EPA-AA-EOD/TPB-87/1
                               Technical Report
                       The Effect of Sampling Technique
                   on the Measurement of Gasoline Volatility
                                   July 1987
                                Carl A.  Scarbro
                                 John. T.  White
                                    NOTICE

Technical  reports   do   not   necessarily  represent  final  EPA  decisions  or
positions.   Their   publication  or  distribution   does   not  constitute  any
endorsement  of  equipment  or  instrumentation  that may  have  been  evaluated.
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 improvements in emissions
measurement.

                            Testing Programs  Branch
                        Engineering Operations Division
                           Office of Mobile Sources
                        Environmental  Protection Agency
                              2565 Plymouth Road
                          Ann Arbor, Michigan  48105

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Abstract

    The  U.S.  Environmental  Protection  Agency  is  proposing  the  adoption  of
regulations  which would  reduce  the  amount  of hydrocarbons  released  to  the
atmosphere  due to evaporation  of gasoline.  One regulatory alternative under
consideration  is  to  put  an  upper limit on volatility.  Volatility is typically
quantified  by  measurement  of  Reid  vapor  pressure.   Although  established
procedures  exist  for the sampling  of fuel and  measurement  of this parameter,
there is  concern  about their utility and  efficiency  in large-scale monitoring
and enforcement situations.

    The purpose  of this program  was  to identify and quantify any differences
in  vapor  pressure  caused  by  the technique  used  to  obtain the  sample.   The
objective of  this effort is to  identify  and  document a fast,  inexpensive, and
reliable  method  to obtain enforcement-quality  samples at service station-type
facilities.

    This  program  evaluated  the  effect  of  four sampling  techniques  and  two
methods of  analysis  on  three  types  of fuels.   Six samples  for each condition
resulted  in a total of  144  data points.   One of the four  sampling methods is
described in  ASTM D  4057,  "Standard Practice  for Manual Sampling of Petroleum
and Petroleum  Products."  This, technique is  found  in paragraph 9.2.3.1 as the
all-levels  method  (one-way)  for tank  sampling.   The  other  three  sampling
methods  employed  the  standard  dispensing  nozzle  with  varying  means,  e.g.,
bottom-filling and chilling, to  prevent  the  loss of lighter  components.   One
of  the   two  methods  of  analysis  was  found  in   ASTM  P  176,  a  proposed
specification  for gasolines  which is intended  to replace ASTM D 439 standard.
ASTM P 176  contains  an  updated  version  of ASTM D  323 (the  traditional method
of measuring  vapor pressure).    The  other method was  a semi-automated version
which uses  an instrument manufactured by Herzog.   Two of the  three fuels used
were  standard  gasolines  used  in   vehicle  testing   at  EPA's  Motor  Vehicle
Emissions Laboratory.  The other was  a  sample of gasohol obtained from a local
service station.

    Also  evaluated  as  a   part  of   this  study  were  the   effect of  storage
temperature on samples,  losses due  to residence time in the dispensing system
and the time required to perform each of the sampling  techniques.

    The work was  conducted during the fall of 1986.  The results indicate that
there is  no  practical  difference between  the  volatility of a sample taken from
a  dispensing  nozzle  and  the   volatility  of  one  taken  from  the underground
tank.  This finding applied over the range  of fuels and   the  two methods of
analyses.   Purge   volume had no  effect  on the  nozzle sample  for  the ambient
conditions at the  time of the study.

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                                      -2-
Background

    As  control  of  exhaust  and evaporative  emissions  from motor  vehicles has
progressed, the  percentage  of air pollution resulting  from emissions from the
evaporation of  gasoline has  increased.   Exacerbating  this trend is  the fact
that  volatility  of typical  gasolines  has  increased   steadily  over  the past
fifteen  years,  with the  most significant  increases  in the  last  five.   These
increases are caused  by lighter and less  expensive  components which are being
used  to  maintain octane ratings  as  lead is phased out.   The  result of higher
volatility is more  emissions  from all  stages in the distribution chain as well
as those from vehicles themselves.

    EPA  is  studying a  number of  efforts  to minimize   the  release  of gasoline
vapors.   Two  of  the  most  notable are  vapor  recovery,  either by  the vehicle
(known as  "on-board")  or at  the  pump (known  as  "Stage II"),  and restrictions
on  the  volatility  of  commercial gasoline.   Although  established  procedures
exist  for the  sampling  of fuel  and the  measurement  of  volatility,  there  is
concern  about the utility and efficiency  of these  procedures in a large scale
monitoring and enforcement  situation.  Sampling for volatility must be done to
minimize  the  loss  of  those  components  that  have  the greatest  effect  on  a
fuel's  vapor  pressure.   All  sampling  methods,  including ASTM methods,  are
subject  to errors which will tend toward  lower vapor  pressure measured in the
sample versus the true vapor pressure of.the product.

