the breakthrough time, refer to Appendix Table E-2
cHC-Methanol blend exposure in grams can be calculated for each canister by multiplying the
exposure rate, 38.3 mg/min., times the breakthrough time (Appendix Table E-2) and dividing by 1000
-------
TABLE A-5. TASK 2 TESTING, SWITCHING OF HC-METHANOL BLEND
BACK TO HC-ONLY BLEND*
HC-Methanoi
Blend Exposure Purge Manifold
Date Cycle Load Time13, min. Range0, R Purge Time, min. Concentration, ppmC
7/1
7/2
7/3
7/10
7/11
7/12
7/15
1
2
1
2
1
2
1
2
1
2
1
2
1
38.2 to 139.8
38.4 to 136.6
38.6 to 130.1
34.0 to 137.3
31.7 to 136.8
30.7 to 133.0
33.5 to 130.8
27.4 to 133.0
29.1 to 140.0
33.8 to 134.6
33.3 to 139.3
32.6 to 140.9
30.9 to 133.0
1.47 to 5.37
1.47 to 5.25
1.48 to 5.00
1.31 to 5.27
1.22 to 5.25
1.18 to 5.11-
1.29 to 5.02
1.05 to 5.11
1.12 to 5.38
1.30 to 5.17
1.29 to 5.35
1.25 to 5.41
1.19 to 5.11
110
110
110
110
110
110
110
110
110
110
110
110
110
165
185
150
150
160
160
135
140
120
145
120
135
155
aCharcoal previously exposed to HC-only blend in Work Assignment 12
''Load time for each canister is the same as the breakthrough time, refer to Appendix Table F-2
cHC-Only blend exposure in grams can be calculated for each canister by multiplying the
exposure rate, 38.4 mg/min., times the breakthrough time (Appendix Table F-2) and dividing by 1000
-------
APPENDIX B
Daily Working Capacities, Breakthrough Times,
and Weight Gains for Task 1 Testing
-------
TABLE B-l. TASK 1 WORKING CAPACITIES, CONTINUATION OF METHANOL
BLEND CHARCOAL TESTING
Working Capacity, grams5
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
1/1
2.9
2.8
5.6
6.2
5.5
2.9
2.7
2.8
6.6
6.2
5.6
5/2
3.34
3.16
5.56
6.05
5.27
3.48
3.22
3.38
6.23
5.92
5.40
5/3
3.41
3.28
5.62
6.10
5.35
3.79
3.51
3.67
6.12
5.95
5.44
5/6
2.95
2.68
5.29
5.69
5.05
3.03
2.75
2.89
5.76
5.82
5.38
5/7
2.70
2.51
5.26
5.75
5.06
2.73
2.45
2.56
6.38
6.02
5.47
5/8
2.46
2.34
5.15
5.61
4.92
2.38
2.17
2.28
6.31
5.99
5.40
5/9
2.63
2.49
5.40
5.90
5.17
2.62
2.38
2.44
6.35
5.90
5.37
5/10
2.38
2.24
5.09
5.57
4.92
2.34.
2.14
2.25
6.20
5.92
5.40
5/13
2.23
2.20
5.01
5.50
4.87
2.26
2.17
2.19
6.55
6.09
5.73
Average
2.78
2.63
5.33
5.82
5.12
2.84
2.61
2.72
6.28
5.98
5.47
+ 0.41
+ 0.39
+ 0.23
+ 0.25
+ 0.22
+ 0.53
+ 0.49
+ 0.52
+ 0.25
+ 0.11
+ 0.12
aWorking capacity is defined as the weight of hydrocarbons that can be purged after
hydrocarbon loading
-------
TABLE B-2. TASK 1 BREAKTHROUGH TIMES, CONTINUATION OF
METHANOL BLEND CHARCOAL TESTING
to
I
U)
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
GM 1
Gm 2
GM 3
Toyota 1
Toyota 2
Toyota 3
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Gm 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
5/1
Cycle 2
55.3
*3.7
I20.it
133.3
119.1
*5.1
*5.*
*5.8
170.1
1*1.8
138.2
5/8
Cycle 1
52.1
58.5
132.U
150.5
125.8
62.5
57.5
62.5
178.6
153.8
1*1.7
5/2
Cycle 1
57.9
56.7
1*0.2
158.0
131.0
59.0
55.0
58.7
183.8
142.9
139.0
5/8
Cycle 2
*6.1
5*.8
131.2
148. 9
12*.*
59.6
51.2
56.2
17*. 3
157.H
Iit5.it
5/2
Cycle 2
66.8
62.5
1*3.3
153.0
136.2
65.6
61.1
61.0
182.6
1*5.2
1*3.1
5/9
Cycle 1
*6.9
56.0
129.9
1**.0
127.9
52.8
60.0
58.*
176.8
157.7
1*8.7
5/3
Cycle 1
68.8
68.*
137.*
1**.3
133.9
69.3
67.3
66.9
177.0
139.3
138.*
5/9
Cycle 2
*3.0
52.8
122.6
1*0.5
120.7
50.6
55.8
5*.6
167.7
< 156.3
1*0.8
5/3
Cycle 2
68.2
67.8
1*0.3
157.6
129.5
75.7
68.0
70.8
169.5
152.8
1*0.5
5/10
Cycle 1
*6.7
<5*.8
132.6
1**.*
119.8
<5*.8
57.5
<5*.8
177.*
15*.*
1*3.8
5/6
Cycle 1
58.2
70.1
1*3.1
152.3
125.2
72.5
66.9
68.5
179.0
1*3.*
1*2.2
5/10
Cycle 2
*6.6
53.8
130.6
138.8
125.*
56.0
*6.8
51.5
175.9
155.*
!**.!
