EPA-AA-SDSB-87-10
                   Technical Report
        Effects of Gasoline Volatility on the
            Hydrocarbon Exhaust Emissions
            From a 1984 Oldsmobile Cutlass
                          By

                   Alan E. Schuler


                     August 19S7
                        NOTICE

Technical Reports  do  not necessarily  represent final  EPA
decisions  or  positions.    They  are  intended  to  present
technical  analysis   of   issues   using   data  which   are
currently available.   The purpose  in  the release  of  such
reports  is  to   facilitate  the  exchange   of  technical
information  and   to  inform   the  public   of  technical
developments which may  form  the  basis  for  a final  EPA
decision, position or regulatory action.
       Standards Development and Support Branch
         Emission Control Technology Division
               Office of Mobile Sources
             Office  of Air  and Radiation
        U. S. Environmental Protection Agency

-------
                              -2-
I.    Executive Summary

     This   report   describes   the   results   of   a   gasoline
volatility/exhaust  emission   test  program   done  under   EPA
contract by ATL Laboratories  in Columbus,  Ohio.   The  program
was  developed   to   help  explain  why  HC   exhaust   emissions
frequently increase when using fuels with  high volatility.   The
testing involved a  1984  3.8L  Olds  Cutlass  with multi-point fuel
injection.   Two  different fuels  (9.0 and 11.5 psi  RVP)  were
used, along with three different conditions  of  the evaporative
canister (no purge, "standard" canister  loading, and  a  loading
beyond  breakthrough).   In addition,  tests were performed  with
both fuels with  the catalytic  converter  removed and a standard
canister loading  to determine the  effect  of RVP  on  engine-out
emissions.

     For this  vehicle,  it appeared  that  the  increase  in  HC
exhaust  emissions  with  increased  fuel  RVP  is   due  to  the
increase in vapors  generated   in  the fuel tank during  vehicle
operation.   Canister  weight  (loading)   did  not affect  exhaust
emissions.   Thus, this  increase in fuel  tank vapors  may  help
explain the RVP  differences  seen in EPA's Emission Factor data
base.[l]   This  means  that the  temperature  of the   fuel  tank
simulated  during   FTP   testing  may  be  more critical  than
previously believed.

     This   report   is   divided   into   four   major   sections:
Background  and   Test  Format;  Test  Results;  Discussion  of
Results; and Conclusions.  The fuel summary  sheets are included
in the Appendix.

II.   Background and Test Format

     As previously  mentioned,  the purpose of  this  study was to
determine why HC exhaust emissions  increase  with increased fuel
volatility.  Related  test  programs  indicate  that unmetered fuel
may  be  the cause,  although  direct fuel  effects  could  not  be
confidently ruled out.[2,3,4]   Most of  this  unmetered fuel was
thought to have come from the  canister  purge,  with the  rest
being generated  in  the fuel  tank during vehicle operation.  To
better  evaluate  the  RVP/exhaust  emission  interaction,   a  test
program was developed calling  for  testing  with 9.0 and 11.5 RVP
fuel,  each with  no  purge,  standard  canister  loading,  and  a
canister   loading   beyond  breakthrough  condition   (hereafter
referred to as  saturated though  this  was   not   strictly  the
case).   Under  the  no purge  condition,  unmetered fuel  to the
engine from the fuel tank was  also interrupted.

     In addition to the  canister  variations  described above,  a
series  of  tests  with the  catalyst  removed were performed using
a standard canister loading  for both fuels.   These  engine-out
emission values  would  indicate  whether  the  differences  in HC
exhaust emissions occurred in  the engine or  catalyst.   Assuming

-------
                              -3-
increased  purged  hydrocarbons  (HC)  to be  the major  cause  of
increased HC tailpipe emissions,  two  mechanisms  were considered
possible.  According to the first mechanism, the  increase  in HC
emissions  could  be occurring  mostly during  combustion.   The
catalytic converter - being  primarily a proportional  reduction
device -  would then allow a  proportional  increase  in  tailpipe
emissions.  According to the second mechanism, formation of the
excess  hydrocarbons could  be  the  same  as  with  the  smaller
purged HC quantities,  but a reduction in excess oxygen  could be
reducing  catalyst  efficiency,   resulting   in  an  increase  in
tailpipe emissions.

     During  combustion,  the  hydrogen atoms   in  the  fuel  are
oxidized  before the  carbon   atoms.   Therefore,  as the oxygen
level starts to decrease, incomplete  oxidation will  occur  first
for  the  carbon atoms  causing  an increase in CO levels  (with
little or no  increase  in HC  levels) .   Because of this  greater
sensitivity, CO emissions from all  tests  were  also  evaluated
along with HC emissions.

     Due   to   the   large   number   of   unknowns   and   the
correspondingly high  test  costs for  a comprehensive  program,
only one  vehicle  was tested  at this stage  of the  evaluation.
To further  reduce  costs,  hot-start  LA-4's  were used rather than
full  FTPs.   A revised  version  of  this   program  using  more
vehicles was  left  as  a future  option, depending  on  these   test
results.

     To select a vehicle for  this test program, an  analysis was
made of the  test  results  of  308 cars from  EPA's Emission Factor
(EF)  data  base to  determine  which,  if   not  all,  types  of
vehicles have  an exhaust  emission sensitivity to  fuel RVP.  The
analysis  of  these  vehicles  showed  that  several  groups  of
vehicles had  a fairly  high statistical sensitivity  to  fuel RVP
(volatility).   The most, notable  were 3.8  L  GM  vehicles  with
multi-point  fuel  injection  (PFI).  -A car  was then  chosen from
this  group  (a  1984 Oldsmobile  Cutlass  Cierra)  for  testing.
Before starting the actual test program, back-to-back hot start
LA-4's on both 11.5 and 9.0 RVP  fuels were  run at ATL  to verify
the vehicle's continued sensitivity.

     Each test  condition was  to receive  a  single  replicate run,
except for  the "baseline"  (standard canister loading),  which
was  to  receive two replicates.    The  second and  third  baseline
runs (for a  given  fuel)  were  made in between  the no purge and
saturated canister runs to confirm  the  vehicle's  repeatability.
The  adaptive memory software in  the vehicle's  computer  was  a
particular  concern,  since  it   could be  causing  the  exhaust
emissions of  one   test  to be   affected  by  the  previous  tests
conditions.