Purpose

    The  purpose  of this program  was to identify and  quantify any differences
in volatility caused  by the  technique  used to obtain  the sample.   The result
of this  effort  is  intended to identify and document  a fast,  inexpensive, and
reliable method to  obtain samples  for monitoring and enforcement actions.

Program Design

Methods of Analysis:

    Historically, volatility  has  been  associated with  the results  of  a test
for  vapor pressure using  the Reid method.   This test   was  adopted  by the
American Society  for Testing  and  Materials (ASTM) in 1930 and is documented in
their procedure  D 323.   A  reference to  Reid vapor  pressure (RVP) implies this
test  procedure,  which  prescribes  a  closed  cylinder  and the measurement of the
pressure above  a  sample which has been  heated from 32°F to 100°P.  RVP values
are  typically expressed  in  pounds per square  inch  (psi).   Because it involves
a  traditional   procedure  which  addresses  volatility   in  a  typical  range  of
ambient  temperatures,  RVP  is  the  parameter  which was  examine.d  during this
program.  Two test  procedures, both  based on ASTM D 323» were used.

    One  procedure,  known  as  the "dry"  method,  is contained in  ASTM's 1986
Annual  Book  of  Standards  as part of  P  176,  "Proposed Specification  for
Automotive  Spark-Ignition  Engine  Fuel."   It  is  described  in  Annex  A3,
"Proposed Test  Method for  Vapor  Pressure  of Spark Ignition  Engine Fuel (Dry
method)."   This  procedure  is analogous to  ASTM  D  323 in almost all  respects,
the differences  lying  in  the handling of  the  vapor chamber and sample  chamber

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                                      -3-
 to minimize  contact  of the  sample with  the  water used  in the process.   The
 procedure also  prescribes a  test to  determine if water did contaminate  the
'sample during  the analysis.   These  changes  in  D 323  were deemed  necessary
 since alcohol/gasoline blends are sensitive to  water and  could undergo  a phase
 separation in  the  assembled vapor  pressure bomb  which  might reduce .measured
 volatility.

     The other procedure is  known as the "Herzog"  method.   The title  refers to
 the  manufacturer of  the  instrument  designed   to perform  ASTM  D 323  in  a
 semi-automated  manner.*  Handling of  samples  for analysis on this  machine  was
 also modified  to prevent water  from affecting the readings.   It  is used  by
 some refiners and laboratories and is expected  to  be  formally accepted  by ASTM
 as an equivalent method in  the near future.  Use  of this instrument  gives  the
 analyst a 30-50!? improvement in the time required for  an analysis.

 Fuels:

     A total of  three  types  of fuel were chosen for the  evaluation of sampling
 techniques,   two gasolines  routinely  used  in   EPA testing and  one  gasohol
 (nominally 10$  ethanol  and  90$  unleaded gasoline)  obtained  from  a  local
 service station.

     The  "Unleaded  Test Gasoline  (96 RON)"  used  as  one of  the fuels  is  the
 primary test  gasoline at the EPA  Motor  Vehicle  Emission  Laboratory (MVEL).   It
 is  used   in  Certification  and   Recall  testing   of  Light  Duty  vehicles  in
 accordance with  the Federal Test Procedure.  The  specifications for  this fuel
 are  stringent  but  were originally  based on  typical  high octane  summer grade
 gasoline  in  the  late  1960's.   The CFR  specifies  the  RVP to be  within  a range
 of 8.7 to 9.2 psi.

     The second  gasoline, "Unleaded Test  Gasoline  (Commercial),"  is  designed to
 represent  a   typical  modern   gasoline   of   intermediate  volatility   (the
 procurement  specification for  RVP is  11.5-12.0 psi).   It  is used at  MVEL as
 one of the fuels in  the Emission Factors Testing  Program.   This fuel was also
 used in the portion of the study which evaluated the effect of weathering.

     Gasohol   was  chosen for the  third  fuel  to  evaluate the  ability   of  the
 analysis   methods  and  sampling  techniques  to  properly  address  a  typical
 oxygenated blend.   The samples   were  obtained   from  a  local service  station
 where  the  product is  sold  as "Super  Unleaded" and  is  labeled as containing
 ethanol.