5/6
Cycle 2
5*. 8
69.2
1*2.3
1*6.1
125.2
77.0
68.1
73.1
162.7
1*7.6
131.8
5/13
Cycle 1
*7.5
50.9
126.3
138.*
122.*
53.*
*6.9
51.*
181.0
156.0
1*7.5
5/7
Cycle 1
55.2
68.8
136.3
153.3
118.7
73.6
68.3
72.8
181.1
157.6
137.*
5/13
Cycle 2
*7.7
50.7
128.5
1*2.1
122.8
52.0
*5.9
*9.0
183.0
159.1
1*6.2
5/7
Cycle 2
51.0
60.7
135.9
1*9.*
130.3
66.*
59.0
66.5
179.7
161.3
139.6
Average
53.7 + 8.1
58.8 + 7.9
133.7 + 7.0
1*6.8 + 7.0
125.8 + 5.1
61.5 + 9.7
57.7 + 8.3
60.2 + 8.5
176.5 + 5.9
151.9 + 7.0
1*1.7 + *. 2
-------
TABLE B-3. TASK 1 WEIGHT GAINS, CONTINUATION OF METHANOL BLEND
CHARCOAL TESTING
Weight Gain, grams3
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
5/1
0.5
0.6
1.1
1.1
0.9
1.0
1.1
0.9
0.4
0.3
0.2
5/2
-0.8
-0.7
0.5
0.9
0.4
-0.4
-0.3
-0.5
0.3
0.2
0.1
5/3
-1.6
-1.3
0.3
0.3
0.3
-1.3
-1.1
-1.4
0.2
0.1
0.1
V6
-0.9
-0.7
0.8
0.8
0.7
-0.7
-0.5
-0.7
0.3
0.2
0.2
5/7
-0.2
-0.1
1.2
1.2
1.0
0.2
0.4
0.2
0.4
0.3
0.2
5/1
1.0
0.4
1.5
1.6
1.3
1.1
1.2
1.0
0.5
0.3
0.3
5/9
0.7
0.5
1.5
1.6
1.3
1.3
1.5
1.3
0.4
0.4
0.3
5/10
0.9
0.7
1.7
1.7
1.4
1.6
1.7
1.6
0.5
0.4
0.3
5/13
1.4
1.2
2.2
2.3
1.9
2.2
2.2
2.1
0.6
0.5
0.1
aWeight gain relative to April 29, 1985 canister weights
B-4
-------
APPENDIX C
Daily Working Capacities, Breakthrough Times, and Weight
Gains for Task 2 Testing (HC-Methanol Mini-Canisters
Exposed to HC-Only Blend)
-------
TABLE C-l. TASK 2 WORKING CAPACITIES, SWITCHING OF HC-METHANOL BLEND
TO HC-ONLY BLEND3
Working Capacity, grams,k
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
n Ford 3
i
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
5/15
Cycle 1
2.46
___
5.78
4.88
2.63
—
2.59
5.60
5.18
5/15
Cycle 2
2.33
__
5.27
4.86
2.59
—
2.48
5.47
5.16
5/16
Cycle 1
1.79
__
5.23
4.39
1.87
—
1.77
5.66
4.97
5/16
Cycle 2
1.92
—
5.08
4.41
2.08
__
1.96
5.57
5.04
5/17
1.73
___
4.88
4.14
1.77
—
1.71
5.62
4.73
5/20
1.39
— —
4.79
4.05
1.33
__
1.27
5.40
5.01
5/21
1.98
— —
5.25
4.44
1.94
—
1.92
5.50
5.19
5/22
1.52
__
4.88
4.00
1.51
—
1.43
5.45
4.97
5/23
1.77
— —
4.70
4.29
1.82
__
1.73
5.37
5.05
Av*.
1.88 + 0.35
—
5.10 + 0.33
4.38 + 0.32
1.95 + 0.44
__
1.87 + 0.43
5.25 + 0.10
5.03 + 0.14
aCharcoal previously exposed to HC-methanol blend in Work Assignment 12 and in
Task 1 of this Work Assignment
''Working capacity is defined as the weight of hydrocarbons that can be purged after
hydrocarbon loading
-------
TABLE C-2. TASK 2 BREAKTHROUGH TIMES, SWITCHING OF HC-METHANOL
BLEND TO HC-ONLY BLEND3
Breakthrough Times, minutes
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
5/15
Cycle 1
55.5
__
127.7
124.9
55.8
—
54.8
154.8
144.8
5/22
Cycle 1
__
52.0
136.8
121.8
51.0
—
49.4
157.5
148.5
5/15
Cycle 2
„
66.2
146.5
173.0
67.2
—
63.0
—
149.0
139.0
5/22
Cycle 2
__
51.8
— —
137.7
116.2
50.4
—
47.2
153.0
143.0
5/16
Cycle 1
_.