-------
                              -4-
     To ensure  consistent canister  loadings,  the canister  was
artificially  loaded  prior to  each  test.   A baseline  canister
weight was obtained" by purging the canister for one  hour  at  one
scfm,  and  then  increasing  the  weight  by  30/46 grams  for  a
"standard" load  (9.0/11.5 RVP,  respectively),  and 80 grams  for
the  loading  beyond breakthrough  (both 9.0  and 11.5  RVP).   The
standard  load represents the  estimated uncontrolled emissions
from one  diurnal and one hot soak, plus an  additional  10 grams
to  account  for  the  estimated  residual  in  a  "typical"  in-use
canister.

     In addition  to  measuring exhaust  emissions and  canister
weights,  fuel  tank,  engine block,  and  engine oil  temperatures
were also  recorded,  along with purge and manifold vacuum.   All
tests  were  performed  with  the  same  driver  and on  the  same
dynamometer.

     The general testing sequence consisted of:

      1.   Drain vehicle fuel.
      2.   Weigh canister (record wet and dry bulb temps).
      3.   Purge canister for 1 hour at 1 scfm.
      4.   Weigh canister.
      5.   Install canister on portable fuel tank.
      6.   Load  canister to desired  weight  by adding 75°F  test
           fuel  to the portable  tank.   This pushes  fuel  vapors
           out of the tank into the canister.
      7.   Weigh canister.
      8.   Fuel  the  vehicle  to  40  percent  of  tank  capacity
           using 75°F test fuel.
      9.   Vent  tank line to  air  intake of  car  and  plug purge
           line.   (Canister is  not installed on vehicle.)  Push
           vehicle onto dyno.   LA-4  prep to warm-up  engine  and
           catalyst.
     10.   10-minute   soak.   During  soak,   install  canister  on
           vehicle, connect tank and purge lines.
     11.   Hot-start    LA-4.    Measure   emissions,    traces   on
           temperatures and vacuums.
     12.   One hour  soak  in soak  room.   (Push vehicle  there).
           Immediately after soak, remove canister and weigh.

III. Test  Results

     Summaries  of  hot-start LA-4  emissions, temperatures,  and
canister  weights  areas   are  shown  in  Tables  1,   2,   and  3,
respectively.    The emission results  for bags  1 and 2  of  the
LA-4  are  shown  in  Table  4.    The  tests  generally  went  as
planned.  Four  additional tests  were run,  usually  to  further
replicate  questionable data.  The retest for 9.0 RVP fuel  with
no  catalyst was due  to  a malfunction in  the  temperature chart
recorder.   Since the  "no purge" (NP) conditions  did  not involve
the  charcoal  canister,  the one-hour  post-run  soaks were  not
done.

-------
                                              Table 1
                                   Emission Test Results  (g/mi)
                                1984 Olds Cutlass Cierra (3.8L PFI)
Condition
FTP
EPA Calc.Hot Start
(Bag 2&3)
Qualification
       Retest
No Purge
Standard Loading
No Catalyst
        Retest
        Retest
                    Fuel
                    RVP   Rep
                    11.5
                     9.0
                    11.5
                     9.0
                    11.5
	    9.0
Standard Loading    11.5
                     9.0
                    11.5
                     9.0
Saturated Loading   11.5
                     9.0
                    11.5
                     9.0
1
1
1
2
3
1
2
3
2
3
1
2

1
2
1
2

1
2
1
2
1

1
1
2
HC

.36
.23
.16
i n

CO
EPA EF
7.56
4.05
5.26
•) OK

NOx
C02
MPG
TEST RESULTS
.76
.64
.65
oq

449.8
461.4
	


19.15
18.94




ATL TEST RESULTS*
.15
.10
.19
.17
.13
.13
.11
.19
.13
.13
.13
.11
.10
.10
.13
.16
.11
.13
2.30
1.97
1.86
2.19
2.16
2.12
5.60
3.00
5.57
5,93
5.83
2.72
2.60
4.68
3.00
3.90
2.67
2.44
2.25
2.00
4.10
5.51
2.58
3.67
16.59
16.91
16.60
13.78
13.58
14.61
.65
.55
.70
.71
.71
.62
.54
.61
.54
.55
.68
.67
.64
.63
.70
.76
.62
.63
2.05
2.06
2.09
2.21
2.10
2.17
433.9
442.5
442.1
441.6
451.2
429.8
407.9
449.6
443.2
441.8
456.1
454.9
451.8
451.7
438.4
443.6
432.3
444.9
407.3
417.8
405.6
413.4
412.4
417.7
20.01
19.82
19.64
19.64
19.24
20.41
21.51
19.38
19.78
19.78
19.25
19.32
19.46
19.48
19.92
19.59
20.31
19.66
20.12
19.68
20.27
20.07
20.13
19.82
                                             Odom
                                            23512
                                            23550
                                            23512
                                                                       23550
38431
38461
38490
38505
38610
38639
38713
38728
38742
38757
38520
38535

38654
38669
38580
38595

38683
38698
38831
38846
38860

38772
38787
38802
         Run
        Order
 1
 2
 7
 8
13
14**
13r
14 r
 3
 4

 9
10
 5
 6

11
12
17
18
17r

15
15r
16
         Test
         Date
                10/08/85
                10/11/85
11/19/86
11/20/86
11/25/86
11/25/86
12/01/86
12/02/86
12/04/86
12/04/86
12/05/86
12/05/86
11/26/86
11/26/86

12/02/86
12/02/86
12/01/86
12/01/86

12/03/86
12/03/86
12/09/86
12/09/86
12/10/86

12/08/86
12/08/86
12/08/86
                                                                                                            I
                                                                                                            ui
     LA-4 (2 bag) tests.
     Test results excluded from statistical analysis.