     Neo-Hexane,  a  pure component  with  known volatility, was also used as  a
 reference standard.   Its RVP is 9.86 psi.

     "Fleet Gasoline"  was  used  for the  portion of the  study which  addressed
 purge volume.  This is a commercial fuel used at MVEL for various  purposes. It
 is a  seasonal,  non-oxygenated,  unleaded regular  grade  gasoline.   The  current
 batch had an  RVP of 12.2 psi.   It was chosen because of its high volatility,

     * Walter  Herzog GMBH,  Fabrik fur Laboratoriumaapparate, D 6970  Lauda,
       Badstrabe, 3-5,  West Germany.

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                                      -4-
making  it  more  sensitive  to  sampling and  weathering  phenomena,  and  the
similarity of its dispensing system to normal commercial equipment.

Sampling Techniques:

    Four  different  techniques were  used to obtain  the samples,  one  from the
underground storage  tank and three from the dispensing nozzle.   Sampling from
various  levels  throughout  the  underground tank using  a  chain and  special
flasks  was  based  on  the  All-Levels  Sample  (one-way)  for  tank  sampling
specified  in   Section  9-2.3  of  ASTM  D 4057,  "Standard  Practice  for  Manual
Sampling  of  Petroleum  and  Petroleum  Products."   For  the purpose  of  this
evaluation, this  technique will  be known as "ASTM."   This is considered to be
the "official" method  and  is thought  to provide  the best representation of the
fuel  in  a tank.  However, from  the  monitoring and  enforcement  standpoint,  a
technique  involving  underground  tanks  is  time-consuming and may be extremely
difficult  to   perform,  especially on  tanks  with  the  submerged  drop  tubes
required by Stage I vapor  recovery requirements.

    One  of the   three nozzle, techniques  was  performed  in accordance  with
California Air Resources  Board (CARS)  regulations under  Section  2261  of Title
13-   It uses  a simple nozzle  extender which directs  the  flow to the bottom of
a chilled  one-quart  metal  container.  Another  technique is one that is same as
above but  foregoes  the chilled container.   They  are  referred to as "CARB" and
"Ambient," respectively.

    The  third nozzle  technique  was one which has been  employed at  MVEL and
will  be  known as the  EPA  technique.   It uses  an adapter  that  attaches  to the
nozzle and directs   the  flow  through 25 feet  of 1/4-inch  copper tubing.   The
coil  of tubing is packed  in crushed ice to  chill the sample before it reaches
the sample container.   The  outlet  of  the  tubing  is  fitted  to a  stopper in a
manner  that  bottom-fills  the  container.    The   container  is  also  packed  in
crushed  ice.   At MVEL,  the container  normally  used  for this procedure  is  a
one-quart  glass bottle.  To  reduce the  number  of variables in the study, metal
containers with necks  that could  accept the  CARB sampling device were used for
each  of the nozzle techniques.

    In each of the   four  cases above,  the sample was drawn  to  70/?-80/6  of the
capacity  of  the  one-quart  container.   Each  can was  sealed  immediately and
stored  on  ice  or   refrigerated  until  analysis.   There  was  no transfer  of
samples between the  time  of  sampling and the time of analysis.  Each container
was examined upon filling  and  before reopening to ensure a proper seal.

Number of Samples:

    A total of six   samples  in each condition  was chosen  to achieve a balance
between   the   amount  of  time   and   effort  required   and  the   statistical
significance  desired.   Thus,  six  samples  of  three  fuels using  four sampling
techniques and two methods of  analysis resulted in 144 samples.

Additional Features:

    Two  other aspects of  the issue  were   also  examined  as a  part of  this

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                                      -5-
 project.   One was "weathering" of  the  samples,  as would occur in a real-world
^situation where shipping and storage preceded  the analysis.   This subject was
 studied   by  obtaining  132  identical   samples  of  Unleaded  Test  Gasoline
 (commercial)  and  storing  60 samples  at 40CF,  and 60  at 80°F.   Twelve were
 analyzed  immediately,  six using P176 and six  by the Herzog "dry method."  The
 stored  samples  were  analyzed  after  5, 9,  14,  28,   and 59  days.   In this
 process,  one-quart cans were filled to  70-80/6  of capaciby using the "Ambient"
 sampling  methodology.