64.8
152.5
130.2
65.3
—
64.3
—
161.5
140.9
5/23
Cycle 1
50.0
137.2
111.2
49.5
—
49.0
_..
146.3
143.5
5/16
Cycle 2
„
70.0
1455.3
155.9
69.0
—
68.0
—
161.0
154.0
5/23
Cycle 2
48.5
120.8
112.0
46.0
--
47.0
—
143.2
141.0
5/17 5/17 5/20 5/20 5/21 5/21
Cycle 1 Cycle 2 Cycle 1 Cycle 2 Cycle 1 Cycle 2
.
59.0 57.3 53.0 49.3 48.2 52.0
143.2 133.8 143.5 144.0 135.9 138.0
133.0 118.3 119.6 117.3 112.8 118.7
57.0 53.0 52.0 48.7 46.5 45.7
—
56.5 53.8 50.7 47.7 44.4 46.0
—
168.5 153.3 151.8 151.0 153.4 152.0
147.0 132.7 143.2 144.7 145.5 145.3
Average
55.5+ 7.0
—
139.5 + 9.1
123.5 + 12.2
54.1 + 7.9
--
53.0+- 7.5
_-
154.0 + 6.5
143.8+ 4.9
aCharcoal previously exposed to HC-methanol blend in Work Assignment 12 and in
Task 1 of this Work Assignment
-------
TABLE C-3. TASK 2 WEIGHT GAINS, SWITCHING OF HC-METHANOL BLEND TO HC-ONLY BLEND*
Weight Gain, grams^
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
5/15
Cycle 1
__
-0.5
—
0.9
0.8
0.4
—
0.2
__
0.3
0.3
5/15
Cycle 2
-0.7
—
0.7
0.6
0.0
—
-0.2
_ __
0.0
0.0
5/16
Cycle 1
_-.
0.0
1.3
1.1
0.7
—
0.6
__
0.4
0.3
5/16
Cycle 2
__
0.1
1.5
1.2
0.8
—
0.7
__
0.4
0.4
5/17
__
0.5
__
1.7
1.4
1.4
—
1.3
__
0.4
0.4
5/20
__.
1.2
—
2.3
1.9
2.2
—
2.1
___
0.6
0.5
5/21
__
0.6
__
1.6
1.4
1.5
—
1.4
0.3
0.3
5/22
_._
0.9
—
1.9
1.6
1.9
—
1.8
0.5
0.5
5/23
__
0.8
—
1.9
1.6
1.8
—
1.7
__
0.5
0.4
aCharcoal previously exposed to HC-methanol blend in Work Assignment 12 and in Task 1
of this Work Assignment
b Weight gain relative to April 29, 1985 canister weights
-------
APPENDIX D
Daily Working Capacities, Breakthrough Times, and Weight
Gains for Task 2 Testing (Continuation of HC-Only
Blend Exposures for HC-Only Mini-Canisters)
-------
TABLE D-l. WORKING CAPACITIES, CONTINUATION OF HYDROCARBON-ONLY BLEND
CHARCOAL TESTING*
Working Capacity, grams0
a
i
t-o
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford ^
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 4
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
5/24
0.99
0.78
2.86
2.93
2.52
2.70
0.49
0.49
0.56
3.01
2.85
2.80
6/3
—
—
—
—
..
—
—
..