-------
                                                     Table 2
                                                 Temperature  Data
                                             1984 Olds  Cutlass  Cierra
Condition
(jualif ication
Fuel
RVP

11.5
 9.0
Standard Loading    11.5
                     9.0
       Retest
No Purge
 9.0
11.5
                     9.0
Saturated Loading   11.5
                     9.0
Standard Loading
Mo Catalyst
       Retest
       Retest
11.5
                     9.0
Rep

1
1

1
2
3

1
2
3
2
3

1
2

1
2

1
2

1
2

1
2
1

1
1
2
TEMPERATURES i
Fuel Tank
Soldered T/C
Test
Start
87
89
88
91
88
90
86
90
86
90
88
91
92
97
85
89
86
90
88
90
88
_
88
91
Test
End
97
98
97
100
98
100
98
102
98
100
98
100
103
107
95
99
98
100
97
98
98
_
96
99
Magnetic T/C
Test
Start/
87
88
87
91
88
89
86
90
85
90
87
90
91
96
84
89
86
90
88
89
88
	
87
90
Test
End
95
97
96
98
96
99
97
101
97
99
97
99
102
105
93
98
97
99
96
97
97
	
95
98
(°F)
Engine
Block
Test
Start
196
192
187
189
197
192
189
194
191
194
196
195
193
197
191
195
190
193
195
193
192
	
191
193
Test
End
185
. 183
181
182
186
187
183
189
184
179
180
182
185
184
186
185
183
183
185
181
183
	
181
180
Oil
Test
Start
199
197
192
200
197
198
193
198
194
201
195
204
200
205
193
199
194
202
200
202
194
_
201
199
Test
End
243
242
242
242
242
243
242
243
241
244
242
243
243
244
242
243
242
242
242
242
242
_
242
243
Run
Order
A
B
1
2
7
8
13
14
13r
14r
3
4
9
10
5
6
11
12
17
18
17r
15
15r
16
  Test
  Date

11/19/86
11/20/86

11/25/86
11/25/86
12/01/86

12/02/86
12/04/86
12/04/86
12/05/86
12/05/86

11/26/86
11/26/86

12/02/86
12/02/86

12/01/86
12/01/86

12/03/86
12/03/86

12/09/86
12/09/86
12/10/86

12/08/86
12/08/86
12/08/86
                                                                                                                     I
                                                                                                                     (Ti

-------
                                                          Table  3
                                                    Canister Weights*
                                                 1984 Olds Cutlass Cierra
'•.mdition
 uilif ication
  Purge
  .mclard Loading
  Catalyst
      Retest
      Retest
Fuel
RVP

11.5
 9.0
 •uKlard Loading     11.5
      Retest
                     9.0
                    11.5
                     9.0
11.5
                     9.0
Rep

 1
 1

 1
 2
 3

 1
 2
 3
 2
 3

 1
 2

 1
 2
  indard Loading     11.5     1
                            2

                     9,0     1
 1
 2
 1

 1
 1
 2
Fully
Purged
Weight**
791.24
799.39
788.14
788.14
799.03
793.35
788.55
788.55
788.55
788.55
___
	
	
	
793.15
793.15
789.54
789.54
798.42
798.40
798.42
791.68
791.88
791.68
Wet
Bulb
(°F)
61
61
61
60
58
57
59
59
59
59
_._
	
	
	
63
63
58
57
65
65
65
57
57
59
Dry
Bulb
<°F)
76
72
71
71
73
72
72
72
72
72
___
	
	
	
72
72
71
70
75
75
75
71
70
70
Begin
Test
Seq.
802.13
802.83
834.78
834.84
844.64
823.08
819.49
817.89
819.39
819.76
__.
	
	
	
864.44
864.67
850.88
850.54
844.90
844.51
844.34
821.98
821.75
822.00
Wet
Bulb
(°F)
62
62
62
63
58
59
58
58
59
56

	
	
	
56
59
57
56
65
64
61
58
57
58
Dry
Bulb
(°F)
76
72
77
74
71
73
71
72
69
70
...
	
	
	
72
70
70
71
75
74
71
70
70
70
End
Test
Seq.
816.86
801.07
845.70
851.79
851.72
818.14
815.17
819.64
823.17
819.47
_._
	
	
	
867.03
870.06
838.11
839.28
851.11
854.48
857.31
815.09
815.67
825.21
Wet
Bulb
(°P>
61
59
63
63
59
61
58
58
57
56
___
	
	
	
58
59
57
59
66
65
56
56
59
57
Dry
Bulb
(°F)
77
68
74
74
70
72
72
71
69
69
___
	
	
	
70
71
70
71
76
75
68
69
70
69

Weight
Change
+14.73
- 1.76
+10.92
+16.95
+ 7.08
- 4.94
- 4.32
+ 1.75
+ 3.78
- .29
___
	
	
	
+ 2.59
+ 5.39
-12.77
-11.26
+ 6.21
+ 9.97
+12.97
- 6.89
- 6.08
+ 3.21

Run
Order
A
B
1
2
7
8
13
14
13r
14r
3
4
9
10
5
6
11
12
17
18
17r
15
15r
16
    All weights are  in grams.
    The canister was  fully  purged at the beginning of each day, except for days with retests

-------
Condition
Qualification
No Purge
Standard Loading
No Catalyst
       Retest
       Retest
Fuel
RVP

11.5
 9.0
Standard Loading    11.5
       Retest
                     9.0
11.5
                     9.0
Saturated Loading   11.5
                     9.0
11.5
                     9.0
-8-
Table 4
Emission Results by LA-4 Bag (g/mi)
1984 Olds Cutlass Cierra
Rep
1
1
1
2
3
1
2
3
2
3
1
2
1
2
1
2
1
2
1
2
1
1
1
2
Bag
HC
.095
.074
.121
.106
.108
.111
.083
.134
.105
.109
.117
.093
.097
.095
.081
.108
.077
.102
..956
.829
.808
.978
.945
.902
1
CO
2.
1.
2.
2.
2.
1.
1.
2.
1.
2.
2.
1.
1.
1.
1.
2.
1.
2.
7.
7.
7.
5.
5.
6.

