United States
              Environmental Protection
              Agency
                  Office of Mobile Source Air Pollution Control
                  Emission Control Technology Division
                  2565 Plymouth Road
                  Ann Arbor, Michigan 48105
EPA 460/3-88-005
August 1988
oEPA
              Air
Butadiene  Measurement
Technology

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                                       EPA 460/3-88-005
Butadiene Measurement Technology
                       by

                 Lawrence R. Smith

             Southwest Research Institute
                 6220 Culebra Road
               San Antonio, Texas 78284

               Contract No. 68-03-4044
                Work Assignment B-1

           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
                   August 1988

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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. B-l  of Contract 68-03-4044.   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 460/3-88-005
                                    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 B-l  under  Contract 68-03-4044, was initiated June
11, 1987  and completed in February 1988.   It was identified within Southwest
Research  Institute as Project 08-1567-001.   The  EPA  Project  Officer for the
program was Mr. Craig A. Harvey of the Emission Control Technology Division, Ann
Arbor, Michigan. 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  development  and   validation  of   a  gas
chromatography procedure to  measure  1,3-butadiene  levels in vehicle exhaust.
After development and validation, the procedure  was used to measure 1,3-butadiene
emissions from each of two gasoline-fueled light-duty test vehicles over duplicate
cold-start FTP tests.  The 1,3-butadiene  emissions are reported  in  rag/mile and as
total  grams  for each  FTP test.  In addition  to  the 1,3-butadiene measurements,
regulated exhaust emission (HC, CO, and  NOX  in g/mile), other 04  hydrocarbon (n-
butane, isobutane, etc. in mg/mile), and fuel economy  (in mi/gallon) measurements
were conducted for each FTP test.
                                    IV

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                          TABLE OF CONTENTS

                                                                     Page

FOREWORD                                                           iii

ABSTRACT                                                            iv

LIST OF FIGURES                                                      vi

LIST OF TABLES                                                       vii

SUMMARY                                                            viii

I.    INTRODUCTION                                                    1

II.   GENERAL EQUIPMENT, INSTRUMENTS, PREPARATIONS
     AND PROCEDURES                                                 2

     A.   Automobiles                                                   2
     B.   Test Fuel                                                      2
     C.   Dynamometer and CVS System                                    4
     D.   Instrumentation for Regulated Emissions                           5
     E.   Vehicle Test Procedure                                          5
     F.   1,3-Butadiene Analytical Procedure                               6

m.   PROCEDURE DEVELOPMENT AND VALIDATION                       7

IV.   RESULTS                                                          16

     A.   Regulated Emissions and Fuel Economy                           16
     B.   1,3-Butadiene Test Results                                      16
     C.   €4 Emission Results                                            17

V.   QUALITY ASSURANCE                                             21

REFERENCES                                                           23

APPENDICES

     A.   1,3-BUTADIENE PROCEDURE
     B.   COMPUTER PRINTOUTS OF THE REGULATED EMISSION AND FUEL
          ECONOMY TEST RESULTS
     C.   COMPUTER PRINTOUTS OF REGULATED EMISSIONS AND
          FUEL ECONOMY - VOIDED TEST RESULTS

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                             LIST OF FIGURES

Figure                                                                Page

  1       Automobiles Evaluated in This Project                             3

  2       Partial Views of the Chassis Dynamometer, the
          Dilution Tunnel, and the Intake to the CVS                         5

  3       FTP Driving Cycle vs Time Trace                                 6

  4       Gas Chromatogram of C$ Hydrocarbons, ~Z5 ppmC
          Each Hydrocarbon                                               8

  5       Chromatogram of ~2.6 ppmC,  1,3-Butadiene Standard               9

  6       Chromatogram of FTP - Bag 1 Sample from  1987
          Plymouth Reliant                                              10

  7       Chromatogram of 1,3-Butadiene and n-Butane Standard             1Z

  8       Chromatogram of Dilute Exhaust Sample                          13

  9       Decay of 1,3-Butadiene in a Dilute Exhaust Sample Bag
          (Cold-Start 505 Sample Bag from FTP Testing of 1986
          Chevrolet Celebrity) Spiked with 1,3-Butadiene                    15

  10      Separation of C± Hydrocarbons                                  20
                                  VI

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                              LIST OF TABLES

Table                                                                   Page

 1        Automobiles Evaluated                                           2

 2        Description of Unleaded Gasoline Test Fuel,
          EM-781-F                                                       4