—
—
5/27
Cycle 1
1.69
1.21
14.27
14.22
4.14
4.20
0.93
0.80
0.94
4.93
4.85
4.86
6/4
1.53
1.43
4.15
3.96
3.90
3.95
1.19
1.06
1.24
4.80
4.73
4.73
5/27
Cycle 2
1.14
1.17
4.31
4.00
3.91
4.01
0.72
0.68
0.85
4.89
4.69
4.85
6/5
1.43
1.33
4.24
4.09
3.86
3.89
1.07
1.00
1.15
4.87
4.67
4.61
5/28
Cycle 1
1.40
1.24
4.45
4.20
4.41
4.43
0.96
0.88
1.01
4.97
4.82
4.96
6/6
1.00
0.90
3.81
3.48
3.58
3.61
0.70
0.64
0.75
4.77
4.39
4.52
5/28
Cycle 2
1.37
1.29
4.42
4.16
3.97
4.21
1.00
0.94
1.06
4.92
4.92
4.76
6/7
1.27
1.18
4.00
3.83
3.82
3.81
0.97
0.91
1.01
4.66
4.70
4.48
5/29
Cycle 1
1.48
1.34
4.38
4.13
4.18
4.00
1.05
1.00
1.11
4.96
4.79
4.96
6/10
1.69
1.54
4.36
4.03
3.79
4.16
1.42
1.28
1.44
5.10
4.94
4.95
5/29
Cycle 2
1.47
1.37
4.26
3.97
3.99
4.22
1.14
1.03
1.17
5.05
4.96
4.87
6/11
1.54
1.38
4.11
3.99
3.94
4.01
1.21
1.05
1.21
4.88
4.66
4.78
5/30
1.79
1.69
4.78
4.55
4.46
4.48
1.46
1.33
1.51
5.11
4.88
4.89
12
6/1 2C
1.32
—
3.77
3.67
—
3.75
0.91
1.05
—
4.60
4.69
5/31
1.33
1.19
4.22
4.04
—
4.04
0.98
0.85
0.92
4.97
4.59
4.57
Average
Determinations
5/28 to 6/1 1
1.44 + 0.20
1.32 + 0.20
4.27 + 0.25
4.04 + 0.25
3.99 + 0.26
4.07 + 0.25
1.10 + 0.21
1.00 + 0.18
1.13 + 0.21
4.92 + 0.14
4.75 + 0.17
4.76 + 0.18
aCharcoal previously exposed to HC-only blend in work assignment 12
''Working capacity is defined as the weight of hydrocarbons that can be purged after hydrocarbon loading
cThe charcoal from four of the canisters was removed before purging for speciation in Task 3
-------
TABLE D-2. BREAKTHROUGH TIMES, CONTINUATION OF HYDROCARBON-ONLY BLEND CHARCOAL TESTING3
o
I
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford it
CM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford it
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
5/2*
76.0
61.0
130.0
129.0
112.3
120.3
52.0
*6.8
50.3
1*3.5
135.8
1*8.0
6/*
Cycle 2
*6.7
38.6
119.8
109.3
107.2
111.*
35.0
33.5
38.3
135.0
13*.5
135.0
5/27
Cycle 1
72.6
61.3
136.5
135.8
13*.6
139.7
5*.*
51.6
57.8
1*5.6
1*0.1
150.3
6/5
Cycle 1
*6.6
32.0
12*.6
106.5
106.2
105.9
32.2
31.9
36.2
135.1
13*.5
135.2
5/27
Cycle 2
59.2
*9.5
1*0.8
127.2
__b
130.1
*5.8
*5.8
*9.5
1*8.3
138.1
152.8
6/5
Cycle 2
**.3
29.5
122.5
111.0
109.*
109.9
29.3
29.1
36.8
1*0.7
136.7
129.5
5/28
Cycle 1
51.8
*8.0
131.5
12*. 5
1*0.0
127.*
38.2
35.8
*5.0
1*3.5
135.0
1*7.0
6/6
Cycle 1
*7.8
35.7
125.0
110.5
117.7
109.8
3*. 6
30.5
38.5
13*. 5
13*.9
1**.0
5/28
Cycle 2
*6.5
*5.5
127.6
119.0
117.0
12*. 5
35.0
30.0
*0.0
1*2.9
139.6
1*6.0
6/6
Cycle 2
*0.7
29.*
120.8
110.7
113.8
112.0
27.5
26.5
32.8
137.8
128.5
135.8
5/29
Cycle 1
*7.7
*2.1
128.1
118.0
123.0
113.0
32.8
31.9
39.1
1**.6
1*0.5
1*9.0
6/7
Cycle 1
36.5
26.*
133.5
106.3
116.6
106.0
2it.it
22.1
27.7
1*1.0
1*1.0
1*1.0
5/29
Cycle 2
**.5
37.0
123.5
116.5
116.5
122.5
36.8
32.2
37.9
1*6.0
1*5.0
1*8.0
6/7
Cycle 2
38.7
26.9
116.1
110.6
110.*
112.8
25.9
2*.6
31.0
138.1
133.9
127.2
5/30
Cycle 1
*5.3
36.2
120.0
120.3
__c
121.3
35.7
29.9
36.2
1*0.1
130.0
137.5
6/10
Cycle 1
39.9
26.7
115.3
108.1
104.0
109.2
29.5
26.3
31.6
1*1.6
133.2
122.7
5/30
Cycle 2
50.8
36.*
127.0
11*. 3
119.5
119.8
37.*
32.7
37.2
1*1.9
13*.5
139.8
6/10
Cycle 2
38.*
27.6
118.*
103.5
96.2
105.7
29.6
27.3
31.9
1*0.2
133.5
13*.9
5/31
*9.5
37.8
131.5
123.5
117.6
12*.5
39.2
3*.l
*0.3
1*6.2
132.7
132.7
6/11
Cycle 1
**.*
25.7
117.*
107.9
112.9
117.0
33.5
32.7
35.2
1**.0
137.*
1*5.5
6/3
Cycle 1
*6.8
37.3
127.0
113.0
11*. 3
113.7
35.7
33.2
38.2
137.5
132.8
139.0
6/11
Cycle 2