74
46
32
44
94
42
33
59
61
37
05
90
82
64
61
68
19
04
27
30
43
76
67
50
Bag 2
HC
.058
.026
.067
.064
.052
.018
.024
.053
.029
.022
.017
.015
.005
.006
.047
.053
.028
.029
1.34
1.05
1. 14
1.22
1.22
1.22
CO
2.86
1.54
3.25
3.50
2.89
1.30
1.27
2.09
1.40
1.53
.62
.54
. -2
.36
2.49
2.83
1.39
1.62
9.32
9.18
9.61
8.02
7.90
8.11
Run
Order

  A
	B

  1
  2
  7

  8
 13
 14

 13r
 14r

  3
  4

  9
 10

  5
  6

 11
 12

 17
 18
 17r

 15
 15r
 16
  Test
  Date

11/19/86
11/20/86

11/25/86
11/25/86
12/01/86

12/02/86
12/04/86
12/04/86

12/05/86
12/05/86

11/26/86
11/26/86

12/02/86
12/02/86

12/01/86
12/01/86

12/03/86
12/03/86

12/09/86
12/09/86
12/10/86

12/08/86
12/08/86
12/08/86

-------
                              -9-
     Scatter plots of the  HC  and CO emissions for the tests run
with  the  catalytic  converter  on  the  vehicle  are  shown  in
Figures  1  and 2,  respectively.   In both figures,  the value for
run   14   -    standard    loading,    9.0   RVP   fuel    -    is
uncharacteristically high  compared to  the other  indolene  (9.0
RVP) values.   Using  the 9  actual  test values  for  indolene  (5
with std.  loading,  2 with  sat.  loading, 2 with  no  purge),  the
mean HC value  is  0.125  g/mi  with  a  standard  deviation  of
0.027.    Since the 0.187 HC value for  run  14 was greater  than
two standard  deviations  above the  mean (.179  g/mi),   run  14  was
excluded from the statistical  .analysis.  Figures  3  through  6
are scatter plots of the HC and CO emissions  from each  bag  of
the LA-4.

     Although  run  14   was  statistically  excluded  from  this
analysis, an investigation  was made of the possible  reasons for
the higher  emissions.   No  correlation  was found  with canister
weights.   However,  run  14 had the  highest   ending  fuel  tank
temperature  (except  for  the  no  purge tests  which did  not
include a  1-hour  soak between  runs),  which may have  caused the
unusually  high emission  results.   (The  effect  of  fuel  tank
temperature on  the  emission  results  will be fully discussed
later).   It is  plausible that  some change in  test cell air.flow
occurred for this  test,  possibly a slightly misplaced fan — the
engine  block  temperatures  are also high, which  could alter the
test conditions.  Based  on the  consistency,  trends,  and  values
of the  other  results,  a change in vehicle (fuel tank)  cooling
is the  most  likely  identifiable cause  of the  unusually  high
emissions.

IV.  Discussion of Results

     The scatter  plots  shown in Figures  1 through  6 provide a
good visual indication of  how  the  various conditions  relate  to
each other.   The  exhaust  emissions were  further  analyzed using
a  series  of  one-way  analyses  of  variance (ANOVAs)  with  a  10
percent  significance   level,   which   compared   the  variances
between cases to those within cases.  However,  these statistics
must be  considered  carefully due  to  the small  amount of data.
Also,   ANOVAs  assume  normal   distributions,   which  cannot  be
confirmed with only single  replicates  at each  condition.

     A  summary of  the  F-ratios  from  the one-way   ANOVAs  are
shown in Tables 5 and  6  for HC and CO  emissions,  respectively.
Analyses were  made  of  the  LA-4  composite   emissions,  Bag  1
emissions,  and  Bag  2 emissions.   Figures  1 through 6 will  be
used  simultaneously with   Tables   5   and  6   in  the  following
discussion.

     As  shown in Figures 1 and  2,  the HC and  CO   emissions are
generally  larger  with  11.5  RVP fuel  than with  9.0  RVP fuel.
Comparisons can also be  made  for  the  three canister conditions

-------
                                     -10-

                                   "iGURE  1
                             LA —4 HC Tailpipe  Emissions





.-•-.
s
CD
"~
!-
5
.5
£
S
o
.<
u
0
I





u.^i -
0.21 -
0,20 -
0.19 -


0.18 -

0.1 7 -

0.16 -

0.15 -
0.14 -

0.13 -

0.12 -

0.1 1 -

0,10 -
0,09 -

Qual — Qualification, NP = No Purqe. Std «• Standard Loading, Sat — Saturated Loading

Std Std
a -*- i
i

Std
n
'Sot std
Quai. D
a

NP o Std
0 Sat Std ^ \ '^d
Of ^



NP - , -M
n ""dot JtO
Qual. N^" NP + +
+ • +

d-OS 1 I ! 1 i i 1 ! 1 I I 1 1 i I 1 ! 1
A B 1 2 Ji 4 5 6 7 8 9 10 11 12 13 14 1 3r 1 4r
                                   AIL Run Order
                1.5 RVP  fuel
                                                +   9.0 RVP fuel
 ',00 -
                                       URE  2
                              L^- — 4 CO Tai
                                             Erni^sions
              Qualification, NP — No Purge, *3td =• Standard Loading, Oot =• Sati rated LoadifXJ
5/jo H
4,00 -
                                                                     Std
0 00
•• nn -
                                                      10
                                                                  1.5  14  1 .5r  ' 4r
                                                -t-    90

-------
                                        -11-
                                   FIGURE 3
                              Bag  1 HC Tailpipe Emissions
1 J . 1 O —
0.15 -
0.14 -
'?
.3 0.13 -
',1
C
0
'3 0.1 2 -
VI
f
t
u
v O.1 1 -
VI
D
3
E
,3 o-io J
0
O.09 -
0.08 -

0.07 -
Qual — Qualification, NP — No Purge, Std — Standard Loading, Sat = Saturated Loading

Std
-f-
Std
n NP
D
Std
Sat Std 4- itd
std a a std *•
a Sat 4-
4-
NP
Q«l. Np ^ NP

S«
a Sat
Uuai, 4-
-f
1 i ! 1 ! 1 1 1 i i I ! 1 1 1 1 ! 1
A B 1 2 o 4 5 6 7 3 9 10 11 12 So 1 4 1 3r 1 4r
                                     ATL Run Orcter
           D    1 1,5 RVP fuel
                                                  +   9.0 RVP fuel
5.UU
                                   HGURL  4
                              Bag,  ! CO Tailpipe Emissions
      I  Dual — Duohfkotion, NP  = No Purge, Sid => Standard Loading, Sat = Saturated Loading
4 00 -}
        Qual,
          D
>.0u -4
! .00
                 std
                  a
                     Std
Oat
 c
                                           Std
                                           G
                                   Sat
            Qua!.
                                                    4-  NP
Std
                                                                    Sid
              8   1
                                     ATL Run Order
                1 !,5 RVP f
                 10  i 1   12   13  14  i 5r 1 4r
                9.0 RVF1 fue-!