    The  last aspect of  this  study is purge volume  and  its effect on measured
 vapor pressure.  It is possible that  the volatility of fuel that has remained
 within  a dispensing system may not  properly represent  the  volatility of the
 fuel  in  the  underground  tank.    This   study   sampled  fuel  from  an  outdoor
 dispenser at MVEL.  This  dispenser was not used  over  a period of 12-24 hours
 before  each  set  of three  samples were  drawn.   The samples  consisted  of six
 sets  of  three samples of  which one was  a tank sample,  drawn as in  the earlier
 study;  a  nozzle  sample  with no   purge;  and a nozzle  sample from  the same
 dispenser after a  discharge of three gallons.

 Conduct of  the  Program

    Preliminary work was  conducted during July and August of 1986.  The  actual
 sampling  and analysis were  performed  from August  18  through September 7.   In
 general,  the  program   proceeded   smoothly.   A  sufficient number  of sampling
 flasks  were  fabricated  and  suitable  one  quart cans  from  the same  lot were
 readily available.

    The CARB, Ambient  and  EPA sampling techniques  proved to be  straightforward.
 For the  ASTM technique, we received good cooperation from Gallup-Silkworth, a
 local fuel  distributor who also  operates a number of service stations.   One  of
 their  stations  was the  source  of the  gasohol  samples  which were  found  to
 contain 9%  ethanol.

    The  adaptations of  the Herzog and  D 323 measurement apparatus to  permit
 analyses  by the   "dry"  method  were  found  to  be minor.    The   only  major
 difficulty  encountered in  the  conduct  of  the  program  was a  problem with the
 temperature controller on  the manual  bath.  We  could  not maintain 100°F and,
 therefore,  were unable  to perform P  176.   As  a result,  63  of the  72  P 176
 samples   had  to  be  stored  for  almost two  weeks  before  this  problem was
 corrected.

 Results

    Attachment   A,   "Results  of  Individual  Analyses   for  Vapor  Pressure,"
 displays  the values from each of  the  144 samples which were the primary focus
 of  this   project.   The results on each  of  the  three fuels  are  sorted by  the
 four  sampling  techniques  within  the  two  analysis  procedures.  The  mean and
 standard  deviations from  the  six samples in each of  the  24 groups are  shown.

    Attachment  B,  "Summary of Results," is a table presenting  these  results  in
 a  manner  which allows  a  comparison of the Herzog procedure  to the ASTM P 176
 Procedure for each  type of  fuel.

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                                      -6-
    Attachment  C,  "Analysis  of  Neo-Hexane,"   displays   the  results  of  the
analyses of  twelve  samples of Beo-hexane, a  pure  component of gasoline with a
known  vapor  pressure.   Six  samples  were  analyzed  by  each  procedure  to
establish a measure of accuracy.

    Attachment  D,  "Evaluation  of  Storage  Conditions  on  Vapor  Pressure,"
contains the  results  on the  lot of 132 samples; groups  of them were analyzed
at 0, 5, 9, 15, 28, and 59 days.

    Attachment  E,  "Effect  of  Purge   Volume,"  contains  the   result  of  the
analyses of the 18 samples.

    Attachment F, "Estimated  Time  for  Various Sampling Scenarios," is based on
our  experience  with   the  four  techniques.   It will  be  useful in  planning
enforcement activities.

Discussion

    The  statistics  discussed  in the following  sections  are based  on results
from  MIDAS,  the  statistical  package  available  through  the Michigan Terminal
System.  The  basic  program  is  a  univariate,   one-way,  analysis of  variance
(ANOVA) which was performed  to identify significant differences  in the average
performances.  The 95^ confidence level was chosen.

Sampling Techniques:

    The  data  on individual   samples  as  shown  in  Attachment  A permitted  a
comparison of the four sampling  techniques and  two methods of analysis on each
of the three fuels.

    In  general,  the   P  176  procedure  resulted   in   less  precision  (higher
standard  deviations)   than  the   corresponding  analyses   using  the  Herzog
instrument.  There can be several possible reasons for  this phenomenon:

    1.   An inherent advantage to the semi-automated method.

    2.   Our inexperience  with the P  176  technique and  the number  of samples
         to be analyzed in such  a short period.

    3.   Problems with the samples  themselves,  since  most  of  them  had  to be
         stored for almost two weeks while the bath was not operating properly.

    This latter reason is  supported by  the  fact that the greatest precision
for  the  P  176  Procedure  was  achieved  on  the only full  set  of  samples,  which
was  analyzed  promptly  after  sampling.   This was  the set  taken from Tank 7
using the ASTM sampling technique.