*2.9
23.6
115.8
112.3
112.9
113.5
32.7
27.1
3*.*
1*1.1
128.*
1*2.2
6/3
Cycle 2
*5.0
38.*
127.7
111.2
112.7
115.1
35.0
27.9
36.5
137.3
130.0
129.0
6/12
*8.3
28.5
112.3
110.5
116.0
111.0
32.1
31.3
33.3
1*1.1
139.3
137.5
6/*
Cycle 1
*6.5
37.7
126.*
11*.*
107.3
111.7
37.3
32.9
38.5
137.5
1*1.7
131.1
Average
21 Cycles
5/28 to 6/11
**.8 + *.l
3*.2 ± 6.8
123.8 + 5.5
112.9 + 5.7
113.8 +• 8.7
1H.6 + 6.5
33.2 + *.l
30.1 + 3.5
36.* + 3.8
1*0.3 + 3.5
135.2 + *.*
137.7 +• 7.*
aCharcoal previously exposed to HC-only blend in Work Assignment 12
''Atypical breakthrough time observed, 162.5 minutes
cAtypical breakthrough time observed, 153.5 minutes
-------
TABLE D-3. WEIGHT GAINS, CONTINUATION OF HYDROCARBON-ONLY BLEND
CHARCOAL TESTING*
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford it
5/21
-0.30
-0.07
-0.12
0.00
-0.09
-0.11
Weight Gains, grams*3
0.29
0.89
0.57
0.7*
0.66
0.61
1.28
1.57
1.06
1.21
1.1*
1.08
1.56
1.85
1.26
l.*2
1.35
1.25
1.73
2.02
1.38
1.56
1.15
1.39
1.76
2.03
l.*2
1.59
l.*9
l.*3
1.76
2.05
l.*3
1.62
1.17
1.16
5/30
1.50
1.83
1.2*
l.*5
1.25
1.29
5/31
1.79
2.09
[.17
1.67
1.17
1.52
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
0.07
-0.07
-0.07
-0.16
-0.18
0.07
1.0*
0.87
0.92
0.19
0.12
0.37
1.80
1.58
1.6*
0.37
0.37
0.56
2.09
1.83
1.97
O.*0
O.*0
0.59
2.29
2.00
2.15
0.*2
O.*0
0.6*
2.33
2.02
2.20
0.*2
0.*2
0.61
2.31
2.00
2.18
0.*3
O.*0
0.66
2.12
1.80
1.96
0.31
0.29
0.58
2.37
2.03
2.18
0.39
0.38
0.69
a
-O
Canister
6/3C
6/1
6/5
6/6
6/7
6/10
6/11
6/12C
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford *
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
1.66
1.99
l.*6
1.67
l.*5
l.*9
2.33
1.99
2.13
0.32
0.38
0.61
1.63
1.93
l.*l
1.61
1.38
l.*3
2.33
1.99
2.13
O.*0
0.**
0.73
2.01
2.30
1.79
1.89
l.*6
1.79
2.63
2.27
2.*3
0.58
0.55
0.87
2.75
2.97
2.5*
2.65
2.38
2.51
3.35
2.93
3.10
0.92
0.91
1.21
2.81
2.99
2.79
2.87
2.6*
2.81
3.38
2.92
3.15
0.9*
0.92
1.22
2.25
2.52
2.17
2.53
2.27
2.38
2.87
2.11
2.65
0.6*
0.61
0.91
2.08
2.*0
2.33
2.37
2.16
2.27
2.79
2.37
2.55
0.58
0.50
0.86
2.23
2.*0
2.11
—
2.33
2.*5
2.60
0.58
0.88
aCharcoal previously exposed to HC-only blend in Work Assignment 12
DWeight gain relative to May 21, 1985 canister weights
cThe charcoal from four of the canisters was removed before purging for speciation is Task 3.
-------
APPENDIX E
Daily Working Capacities, Breakthrough Times, and Weight
Gains for Task 2 Testing (HC-Only Mini-Canisters
Exposed to HC-Methanol Blend)
-------
TABLE E-I. WORKING CAPACITIES, SWITCHING OF HC-ONLY BLEND TO HC-METHANOL BLEND3
Working Capacity, grams'5
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford ^
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 4
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
6/13
Cycle 1
2.86
—
5.06
4.88
—
5.05
2.20
2.36
__
4.75
5.02
6/24
1.36
—
3.89
3.39
—
3.90
__
0.99
1.21
4.58
4.50
6/13
Cycle 2
2.78
—
5.14
4.70
—
5.04
1.98
2.30
4.58
4.68
6/25
1.52
—
3.95
3.83
—
3.84
„
1.02
1.23
4.54
4.43
6/14
Cycle 1
1.92
—
4.31
3.95
—
4.21
1.12
1.37
4.67
4.73
6/26
1.67
—
4.06
3.93
—
3.99
1.05
1.36
__
4.47
4.45
6/14
Cycle 2
2.18
—
4.53
4.25
—
4.38
__
1.46
1.64
4.60
4.80
6/27
1.48
—
3.94
3.66
—
3.92
1.07
1.22
__
4.46
4.69
6/17
1.38
—
3.98
3.85
—
3.65
0.77
1.07
4.41
4.40
6/28
2.47
—
4.88
4.40
—
4.78
1.77
2.13
4.66
4.78
6/18 6/20
1.57 1.56
—
3.94 4.03
3.76 3.82
—
3.70 3.84
1.01 0.92
1.28 1.19
4.48 4.41
4.63 4.51
Average
1.86 + 0.54
—
4.28 + 0.47
4.02 + 0.43
—
4.16 + 0.50
..