-------
                                    -12-

                                 FIGURE  5
                             Bag 2 HC Tailpipe Emissions



c'
s
ssions i
fc
UJ
*-»
VI
o
i
O
r



u . i o —
0.15 -
0.14 -
0.13 -
0.12 -
0.1 1 -
0.10 -
0.09 -
0.08 -
O.O7 -
0.06 -
0.05 -
O.04 -
0.03 -
0,02 -
0.01 -
0.00 -
Qual — Qualification, NP = No Purge, Std — Standard Loading, Sat =• Saturated Loading






"a std
Qual. Q
Q Sat -T^-J Std
Sat Da +

,- - Sat Sot ' Std
NP ,jp Std -t- 4-
0 'p "*"
MP NP
-t- -1-
i t t 1 ! ! 1 t 1 t 1 ! 1 1 I 1 1 1
A 3 1 2 o 4 5 6 7 3 9 10 11 12 13 14 13r 1 4r
                                  ATL Run Order
               11.5 RVP fuel
                                               +   9,0 RVP fuel
                                 HGURL  6
                             8-jO  'j: CO Tailpipe Emissions
       Quo. I  — Qualification, NP ** No Purae. Std =- Standard Load! no.  Sat — Saturated Loadina
id
0
                    Std
                     a
.3,00 -
             Qual.
               Q
            (Jual.
                                                                    Std
                                                                 Sat
                                                                  f
                                                                        Gtd
                                                MP

-------
                                          -13-

                                        Table  5
                             ANOVA Results of HC Emissions*
                                (10% Significance Level)
Comparison
Variance in Canister Loadings
 (11.5 psi RVP fuel)
  LA-4 Values
   NP vs.  Std. vs. Sat.
   Std. vs. Sat.
   Purge vs. NP
 Bag 1 Values
   NP vs.  Std. vs. Sat.
 Bag 2 Values
   NP vs.  Std. vs. Sat.
   Std. vs. Sat.
   Purge vs. NP

Variances  in Canister Loadings
 (9.0 psi  RVP Fuel)
  LA-4 Values
   NP vs.  Std. vs. Sat.
  Bag 1 Values
   NP vs.  Std. vs. Sat.
  Bag 2 Values
   NP vs.  Std. vs. Sat.
   Std. vs. Sat.
   Purge vs. NP

9.0 vs. 11.5 RVP Fuel
  LA-4 Values
   NP/Std./Sat. Subset
   Std./Sat. Subset
   No Purge Subset
   No Catalyst Subset
  Bag 2 Values
   No Catalyst Subset
Sample
Size
7
5
7
7
7
5
7
3
8
8
6
8
15
11
4
6
Deg. of
Freedom**
2,4
1,3
1,5
2,4
2,4
1,3
1,5
2,5
2,5
2,5
1,4
1,6
1,13
1,9
1,2
1,4

F-ratio
5.21
2.97
5.08
1.02
34.2
3.04
41.1
2.21
.60
23.5
2.55
34.1
8.4
13.2
2.3
.80
                                                                  Fo***  Conclusion
                                                             4.32   Differences
                                                             5.54   No Difference
                                                             4.06   Diff. is Purge

                                                             4.32   No Difference
                                                             4.32
                                                             5.54
                                                             4.06
                                                             3.78

                                                             3.78

                                                             3.78
                                                             4.54
                                                             3.78
                                                             3.14
                                                             3.36
                                                             8.53
                                                             4.54
               Differences
               No  Difference
               Diff.  is  Purge
               No Difference

               No Difference

               Differences
               No Difference
               Diff.  is Purge
               Differences
               Diff.  w/fuels
               No Difference
               No Difference
                                            1,4
.22
4.54   No Difference
*
**
***
Excludes run 14.  NP means No Purge.
x,y  =  the   degree  of  freedom  (number  of  independent
observations) of the F distribution.   x  equals  the degrees
of  freedom  for the  number  of cases  studied, y equals the
degrees of free'dom for the number of results.
Fo  =  the  theoretical  F  ratio  for  the  given  degrees  of
freedom.

-------
                                          -14-
                                         Table  6

                             ANOVA Results of CO Emissions*
                                (10% Significance Level)
Comparison
Variance in Canister Loadings
 (11.5 psi RVP fuel)
  LA-4 Values
   NP vs. Std. vs. Sat.
   Std. vs. Sat.
   Purge vs.  NP
 Bag 1 Values
   NP vs. Std. vs. Sat.
 Bag 2 Values
   NP vs. Std. vs. Sat.
   Std. vs. Sat.
   Purge vs.  NP

Variances in Canister Loadings
 (9.0 psi RVP Fuel)
  LA-4 Values
   NP vs. Std. vs. Sat.
  Bag 1 Values
   NP vs. Std. vs. Sat.
  Bag 2 Values
   NP vs. Std. vs. Sat.
   Std. vs. Sat.
   Purge vs.  NP

9.0 vs. 11.5 RVP Fuel
  LA-4 Values
   NP/Std./Sat. Subset
   Std./Sat.  Subset
   No Purge Subset
   No Catalyst Subset
  Bag 2 Values
   No Catalyst Subset
Sample
 Size
 7
 5
 7
Deg. of
Freedom** F-ratio
   2,4
   1,3
   1,5

   2,4

   2,4
   1,3
   1,5
22.8
 3.14
25.8

 1.17

69.4
 4.43
67.2
                                                                  Fo***  Conclusion
                             4.32   Differences
                             5.54   No Difference
                             4.06   Diff. is Purge

                             4.32   No Difference
4.32
5.54
4.06
8
8
8
6
8
2,
2,
2,
1,
1,
5
5
5
4
6
2

58

103
.06
.03
.1
.80

3.78
3.78
3.78
4.54
3.78
15
11
4
6
1,13
1,9
1,2
1,4
8.79
34.3
5.38
66.4
3.14
3.36
18.51
4.54
Differences
No Difference
Diff. is Purge
            1,4
          93.7
          4.54
                                    No Difference

                                    No Difference

                                    Differences
                                    No Difference
                                    Diff. is Purge
                                    Differences
                                    Diff. w/ fuels
                                    No Difference
                                    Diff. w/fuels

                                    Diff. w/fuels
*    Excludes run 14.  NP means No Purge.
**   x,y  =  the  degrees  of  freedom   (number  of  independent
     observations) of the F distribution.   x  equals the degrees
     of  freedom  for the  number  of cases  studied,  y equals  the
     degrees of free'dom for the number of  results.
***  Fo - theoretical F ratio for the given degrees of  freedom.