    The  statistical analysis  of the  P 176   data  showed  the  results  from the
Ambient  technique  on  the  Unleaded Test  Gasoline  (96  RON)  were significantly
higher than each of the other  three techniques.

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                                      -7-
    For the Herzog method, the following significant differences were found:

    1.   For  Unleaded  Test Gasoline  (96 RON),  the  CARB technique  had  higher
         results than the Ambient technique.

    2.   For  Unleaded  Test  Gasoline  (Commercial),  the  EPA  technique  showed
         higher results than each of the other three.

    3.   For  the  Super  Unleaded Gasoline  (Gasohol),   the  ASTM  technique  had
         higher results than the EPA or CARS techniques.

    Notwithstanding  the  statistical significance  of the findings,  it appears
that any  of the nozzle  techniques  can be  employed  to  obtain a representative
sample of a typical gasoline.

Comparison of the Two Methods of Analysis:

    The  data  in  Attachments  B,   C,  and  D  were  analyzed   statistically  to
determine any differences  between the Herzog  "dry"  method  and the manual tank
and  gauges.   The  data  from  the  sampling technique  of this  study indicated
better  precision and  a positive  bias  of the  Herzog  method vs.  the  manual
method.

    The data  generated  during  the sample  weathering study  and the measurement
of  neo-hexane displayed no  significant  difference  except in precision.   The
Herzog, once again, displayed better precision over the manual tank and gauges.

    Upon reviewing the above data  in light of the precision from other EPA and
ASTM Correlation  efforts,  it  was observed  that none   of the  differences were
greater  than  the published  repeatability; therefore,   the  two methods  can be
considered essentially equivalent.

Sample "Weathering:"

    Presuming  that  most  samples  obtained for  use  in  enforcement  situations
will not be  analyzed  immediately  and  that  continuous  storage  in  a chilled
condition  is  unfeasible,  a  part of  this  project was  designed  to  assess  any
loss  in  vapor  pressure  due   to  "weathering."  The   fuel   chosen   for  this
experiment  was  the Unleaded Test  Gasoline (Commercial).   Its relatively high
vapor  pressure  increases  the  sensitivity  of the experimental  condition.   In
this project,  care  was  taken,  e.g.  leak  checks, to  ensure  that  any changes
were" due solely to the  temperature.  The results in Attachment D indicate that
the  refrigerated  samples  and  the  non-refrigerated  ones   did  not  produce
significantly different results over the total storage  period.

Evaluation of "Purge Volume:"

    Along  with  weathering,  another concern  is  the   possible  difference  in
volatility between the stored fuel and that obtained by a nozzle sample without
first  purging a  quantity of  gasoline  through the dispenser and  its  supply
lines.   We  chose  to evaluate  this  situation using a gasoline with  a 12.2 psi
Reid Vapor pressure at  MVEL  where the  fuel would be dispensed  through  the

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                                      -8-
course  of  a  day.   A set  of  three  samples  waa obtained after the dispenser was
not  used for  12  hours  to 24  hours.   One  was a  tank sample using  the  ASTM
method.   The  other  two  were  nozzle  samples using  the  Ambient  method.   The
first  sample  was  taken  from  the dispenser  nozzle  before  any  gasoline  was
pumped  through the dispenser.   Three  gallons  of  the  gasoline  were discarded
prior  to the second sample.   The  third sample was  the tank sample.  This set
of three samples  were taken over  a  six-day period for a  total  of 18 samples.
The samples were then analyzed using the Herzog "dry" method.

    The  results in Attachment  E indicate  that, under the  ambient conditions at
MVEL during  the  sampling (60eP-75eF),  there  is no  difference between the tank
sample and the nozzle samples.

Time Required for Various Sampling Techniques:

    The  times  estimated  in  Attachment F  are based on our  experiences during
the  course  of this  project.   As  can  be  seen,  there is  a  wide  range  in the
amount  of  overhead  required,  although  the times to  obtain  successive samples
are  similar.   The  results from the  vapor  pressure  analyses indicate that the
ASTM method  does not  have  any advantage  when evaluating  typical gasolines.
Moreover,  tank sampling  requires active   cooperation  by  the  service station
operator, e.g., removal of drop tube.