 3        Determination of Detector Linearity                             11

 4        Regulated Emission and Fuel Economy Test Results                16

 5        1,3-Butadiene Emission Results                                  17

 6        1,3-Butadiene Emission Results for Each FTP Segment             18

 7        C4 Emission Results                                            19

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                                  SUMMARY
     An analytical procedure was developed and validated to measure 1,3-butadiene
in dilute vehicle exhaust.  This procedure utilizes a gas chromatograph (GC) with a
flame  ionization detector to separate  1,3-butadiene  from hutane  and other  €4
hydrocarbons.  Dilute exhaust samples  are  collected   in  standard  CVS bags and
analyzed within one hour of collection.  The GC flame  ionization detector gives a
linear  response  for  1,3-butadiene in the region  of  interest.  The procedure has a
detection limit  on the order of 0.03 ppmC  1,3-butadiene in  dilute exhaust  (0.5
mg/mile for the FTP).   In  addition to 1,3-butadiene,  the  procedure allows the
quantification  of  six  other C4  hydrocarbons:   butane,  isobutane,  1-butene,
isobutylene,  cis-2-butene, and  trans-2-butene.   In this program  the  developed
procedure was utilized to evaluate  1,3-butadiene  emissions from two  light-duty
vehicles fueled with an alcohol-free commercial grade gasoline.  The test vehicles, a
1986 Chevrolet  Camaro and a  1987  Ford Taurus, were both fuel injected with
closed-loop operation. The test fuel had a Reid  Vapor Pressure of 12.05 psi and an
olefin content of 13.6 percent.

     The two test vehicles were each evaluated in  duplicate  over the Federal Test
Procedure (FTP) with 1,3-butadiene, regulated emissions (total hydrocarbons, carbon
monoxide, and oxides of nitrogen), emissions of six  other C4  hydrocarbons  (butane,
isobutane,  1-butene,  isobutylene,   cis-2-butene, and  trans-2-butene),  and  fuel
economy determined during each test. The most  significant observations made from
the data generated (not necessarily in order) are as follows:

     •   1,3-Butadiene was detected in the exhaust of both test vehicles.

     •   The  Camaro (port  fuel injection) had a higher 1,3-butadiene emission rate
        than the Taurus (throttle body injection),  1.7 mg/roi versus 0.9 mg/mi.

     •   The  1,3-butadiene fraction of the total hydrocarbon emissions was higher for
        the Camaro than for the Taurus, 0.61 percent versus 0.36 percent.

     •   The  majority (>98%)  of the  1,3-butadiene emissions were generated  in the
        cold-start transient phase (Bag 1) of the FTP.   1,3-Butadiene accounted  for
        0.70 percent of the Bag 1 Taurus hydrocarbon emissions and 0.95 percent of
        the Camaro hydrocarbon emissions.

     •   1,3-Butadiene  emissions  were  significant  (0.35  percent  of  the   total
        hydrocarbons), however, in the hot-start transient segment (Bag 3) of the
        FTP for  a voided test on the Taurus.  The Taurus had to  be restarted several
        times during the initial segment of the hot-start test.

     •   In general, the Camaro had  higher emission rates than the Taurus for the
        unsaturated  C4  hydrocarbons (1,3-butadiene,  1-butene,  isobutylene,  and
        trans-2-butene),  while  the  inverse  was   noted for  the  saturated  C4
        hydrocarbons (butane, isobutane).
                                   viii

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                              L INTRODUCTION
     The objective of this program was to develop and validate a procedure for the
measurement  of  1,3-butadiene levels  in vehicle exhaust.   After development  and
validation, the procedure was used to measure  1,3-butadiene emissions from  two
gasoline-fueled light-duty vehicles.   A measurement technique selective to  1,3-
butadiene is important because previous sample collection and analysis techniques
used  for  characterizing  vehicle  exhaust  hydrocarbons  did  not  permit  the
determination of 1,3-butadiene separately from butane,  and because 1,3-butadiene
has been  determined to have  high carcinogenic potency.  This report describes the
gas chromatography procedure that was developed and validated in  this program for
1,3-butadiene  exhaust  measurements, and  presents the  results from two  test
vehicles.

     The two gasoline-fueled light-duty vehicles tested  in  the program, a 1986
Chevrolet Camaro and a 1987 Ford Taurus, were  rented locally.  The  Camaro had
port (multipoint)  fuel  injection  with  a  closed-loop  3-way  catalyst  and neither
secondary air  injection nor pulsed air.  The Taurus had throttle body fuel injection
with a closed-loop  3-way plus oxidation catalyst  and pulsed air.   Prior to testing,
each vehicle  was tuned  to  manufacturer's  specifications and  minor  mechanical
repairs  were  conducted,  if required.   The  test  fuel used in the program  was  a
commercial grade unleaded gasoline obtained from a local service station.  The  test
fuel had a Reid Vapor Pressure of 1Z.05 psi and an olefin content of  13.6 percent.

     Each of  the two test vehicles was operated in duplicate over  the Federal Test
Procedure  (FTP)   to  generate  exhaust  samples  for  analysis.    1,3-Butadiene
measurements, as well as measurements for six additional C^ hydrocarbons (butane,
isobutane,  1-butene,  isobutylene,  cis-Z-butene,  and  trans-Z-butene)  and  the
regulated emissions (total hydrocarbons, carbon monoxide, and oxides of nitrogen),
were made on each exhaust sample.   1,3-Butadiene and the other C±  hydrocarbon
results were reported in mg/mi and the regulated emissions results  were reported in
g/mi.  Fuel economy determinations  using  the carbon balance method were  also
conducted with the  results reported in miles per gallon.