-------
                              -15-
(no  purge,  "standard"  canister  loading,  "saturated"  canister
loading)  within a  given  fuel  type.   With 9.0  RVP  fuel,  all
three conditions show basically the  same HC exhaust emissions.
CO  emissions  for all  three conditions  were  also  in the  same
range.  With 11.5 RVP  fuel, the  HC  results are  more scattered
than  the  9.0 RVP  results.  Also,  the no  purge condition  (no
purge of the canister or fuel tank vapors) shows  a  reduction of
the HC  emissions to the  9.0 RVP  level.  The  difference  in the
11.5 RVP CO emissions between  purge and no  purge is  even  more
pronounced.   In  addition  to these comparisons,  the  F-ratios in
Tables 5 and 6  also show a basic  difference in  emission  levels
between the  9.0 and  11.5 RVP  fuels,  and a difference  between
purge and no purge conditions with 11.5 RVP.

     The bag 1  HC and CO results  show  no difference  between the
three conditions, for both 9.0  and  11.5 RVP fuel.  However, the
bag 2 emissions  shown in  Figures  5  and  6  show a very definite
difference  between  purge  and   no  purge   conditions.    The
difference between  the  theoretical  and calculated F-ratios  for
bag  2  (see  Tables  5  and  6)   statistically  show  a  large
difference between  the  purge  and  no purge  conditions.   The
amount of canister  loading  appears  to be irrelevant.   In  some
cases,  the   lowest   of   the  purged   emissions   occur  with  a
saturated canister.

     The  difference between purge  and  no  purge  conditions,
regardless of  canister  loading,  indicates that  the  fuel  tank
vapors  generated during  vehicle operation   are  probably  the
overriding factor  in the emission  increases.   Table 2  (test
temperatures)  shows  approximately a 10°F increase  in fuel  tank
temperature   during   the  LA-4.    The  temperature  traces  (not
shown)  are  approximately  linear  with run time.   No data  are
available  to   confirm   that  this   temperature  increase   is
representative    of   in-use  conditions   for  this   particular
vehicle.   However,  both  on-road  and  dynamometer  testing  of  a
1986  Buick  and  a  1984  Plymouth   have   shown  the  current
dynamometer  cooling arrangement to  be more  representative  than
alternative  arrangements which enhance cooling.[3,4]

     As can  be  seen in Table 2,  the  starting and  ending  fuel
tank  temperatures  always  increase  by a  few  degrees when  the
replicate run occurs on the same  day.   Except for the no purge
condition,  the  CO  emissions also  increase according to  this
same  testing  pattern.    The  HC  emissions  are  a   little  more
variable and do not  show this trend.

     A rise  in  fuel tank  temperature  would  also have  a  larger
effect (generate more vapors) on  a  high volatility fuel ( i.e.,
11.5 RVP), along with having a  larger effect  during  the  latter
and  hotter  part of  the  run,  (i.e.,  bag  2).   Comparing  the
figures for  bag  1  and  bag  2 (Figures 3 versus  5 and  4  versus
6), the differences in  emissions  between the  two  fuels  is  most

-------
                              -16-


apparent  in  bag  2.   Once  again,  increased emissions  from the
fuel tank due to  the  higher RVP fuel appear to be  the  cause of
the increased exhaust emissions.

     The bag  2  tailpipe HC  and CO emissions  versus  the ending
fuel  tank   temperatures   are  shown   in   Figures   7   and  8,
respectively.   Run 14  is  also included  in  the plots,  since
temperature was  suspected to have  affected the  results  in the
first place.   The no  purge  conditions  are plotted  separately
from the conditions which  included purge.   It is not known why
the  no  purge  HC  values  are different   for  the  two  fuels.
However, these  values  are  in  a  range  where  any  uncontrolled
test variation  could  cause such  a difference in HC  emissions.
The NP  CO emissions  are approximately the same for both fuels,
with just  a  slight inverse  relation  to fuel  tank temperature.
The reason for  this  apparent  trend is not  known  and may  be by
coincidence.

     As  previously  discussed,  the  HC  and  CO  values  which
include purge are larger than  the no purge  values.    With 9.0
RVP fuel, the HC  emissions  are too scattered to make a definite
correlation  with  fuel  tank   temperature.    However,   the  CO
emissions  appear  to   have  a  slight  positive  slope.   This
CO/temperature correlation  may actually be in the  form  of an
exponential curve, depending  on the  accuracy  of run  14.   With
11.5 RVP fuel,  both HC  and CO  appear  to have a  positive slope
with respect to temperature.   In  all  cases, more data is needed
to draw a strong conclusion.

     Table 3 (canister  weights) shows  that the  canister always
gained weight with 11.5 RVP fuel,  whereas with 9.0 RVP fuel the
canister usually lost weight.   The average  change was 9.0 grams
for 11.5 RVP  fuel and -3.8 grams for  9.0  RVP  fuel.   Therefore,
with 11.5 RVP fuel  the canister  absorbed  more vapors  from the
fuel tank during  the  run  and the 1-hour post-LA4 soak than were
purged  during the LA-4.  With  9.0  RVP  fuel,  the opposite was
true.    For the  saturated  test with 11.5 RVP  fuel,  the  canister
weight  gain  was small,  indicating  the  canister  may have been
close  to  actually  being   saturated,  or  that  equilibrium was
obtained between purge and adsorption.

     The question  still remains as to whether the  increase in
hydrocarbon  emissions  occurred  in  the  engine  or  catalytic
converter.  .The emissions  in  Table 1  for  the no catalyst test
show the  engine-out  HC  levels are  virtually  equal  for  both
fuels,   while  the  engine-out  CO   emissions for  11.5  RVP  are
higher than for 9.0 RVP.   The F-ratios included  in Table 6 show
the CO  emissions  with  11.5  RVP fuel to be  significantly higher
than the 9.0  RVP values.   Therefore,  the  increase  in  tailpipe
HC  emissions  appears  to  be due  to  a  drop  in  catalyst
efficiency,.   since   engine-out   levels   are   not   changing
significantly.   The drop  is catalyst  efficiency  is  likely due
to  reduced   oxygen   availability,   as  evidenced   by  higher
engine-out                       CO                      levels.