Choice of Containers:

    A  minor  difficulty involved the use  of  the rectangular  metal can used in
our application of the.  CARS  method.  .These cans are about 7" tall, 4" wide and
2.25"  deep.   They have  a  flat top with   a  1.75"  screw-on  cap with  a  waxed
cardboard  insert.    Our   technique  for   sealing  was   finger   tight   plus
one-sixteenth  to  one-eighth of  a  turn with  a pipe wrench.   In  general,  they
appear  to be  able  to  store  gasoline  without leakage.   However,  using  the
chilling  techniques  which involve ice  invariably  resulted  in a  pool of water
on the  top of the can.   Some  of this  water  was retained  in the joint between
the cap  and  the threads  on the can.   As the  can was opened,  the vacuum created
by the  cooled  vapor  caused some water  to  be drawn inside.  The phenomenon was
thought  to be  the  source of a  few drops of water  which were found in a number
of samples.   Use of  more rigid containers with sloping  necks  would probably
minimize the problem.  The  effect  of a small amount of water on the results is
uncertain  but  is  expected to  be  insignificant with pure  gasoline  and  cause
only a slight decrease in vapor pressure with alcohol blends.

    Rigidity  of  containers  may  be  more   important  than  neck profile.   The
collapse  and  subsequent  expansion  of  the  can sides, in concert  with  their
large  cap thread area,  is probably most   responsible  for water  from the ice
baths  entering the  samples.   Also,  chilled samples placed  in a warmer (40°P)
refrigerator  results  in  a  positive  pressure  on  the  container's  cap, whereas
ambient  temperature samples placed in  a chilled environment result in negative
pressure, causing a better seal.

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                                      -9-


Concluaions

    1.   Each  of  the  three  sampling  techniques  which  draw fuel  from  the
         dispensing nozzle resulted in a  representative  sample of the contents
         of the underground tank.

    2.   Although  some  additional   care   was   required,   proper  samples  of
         alcohol-gasoline blends were obtained in a manner similar to gasoline.

    3.   Purging of  the  dispensing  system was  not a  factor in  the measured
         volatility of the fuels.

    4.   Storage  time  and   temperature   had   no  measurable  effect  on  the
         volatility of the sample.

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                                                           AttcchMBt A
                                                  ENGINEERING OPERATIONS DIVISION

                         Th«  Effect of  Stapling T*ehniqu« on th«  )tea«ar«Mnt  of Gacolin* Volatility
                                       Results of Individual Analyses  for Reid Vapor 'Pressure
               ASTM P  176  (the  'dry* counterpart of ASTM D 323)
Naa«:
Source:
Container:
Temperature:
Technique:


Unl*ad«d
Tact
Gxolin*
(96 ROM)

EPA Tank 8
Mean:
Std. Dev.:
Unl««d«d
T««t
Gacolin*
(Coma.)

EPA Tank 7
Mean:
Std. Dev.:
8up«r
Unl**d*d
S«»olio«
(C«»ohol)

Local Dealer
Mean:
Std. Dev.:
AST*
Tank
Flask
Ambient
Dipped into
underground
tank.
8. 59
6.54
8.75
8.71
8.39
8.45
8.57
0.14
11.82
11.81
11.91
11.86
11.94
11.72
11.84
0.08
12.63
12.66
12.82
12.77
12.91
12.89
12.76
0.12
EPA
Nozzle
Can
Chilled
Bottom filled
thru chilled
tubing
8.76
8.72
8.93
8.52
8.80
8.56
8.72
0.15
11.68
11.92
11.36
11.83
11.85
11.88
11.75
0.21
12.78
11.87
12.67
12.33
12.29
12.80
12.46
0.36
CARS
Nozzle
Can
Chilled
Bottom filled
using nozzle
extension
8.58
8.67
8.54
8.67
8.36
8.45
8.55
0.12
11.24
12.04
11.67
11.66
11.74
11.73
11.68
0.26
12.93
12.87
12.54
12.68
12.64
12.62
12.71
0.15
Aabicnt
Nozzle
Can
Ambient.
Bottom filled
using nozzle
extension
8.65
8.79
8.92
9.05
9.02
9.01
8.91
0.16
11.85
12.38
11.71
11.41
11.73
11.71
11.80
0.32
12.89
• 12.71
12.05
12.21
12.37
12.64
12.48
0.32
Herzoq (Automated dry method based on D 323)
ASTM
Tank
Flask
Ambient
Dipped into
underground
tank.
9.02
8.93
8.96
8.89
8.86
8.94
8.93
0.06
12.04
12.17
12.07
11.93
11.95
11.99
12.03
0.09
13.07
12.93
12.86
12.94
12.91
13.04
12.96
0.08
EPA
Nozzle
Can
Chilled
Bottom filled
thru chilled
tubing
8.93
8.94
8.93
8.90
9.01
8.86
8.93
0.05
12.17
12.09
12.12
12.15
12.09
12.16
12.13
0.04
12.80
12.80
12.81
12.83
12.89
12.88
12.84
0.04
CARS
Nozzle
Can
Chilled
Bottom filled
using nozzle
extension
8.92
8.95
8.95
8.98
8.89
8.98
8.95
0.04
12.00
11.95
12.00
12.07
12.00
11.92
11.99
0.05
12.82
12.84.
12.47
12.73
12.88
12.95
12.78
0.17
Ambi«nt
Nozzle
Can
Ambient
Bottom filled
using nozzle
extension^
8.89
8.90
8.91
8.88
8.86
8.88
8.89
0.02
12.11
12.04
12.03 '
11.99
12.09
12.03
12.05
0.04
12.88
12.79
12.79
12.81
12.80
12.95
12.84
0.07
Note: Values shown above are expressed  in  psi.
         last update:
                                                                                                    Jul 8
                                                                                                                 16:24