1.26 + 0.45
1.50 + 0.46
4.55 + 0.10
4.64 + 0.18
6/21
1.40
—
3.89
3.78
—
3.83
0.97
1.18
__
4.60
4.68
aCharcoal previously exposed to HC-only blend in Work Assignment 12)
^Working capacity is defined as the weight of hydrocarbons that can be purged
after hydrocarbon loading
-------
TABLE E-2. BREAKTHROUGH TIMES, SWITCHING OF HC-ONLY BLEND TO HC-METHANOL BLEND3
Breakthrough Times, Minutes
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 0
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
W
1
U>
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 0
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
6/13
Cycle 1
08.5
--
115.3
110.7
"
118.0
33.9
00.0
139.6
108.0
6/25
01.7
—
110.1
106.8
—
107.9
20.6
36.5
129.3
129.8
6/13
Cycle 2
58.7
—
131.1
115.0
~
123.9
06.1
52.6
131.7
137.3
6/26
Cycle 1
03.0
—
113.5
103.3
—
109.6
29.1
35.9
,-b
130.5
6/10
Cycle 1
67.5
—
132.0
118.1
—
130.5
06.6
57.0
131.8
137.7
6/26
Cycle 2
02.0
—
110.8
107.0
—
110.0
27.6
36.0
130.3
130.7
6/10
Cycle 2
71.0
—
123.0
111.6
—
118.7
__
03.0
06.8
120.5
135.1
6/27
Cycle 1
06.2
—
116.0
102.7
—
108.9
27.1
36.7
135.0
137.5
6/17
Cycle 1
61.5
—
128.0
110.7
—
116.0
_-
02.0
09.3
125.0
135.0
6/27
Cycle 2
03.8
—
112.5
101.2
—
112.0
__
26.0
36.5
__
125.1
138.2
6/17
Cycle 2
53.6
—
127.6
122.8
—
118.5
30.7
03.3
128.2
128.8
6/28
Cycle 1
03.8
—
112.5
102.0
—
115.3
28.5
36.5
„
128.5
133.0
6/18
50.3
—
119.0
111.6
—
107.8
__
32.2
01.0
__
131.0
139.7
6/28
Cycle 2
06.8
—
115.6
101.5
—
113.1
__
30.2
02.0
128.0
135.0
6/20 6/20 6/21 6/21 6/20 6/20
Cycle 1 Cycle 2 Cycle 1 Cycle 2 Cycle 1 Cycle 2
51.0 50.0 50.6 05.6 05.0 39.3
—
121.0 120.2 120.1 117.0 110.1 110.1
111.0 111.0 112.3 109.6 105.8 91.2
..
116.1 119.7 118.3 117.1 110.2 112.5
32.9 33.2 33.6 30.0 29.1 25.1
00.7 39.0 00.0 36.1 38.1 30.1
125.8 136.0 126.0 136.6 130.3 127.8
139.0 101.0 139.7 101.6 138.0 135.0
Average
50.0 + 8.7
—
119.2 + 6.6
108.7 ± 7.2
—
115.6 + 5.5
32.6 + 6.7
01.0 + 6.2
__
130.3 + 0.0
137.0 + 0.3
aCharcoal previously exposed to HC-only blend in Work Assignment 12
''Atypical breakthrough time observed, 1 16.0 minutes
-------
TABLE E-3. WEIGHT GAINS, SWITCHING OF HC-ONLY BLEND TO HC-METHANOL BLEND3
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 4
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 4
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
6/13
Cycle 1
0.73
1.09
1.21
—
1.01
1.14
1.31
0.39
0.56
6/25
2.46
2.77
2.73
—
2.62
2.52
2.66
0.92
1.24
6/13
Cycle 2
-0.16
0.36
0.62
—
032
__
0.51
0.55
0.49
0.59
6/26
2.19
2.50
2.48
—
2.35
2.29
2.43
0.79
1.10
6/14
Cycle 1
0.22
0.74
0.98
—
0.70
0.96
1.01
0.58
0.71
6/27
2.30
2.53
2.51
—
2.32
__
2.36
2.50
0.84
1.19
Weight Gains, grams"
6/14 6/17 6/18 6/20 6/21
Cycle 2
0.12 1.36 1.58 1.63 2.13
0.61 1.65 1.85 1.97 2.50
0.87 1.83 1.96 2.06 2.53
—
0.59 1.60 1.75 1.85 2.39
-
0.91 1.93 2.04 2.05 2.38
0.93 2.01 2.11 2.11 2.48
0.61 0.75 0.81 0.77 0.85
0.67 0.98 1.01 1.03 1.15
6/28
0.79
1.11
1.18
—
0.90
1.13
1.12
0.62
0.93
6/24
2.65
2.95
2.96
2.82
„
2.71
2.86
1.00
1.29
aCharcoal previously exposed to HC-only blend in Work Assignment 12
''Weight gain relative to May 24, 1985 canister weights
-------
APPENDIX F
Daily Working Capacities, Breakthrough Times, and Weight
Gains for Task 2 Testing (Re-exposure of HC-Only
Mini-Canisters to HC-Only Blend)
-------
TABLE F-I. WORKING CAPACITIES, SWITCHING OF HC-METHANOL BLEND TO HC-ONLY BLEND2
Working Capacity, gramsb
ro
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 1
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
7/1
Cycle 1
1.86
—
>4.20
4.06
—
4.21
1.17
1.07
4.49
4.79
7/1
Cycle 2
2.25
—
4.69
4.23
4.56
„
1.50
1.82
4.52
4.76
7/2
Cycle 1
1.51
—
4.06
3.98
—
4.05
0.89
1.15
4.59
4.56
7/2
Cycle 2
1.83
—
4.25
3.99
—
4.23
..