-------
a
3
j!
O
1
     0,08
     0.07 -
      0.06 -
      0.05 -
      0,04 -
       0.03 -
      0.02 -
      0.01 -
          94
                                          -17-

                                      FIGURE  7
                             HC vs. Ending Fuel Tank Temp., Bag 2
                                                                 NP - No Purge
                      I
                     96
                            I     I      I      I
                                  98
                                            100
                                                         I
                                                        102
CJ    1 1.5 RVP
                               Ending Fuel Tank Temperature (F)
                             9.0 RVP             0-    11.5, NP
                                                                  104
     l
   106


A    9,0, NP
                                      FIGURE  &
                             CO vs. Ending Fuel Tank Temp,, Bag 2
t
3.5 -

3 -
a
a 2.5 -
c
0
yi
£ 2 -
y
VI
| 1.5-
u
0
0 1 -
0,5 -
0 -
9
a
n NP - No Purge
a a
a


•f f
I
*
I | | | , | | | | ! 	 1 	 1
4 96 98 100 102 104 106
a    11,5 RVP
                               Ending Fuei Tonk Temperature (F)
                             9,0 RVP             <>    1 1,5," NP
                                                                                9.0, NP

-------
                              -18-


Thus,  for  this  vehicle  at  least,  this  testing  confirms  the
assumption made  in  the  Draft  Regulatory Inpact  Analysis  in
support of in-use RVP  controls  that  the effect was occurring in
the catalyst  and that no fuel economy credit  should  accrue with
the elimination of these exhaust emissions.[5]

V.   Conclusion

     The  testing of  a  1984  Olds  Cutlass  conducted  in  this
program  indicates  that  the  increase  in  exhaust  HC  emissions
caused by high RVP  fuel  is occurring in the catalyst and not in
the engine.  This was  evidenced by  the absence of  an  increase
in  engine-out  HC   emissions.    Engine-out   CO  emissions  did
increase,  indicating that the  engine  was running  richer  and
that oxygen  levels  in the catalyst  were  likely lower,  thereby
decreasing the efficiency of  the catalyst.

     The richer running  of the  engine  with higher RVP  fuel  was
apparently caused  by  an  increase   in  fuel  tank  HC  emissions
occurring while  the engine  was  running.   The  effect  was  not
apparently due to the purge  of vapors  previously  stored  in the
evaporative control  canister, since  changing  the loading  of the
canister had no  effect on  exhaust  HC emissions.  To  further
verify this  conclusion,  the  amount  of  vapors generated  in the
fuel tank over the course of  a LA-4 could be measured directly.

     Further  testing of additional  vehicles  under  a  procedure
similar to that  described in this  memo  may  not  be necessary,
since  there  may not be a need to  precisely  determine whether
the canister  or the  fuel tank is the primary cause of  the RVP
effect.   A  control   program   which  lowers   in-use  RVP  will
directly reduce  or  eliminate both effects.   A control  program
which  raises certification  fuel RVP   will  also  eliminate  the
exhaust  HC   excess,   regardless   of   whether  the source of  the
additional  unmetered  fuel  is the canister or  the  fuel  tank, as
long as the amount of vapors  generated   in  the  fuel tank and the
sum  of  all  vapors  sent to  the canister  are  representative of
in-use amounts.   The costs of  the vehicle modifications  should
also be similar since  they will focus  on the  amount and control
of purge air during operation.    In  any  event,  given  that  the
fuel tank  is definitely implicated  by  this test program,  extra
care  should  be  given  to ensure that  test  cell  cooling  is
representative of in-use conditions.

-------
                              -19-
                           References

     1.    "Relationship  Between  Exhaust  Emissions  and  Fuel
Volatility," EPA  memo from Thomas  L.  Darlington to  Charles L.
Gray, EPA, QMS, ECTD, June 24, 1985.

     2.    Final   Weekly    Report;    "Task    l   -   EPA/ATL
Correlation/Temperature  Effects,"  EPA Motor  Vehicle  Emission
Laboratory, Ann Arbor, MI,  June 20, 1986.

     3.    Letter  to API  from  Exxon  Research and  Engineering
Company, March 19, 1986.

     4.    "Effect   of   Auxiliary   Cooling   on   Fuel   Tank
Temperatures,"  EPA  Memorandum  from  Edward  Earth  to  Robert
Maxwell, February 21, 1986.

     5.    "Draft  Regulatory  Impact   Analysis;  Control   of
Gasoline Volatility  and Evaporative Hydrocarbon  Emissions from
New Motor Vehicles,"  QMS, OAR, EPA, July 1987.

-------
  -20-






Appendix

-------
                                        -21-
                              ENGINEERING OPERATIONS DIVISION
                                     Fuel Analysis Report
                                        ATL Test Fuel
Supplier: AMOCO
Proposed Use('s): Emission Factors
Quantity: 1  gallon sample     Location: ATL AMOCO Indolene
Date placed in service:        Nov-86
Date of resupply: End of Program
Analysis by: CORE
           Item

RVP (psi)
Distillation
      Initial Boiling Point(°F)
     10% Evap. Point (°F)
     50% Evap. Point (°F)
     90% Evap. Point (°F)
     End Point (°F)
    %Evaporated at 160°F
                                            Blend
                              Method    Specifications
                            ASTM D 323
                            ASTM D 86
8.7-9.0

    (a)
    (a)
    (a)
    (a)
    (a)
    (a)
 Official
EOD Values

      9.0

      92
     133
     218
     318
     439
     20.4
HC Composition
Olefins (vol%)
Aromatics (vol%)
Saturates  (vol%)
                            ASTM D 1319
                                                  (a)
                                                  (a)
                                                  (a)
                     4.4
                    24.2
                    71.4
                            ASTM D 3343
                            ASTM D 3338
                            ASTM D 1298
Weight Fraction Carbon
Net Heat of Combustion
          (BTU/lb)
Specific Gravity  (60°F/60°F)
Fuel Economy Numerator
(grams  carbon/gallon)
Fuel Economy Numerator with R Factor
(grams  carbon/gallon)
    (a)

    (a)
    (a)

    (a)

    (a)
   0.8628

   18539
   0.7428

    2421

    2414
           (a) No requirements or not addressed
Prepared  by:
Validated  by:
                                                              Date:
                                                              Date:

-------
                                       -22-
Supplier: AMOCO
Proposed Use('s): Emission Factors
Quantity: 1 gallon sample Location: ATL AMOCO Indolene
Date placed in  service:    Nov-86
Date of resupply: End of Program
Analysis by: CORE
ITEM                   -—METHOD-—       -----
RVP (PSI)              ASTM D 323
Distillation             ASTM D 86
   initial  boiling point
  5% evaporated
  10% evaporated
  20% evaporated
  30% evaporated
  40% evaporated
  50% evaporated
  60% evaporated
  70% evaporated
  80% evaporated
  90% evaporated
  95% evaporated
  end point
 evaporated at 160 °F
Sulfur                  ASTM D 1266
Lead                   ASTM D 3237
Manganese              AA
Phosphorous            ASTM D 3231
Water (Wt%)            Karl  Fischer
Hydrocarbon Composition ASTM D 1319
   olefins
   aromatics
   saturates
Research octane number
Motor octane number
Antiknock index
Sensitivity
Weight  fraction carbon
Weight  fraction carbon
Weight  fraction carbon
Net heat of combustion
Net heat of combustion
API GRAVITY
Specific gravity (60°F/60°F)
Fuel economy numerator (g  carbon/gal)
Fuel economy numerator (g carbon/gal) with R Factor
ASTM D 2699
ASTM D 2700
ASTM D 439
RON-MON
ASTM D 2789
ASTM E 191
ASTM D 3343
ASTM D 240
ASTM D 3338
ASTM D 1298
                                        ASTM  Official
                                     R     R     EOD
                                                Values
                                9.0  9.0   0.55

                                 92
                                118
                                133
                                159
                                184
                                204
                                218
                                229
                                241
                                264
                                318
                                364
                                439
                                20.4
                                100
                                 4.4
                               24.2
                               71.4
    0.0
    0.0
0.8628

 18539
    59
0.7428
  2421
  2414
                       9.0

                       92
                      118
                      133
                      159
                      184
                      204
                      218
                      229
                      241
                      264
                      318
                      364
                      439
                       20
                        0
                        0
           4.4
          24.2
          71.4
           0.0
            0
           0.0
           0.0
0.0009  0.8628
    20
   0.4
 18539
  59.0
0.7428
  2421
  2414

-------
                                        -23-
                               ENGINEERING OPERATIONS DIVISION
                                      Fuel Analysis  Report
                                        ATL Test Fuel
Supplier: Chevron
Proposed Use('s): Emission Factors
Quantity: 1  gallon sample     Location: ATL Chevron UL7CQ
Date placed in service:       Nov-86
Date of  resupply: End of Program
Analysis by: CORE
            Item

RVP (psi)
Distillation
      Initial  Boiling Point(°F)
     10% Evap. Point (°F)
     50% Evap. Point (°F)
     90% Evap. Point (°F)
     End Point (°F)
    %Evaporated at 160°F
                                            Blend
                               Method   Specifications
                            ASTM D 323
                            ASTM D 86
11.6-11.9

      (a)
      (a)
      (a)
      (a)
      (a)
      (a)
 Official
EOD Values

     11.6

       74
     112
     204
     343
     423
     31.7
HC Composition
Olefins (vol%)
Aromatics (vol%)
Saturates  (vol%)
                            ASTM D 1319
                                                   (a)
                                                   (a)
                                                   (a)
                       5.5
                      28.1
                      66.4
                            ASTM D 3343
                            ASTM D 3338
                            ASTM D 1298
Weight Fraction Carbon
Net Heat of Combustion
          (BTU/lb)
Specific Gravity  (60°F/6p°F)
Fuel  Economy Numerator
(grams  carbon/gallon)
Fuel  Economy Numerator with R Factor
(grams  carbon/gallon)
      (a)

      (a)
      (a)

      (a)

      (a)
   0.8649

   18484
   0.7416

    2423

    2423
           (a) No requirements or not addressed
Prepared  by:
Validated  by:
                                                              Date:
                                                              Date:

-------
                                      -24-
Supplier: Chevron
Proposed Use('s): Emission Factors
Quantity: 1 gallon sample Location: ATL Chevron UUCQ
Date placed in service:   Nov-86
Date of resupply: End of Program
Analysis by: CORE
ITEM                   —METHOD-—       	
RVP (PSI)               ASTM D 323
Distillation             ASTM D 86
   initial boiling point
  5% evaporated
  10% evaporated
  20% evaporated
  30% evaporated
  40% evaporated
  50% evaporated
  60% evaporated
  70% evaporated
  80% evaporated
  90% evaporated
  95% evaporated
  end point
 evaporated at 160 °F
Sulfur                  ASTM D 1266
Lead                   ASTM D 3237
Manganese              AA
Phosphorous             ASTM D 3231
Water (Wt%)            Karl  Fischer
Hydrocarbon  Composition ASTM D 1319
  olefins
  aromatics
  saturates
Research octane number
Motor octane number
Antiknock index
Sensitivity
Weight fraction carbon
Weight fraction carbon
Weight fraction carbon
Net heat of combustion
Net heat of combustion
API GRAVITY
Specific gravity (60°F/60°F)
Fuel economy  numerator  (g  carbon/gal)
Fuel economy  numerator  (g carbon/gal) with  R Factor
                             Chromaspec ASTM
                                     R     R
                  Official
                    EOD
                   Values
ASTM D 2699
ASTM D 2700
ASTM D 439
RON-MON
ASTM D 2789
ASTM E 191
ASTM D 3343
ASTM D 240
ASTM D 3338
ASTM D 1298
                           0
                               11.6 11.6   0.55

                                 74
                                102
                                112
                                132
                                156
                                185
                                204
                                235
                                251
                                291
                                343
                                376
                                423
                               31.7
                      11.6

                       74
                      102
                      112
                      132
                      156
                      185
                      204
                      235
                      251
                      291
                      343
                      376
                      423
                       32
                        0
                        0
   100
    5.5                 5.5
  28.1                28.1
  66.4                66.4
                       0.0
                        0
    0.0                 0.0
    0.0                 0.0
0.8649      0.0009 0.8649

 18484          20  18484
  59.3         0.4    59.3
0.7416             0.7416
  2423               2423
  2423               2423

-------