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6
6
6
6
8.57
8.72
8.55
8.91
0.14
0.15
0.12
0.16
6
6
6
6
11.84
11.75
11.68
11.80
0.08
0.21
0.26
0.32
6
6
6
6
12.78
12.46
12.71
12.48
0.12
0.36
0.15
0.32
                                    Attachment  B

                           ENGINEERING OPERATIONS DIVISION

The  Effect  of  Sampling  Technique on  the  Measurement  of  Gasoline Volatility

                 Comparison of Results  from P  176 and Herzog Analyses


Sampling   Analysis      Unleaded Test          Unleaded Test         Super Unleaded
Technique    Method    Gasoline (96 RON)    Gasoline  (Commercial)   Gasoline (Gasohol)

                        N    Mean  Std Dev      N     Mean Std Dev     N    Mean  Std"bev

ASTM        P 176
EPA Nozzle  P 176
CARS        P 176
Ambient     P 176

Overall  P  176         24    8.68  0.20      24   11.77  0.23       24   12.61   0.28


                        N    Mean  Std Dev      N     Mean Std Dev     N    Mean  Std Dev

ASTM     .   Herzog      6     8.93   0.06       6     12.03   0.09       6    12.96    0.08
EPA Nozzle  Herzog      6     8.93   0.05       6     12.13   0.04       6    12.84    0.04
CARB        Herzog      6     8.95   0.04       6     11.99   0.05       6    12.78    0.17
Ambient     Herzog      6     8.89   0.02       6     12.05   0.04       6    12.84    0.07

Overall   Herzog        24    8.92  0.05      24   12.05  0.08       24   12.85   0.12


Bias   (Herzog-P  176):      0.24                  0.28                  0.25


Note: Values shown above are  Reid vapor pressure and are expressed in psi.
                                                            last update:    Jul  8    16:25

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                                     Attachment  C




                            ENGINEERING OPERATIONS  DIVISION




 The  Effect  of  Sampling  Technique  on  the  Measurement  of  Gasoline  Volatility




             Analysis of Neo-Hexane  (A pure compound of known volatility)









              Method 	Results on Individual Samples	  Mean  Std Dev    Diff.




        ASTM  P  176 9.80   9.80   9.78   9.63   9.91   9.80   9.79    0.09     -0.07







             Herzog 9.96   9.91   9.91   9.89   9.81   9.79   9.88    0.07      0.02
Note: Neo-Hexane has an RVP of  9.86.  The results above are expressed in  psi.
                                                      last update:     Jul 8    16:20

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                                        Attachment  D

                                ENGINEERING OPERATIONS DIVISION

  The Effect  of  Sampling    Technique  on Measurement  of Gasoline Volatility

                      Evaluation of Storage Conditions  on Vapor Pressure
Storage Temperature:
 Method of Analysis:
      Analysis Date:
 Days Since Sampled:
               Mean:
 Standard Deviation:
Storage Temperature:
 Method of Analysis:
      Analysis  Date:
 Days Since Sampled:
               Mean:
 Standard Deviation:
Storage Temperature:
 Method of Analysis:
      Analysis Date:
 Days Since Sampled:
               Mean:
 Standard Deviation:












40°F
Herzog
28-Feb
9
11.78
11.56
11.84
11.54
11.60
11.60
11. 65
0.13
40°F
Herzog
19-Mar
28
11.73
11.67
12.37
11.48
11.67
11.58
11.75
0.32
Analyzed
Herzog
19-Feb
0
11.67
11.79
11.71
11.70
11.78
11.73
11.73
0.05
40°F
P 176
28-Feb
9
11.64
11.68
11.79
11.89
11.50
11.60
11. 68
0.14
40°F
P 176
19-Mar
28
11.84
11.61
11.66
11.57
11.97
11.48
11. 69
0.18
. Immedia
P 176
19-Feb
0
11.74
12.02
11.66
12.01
11.89
11.73
11.84
0.15
80°F
Herzog
28-Feb
9
11.90
11.65
11.84
11.56
11.76
11.64
11.73
0.13
80°F
Herzog
19-Mar
28
11.50
11.69
11.75
11.80
11.81
11.82
11.73
0.12
itely











80°F
P 176
28-Feb
9
11.65
11.96
11.75
11.62
11.76
11.92
11.78
0.14
80°F
P 176
19-Mar
28
11.67
11.79
11.56
11.44
12.44
11.50
11.73
0.37
40°F
Herzog
24-Feb
5
11.70
11.57
11.75
11.82
11.62

11.69
0.10
40°F
Herzog
5 -Mar
14
11.91
11.56
11.52

11.66
11.56
11 . 64
0.16
40°F
Herzog
19 -Apr
59
11.69
11.52
11.47
11.70
11.56
11.71
11. 61
0.10
40°F
P 176
24-Feb
5
12.29
11.52
11.60
11.76
12.22

11 .88
0.36
40°F
P 176
5 -Mar
14
11.52
11.66
11.40
11.43
11.19
11.06
11.38
0.22
40°F
P 176
19-Apr
59 .
11.68
11.66
11.66
11.25
11.78
11.69
11. 62
0.19
80°F
Herzog
24-Feb
5
11.78
12.13
11.85
11.90
11.84
11.92
11.90
0.12
80°F
Herzog
5 -Mar
14
11.85
11.68
11.74
11.68
,11.73
11.72
11.73
0.06
80°F
Herzog
19-Apr
59
11.76
11.75
11.77
11.90
11.90
11.93
11. 84
0.08
80°F
P 176
24-Feb
5
12.46
11.93
11.91
12.22
12.05
11.46
12.01
0.34
80°F
P 176
5 -Mar
14
11.73
11.74
11.75
11.55
11.71
11.56
11.67
0.09
80°F
P 176
19-Apr
59
11.61
11.28
11.91
11.85
11.66
12.00
11.72
0.26

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                                       Attachment   E

                               ENGINEERING OPERATIONS DIVISION

     The  Effect  of  Sampling   Technique  on  Measurement  of  Gasoline  Volatility

                                 The  Effects of Purge Volume
           Method:
           Source:
  Amount of purge:
ASTM
Tank
-
12.32
12.34
12.34
12.38
12.36
12.47
12 .37
0 . 05
Ambient
Nozzle
none
12.26
12.28
12.29
12.38
12.42
12.25
12.31
0. 07
Ambient
Nozzle
3 gallons
12.29
12.36
12.27
12.36
12.42
12.47
12.36
0.08
            Mean :

      Std.   Dev.
The ambient temperature during samplings was between 50 and 60 °F.   The  analyses were
performed using the Herzog apparatus  in accordance with ASTM  P 176.
                                                              last update:
Jul-8 16:20

-------
                                    Attachment  F

                            ENGINEERING OPERATIONS DIVISION

 The. Effect  of  Sampling  Technique  on  the Measurement  of  Gasoline  Volatility

                     Estimated Time for Various Sampling Scenarios
            Activity

Overhead:
 (This aspect includes assembly of equipment
 and supplies at the base,  unpacking and
 set-up at the site, obtaining one sample,
 repacking and return to the base)

Each add'l sample from the  same tank or  nozzle:
 (This includes storage and paperwork)

The first sample from a different source at the
 same location:
ASTM

 2.0
 0.1
 0.4
-Sampling Technique	

  EPA     GARB    Ambient

  1.0       0.7        0.5
   0.1
   0.2
0.1
0.2
0.1
0.2
 Notes: The times shown above are in hours  and assume a team of two inspectors
 and include time for the storage and paperwork associated with each sample.
 Travel time and the actual analyses are  not  included.
                                                      last update:
                   Jul  8
                      16:27

-------