1.22
1.49
4.66
4.74
7/3
Cycle 1
1.22
—
3.65
3.51
—
3.56
..
0.63
0.89
4.55
4.50
7/3
Cycle 2
1.57
—
3.84
3.41
—
3.78
..
1.00
1.22
__
4.44
4.68
7/10
1.49
—
3.84
3.71
—
3.93
..
1.05
1.27
4.83
4.76
7/11
1.57
—
3.93
3.61
—
3.86
1.06
1.25
4.73
4.70
7/12
1.83
—
4.22
4.14
—
4.25
1.31
1.56
4.71
4.77
7/15
1.48
—
3.89
3.88
—
6.62C
„
6.06C
1.53
4.52
4.70
Average
1.66 + 0.29
—
4.06 + 0.30
3.85 + 0.28
—
4.05 + 0.30
__
1.09 + 0.25
1.37 + 0.26
4.60 + 0.12
4.70 + 0.10
aCharcoal previously exposed to HC-only blend in Work Assignment 12
^Working capacity is defined as the weight of hydrocarbons that can be purged after hydrocarbon loading
cZero air from compressed gas cylinder was used as purge air for the 110 minute purge cycle for
these two mini-canisters, values not used in averages
-------
TABLE F-2. BREAKTHROUGH TIMES, SWITCHING OF HC-METHANOL BLEND TO HC-ONLY BLEND3
Breakthrough Times, Minutes
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 4
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 4
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
7/1
Cycle 1
55.5
—
117.0
113.1
—
118.5
..
38.2
49.1
122.6
139.8
7/12
Cycle
47.9
—
. 117.6
110.8
—
118.3
33.0
40.0
—
139.3
138.0
7/1
Cycle 2
55.8
—
128.3
112.4
—
124.1
__
38.4
46.7
124.6
136.6
7/12
Cycle 2
47.6
—
114.1
110.1
—
116.5
32.6
40.2
—
136.7
140.9
7/2
Cycle 1
59.0
—
129.7
119.3
—
128.7
__
38.6
51.3
127.5
130.1
7/15
Cycle 1
40.0
—
103.3
96.5
—
103.7
30.9
39.6
—
120.0
133.0
7/2 7/3 7/3 7/10 7/10 7/1 1 7/11
Cycle 2 Cycle 1 Cycle 2 Cycle 1 Cycle 2 Cycle 1 Cycle 2
54.6 54.1 50.5 49.0 42.2 42.9 46.2
—
122.3 122.5 114.5 108.3 105.8 110.4 113.4
114.0 113.0 98.9 107.6 96.4 103.5 97.8
__
121.7 116.7 111.9 120.3 108.0 109.8 110.7
34.0 31.7 30.7 33.5 27.4 29.1 33.8
47.1 46.2 43.0 41.8 37.6 36.9 37.3
133.3 132.8 115.0 128.0 128.6 129.9 126.8
137.3 136.8 133.0 130.8 133.0 140.0 134.6
Average
49.6 + 5.9
—
115.9 + 8.1
107.2 + 7.7
—
116.1 ±7.0
33.2 + 3.5
42.8 + 4.8
—
128.1 + 6.7
135.7 + 3.5
aCharcoal previously exposed to HC-only blend in Work Assignment 12
-------
TABLE F-3. WEIGHT GAINS, SWITCHING OF HC-METHANOL BLEND TO HC-ONLY BLEND*
Weight Gains,
Canister
Chrysler 1
Chrysler 2
Ford 1
Ford 2
Ford 3
Ford 4
GM 1
GM 2
GM 3
Toyota 1
Toyota 2
Toyota 3
7/1
Cycle 1
0.79
1.08
1.21
—
0.97
__
1.21
1.20
0.69
0.94
7/1
Cycle 2
0.41
0.75
0.97
—
0.73
___
0.97
0.89
0.70
0.91
7/2
Cycle 1
0.94
1.22
1.40
—
1.13
__
1.45
1.42
0.70
1.00
7/2
Cycle 2
0.91
1.19
1.39
—
1.14
_-.
1.40
1.37
0.70
0.98
7/3
Cycle 1
1.56
1.82
1.89
—
1.71
-.—
1.93
1.95
0.82
1.11
7/3
Cycle 2
1.62
1.90
1.96
—
1.86
____
1.98
1.99
0.72
1.09
7/10
2.10
2.43
2.41
—
2.37
___
2.27
2.29
0.74
1.17
7/11
1.89
2.24
2.22
—
2.20
__
2.07
2.15
0.55
1.01
7/12
1.61
1.99
1.98
—
1.92
•».»
1.84
1.87
0.64
0.99
7/15
1.76
2.01
1.87
__
-0.73C
-~~
-3.01C
1.66
0.76
1.12
aCharcoal previously exposed to HC-only blend in Work Assignment 12
''Weight gain relative to May 24, 1985 canister weights
cZero air from a compressed gas cylinder was used as purge air during the 110 minute purge
cycle for these two mini-canisters
-------
APPENDIX G
Mini-Canister Daily Environment
-------
TABLE G-l. MINI-CANISTER DAILY ENVIRONMENT - MASS OF WATER VAPOR IN
AIR, ROOM TEMPERATURE, AND BAROMETRIC PRESSURE
Mass of Water Vagor Barometric Pressure,
inches Hg
29.05
29.08
28.99
29.01
28.99
29.10
29.09
29.03
29.04
29.18
29.25
29.18
29.13
29.05
29.14
29.14
29.27
29.29
29.25
29.13
29.04
29.14
29.12
29.13
29.18
29.03
29.27
29.25
29.16
29.12
29.14
Day
5/27
5/28
5/29
5/30 (am)
5/30 (pm)
5/31
6/3
6/4
6/5
6/6
6/7 (am)
6/7 (pm)
6/10 (am)
6/10 (prn)
6/11 (am)
6/11 (pm)
6/12
6/13 (am)
6/13 (pm)
6/14 (am)
6/14 (pm)
6/17 (am)
6/17 (pm)
6/18
6/20
6/21
6/24 (am)
6/24 (pm)
6/25
6/26 (am)
6/26 (pm)
Room Temperature, °F
73
76
76
75
75
76
76
75
76
75
73
73
74
74
74
73
74
73
76
74
74
76
74
73
75
75
76
75
75
74
75
in Air, grains/ft^
5.78
6.05
6.05
5.87
6.25
6.05
7.13
6.25
6.06
6.25
6.13
6.40
5.96
6.33
6.32
5.51
5.68
4.62
4.20
5.32
5.04
6.73
5.32
5.78
6.53
6.53
7.52
6.91
5.87
5.68
6.25
G-2
-------
TABLE G-l (CONT'D). MINI-CANISTER DAILY ENVIRONMENT - MASS OF WATER
VAPOR IN AIR, ROOM TEMPERATURE, AND BAROMETRIC PRESSURE
Mass of Water Vapor Barometric Pressure,
Day Room Temperature, °F in Air, grains/ft^ inches Hg
6/27 (am)
6/27 (pm)
6/28 (am)
6/28 (pm)
7/1 (am)
7/1 (pm)
7/2 (am)
7/2 (pm)
7/3 (am)
7/3 (pm)
7/10 (am)
7/10 (pm)
7/11
7/12 (am)
7/12 (pm)
7/15
75
75
75
75
75
76
7*
75
75
75
Ik
76
76
76
76
6.33
6.91
5.58
5.30
5.58
5.47
5.96
5.87
6.25
6.53
5.96
6.05
5.76
6.05
6.05
29.2*
29.27
29.37
29.36
29.37
29.35
29.31
29.*0
29.31
29.21
29.23
29.20
29.23
29.19
29.39
G-3
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 460-3-85-010
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Additional Mini-Canister Evaluation
5. REPORT DATE
December 1985
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Lawrence R. Smith
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Southwest Research Institute
Department of Emissions Research
6220 Culebra Road
San Antonio, Texas 78284
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-3162
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
2565 Plymouth Road
Ann Arbor, Michigan 48105
13. TYPE OF REPORT AND PERIOD COVERED
Final(3/85 - 8/85)
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This program involved the continuation of testing on charcoal mini-canisters that
were developed and nreviouslv tested in Work Assignment 12 of this Contract. The
results of the previous study are reported in EPA Report No. 460/3-84-014. In
this study, additional testing was conducted both on mini-canisters previously
exposed to a hydrocarbon-only blend, and on mini-canisters previously exposed to a
hydrocarbon-methanol blend. Switching of exposure blends (between the hydrocarbon-
only and the hydrocarbon-methanol blend) on the same set of mini-canisters was also
undertaken to determine if any of the effects of the previous blend exposure
were reversible. Breakthrough times, working capacities and canister weight
gains were monitored for each of the mini-canisters during all testing.
Laboratory humidity, temperature, and barometric pressure were also monitored to
determine the effect of these parameters on mini-canister working capacity and
weight gain. Hydrocarbon and methanol speciation were conducted on the vapors
purged from eight of the canisters (four from the hydrocarbon-method blend
exposures and four from the hydrocarbon-only blend exposures).
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Air Pollution
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Evaporative Canisters
Methanol
Charcoal Evaluation
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
77
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
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