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H. GENERAL EQUIPMENT, INSTRUMENTS, PREPARATIONS AND PROCEDURES
     This section describes  the automobiles,  the fuels,  the  facilities,  and  the
general instrumentation and procedures  utilized  in  this project.   Sampling  and
analysis for 1,3-butadiene as well as butane, isobutane, 1-butene, isobutylene, cis-2-
butene, and trans-2-butene are also discussed.

A.   Automobiles

     Two  fuel-injected gasoline-powered  automobiles  were  evaluated  in   this
project.  The automobiles are described in Table 1  and are shown in Figure 1.   The
1986 Chevrolet Caraaro was equipped with port (multipoint) fuel injection, and the
1987 Ford Taurus was California certified and equipped with throttle body injection.
Both vehicles were  rented locally.  Prior to testing, the  vehicles were  tuned to
manufacturer's specifications and operated over a cold-start FTP cycle to determine
if the  emission  control systems on the  vehicles were functioning properly.   The
Camaro appeared to  be  in acceptable operating condition (HC, 0.30 g/mi;  CO, 4.56
g/mi; NOX,  0.38  g/mi;  and fuel economy, 22.22 mi/gal), but the Taurus  was not
operating properly (HC, 3.67  g/mi; CO,  115.12 g/mi; NOX, 0.35  g/mi;  and  fuel
economy, 17.98 mi/gal) and required some repair.  Replacement of the fuel injector
on the Taurus drastically reduced the HC  and CO emission rates and increased the
fuel economy (HC, 0.25 g/mi;  CO, 3.35  g/mi; NOX, 0.45 g/mi,  and fuel economy,
23.68 mi/gal). At this point, the Taurus appeared to be operating properly  and was
accepted for use in the program.
                    TABLE 1.  AUTOMOBILES EVALUATED
Model Year
Body Type
Engine Family
ID Number
Odometer Mileage
Emission Controls
Fuel Injection
Transmission
Chassis Dynamometer
   Inertia Setting, Ibs
   Power Setting, Horsepower
 Chevrolet Camaro

1986
2-door
G1G2.8V8XGZX
G1FP8753GN119808
33083
EGR/3CL
Port
L-4

3,500
8.4
                                                            Ford Taurus
1987
4-door
HFM2.5V5HCH9
1FABP52D5HA157262
28568
EGR/PLS/OXD/3CL
Throttle Body
A3

3,000
7.4
B.   Test Fuel

     The test fuel was an alcohol-free commercial grade unleaded gasoline (Gulf)
obtained from a local service  station.   Selected properties of the test fuel are
presented in Table 2.  The test fuel had an RVP slightly higher than the requested
8.9 to  11.7 psi range  (12.05 psi), however, its use was approved by  the Project
Officer.  No. 1,3-butadiene was found in the test fuel.

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                1986 Chevrolet Camaro
                   1987 Ford Taurus
FIGURE 1. AUTOMOBILES EVALUATED IN THIS PROJECT

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            TABLE 2.
DESCRIPTION OF UNLEADED GASOLINE
    TEST FUEL, EM-781-F
                      Item
               Distillation - D86
                    IBP
                    5%
                    10%
                    15%
                    20%
                    30%
                    40%
                    50%
                    60%
                    70%
                    80%
                    90%
                    95%
                    EP

               Recovery, %
               Residue, %

               F.I.A.
                    % Aromatics
                    % Olefins
                    % Saturates

               RVP, psi

               Benzene, %
               Toluene, %

               Isobutane, g/gal
               Butane, g/gal
               1-Butene,  g/gal
               Isobutene, g/gal
               cis-2-Butene, g/gal
               trans-Z-Butene, g/gal
               1,3 -Butadiene, g/gal
                        Test Result
                           23(74)
                           32(90)
                          38(101)
                          43(110)
                          49(120)
                          60(140)
                          73(164)
                          88(191)
                          106(223)
                          115(239)
                          148(298)
                          171(340)
                          189(373)
                          207(405)

                             98.5
                              0.5
                             24.4
                             13.6
                             62.0

                            12.05

                              1.1
                              4.0

                               21
                              140
                              2.5
                              1.1
                              7.2
                              7.9
                             <0.3
C.   Dynamometer and CVS Systems

     A  Clayton Model ECE-50  chassis dynamometer with a direct-drive variable-
inertia  flywheel system  was utilized for the testing.   This direct-drive inertia
system  simulates equivalent weight of vehicles from 455 kg (1,000 Ib) to 4,025 Rg
(8,875 Ib) in 55 kg (125 Ib) increments. The constant volume sampler (CVS) used for
the evaluations was SwRI CVS No. 2.  An 18-inch diameter by 16-foot  long stainless
steel dilution tunnel was used in conjunction  with the CVS, which was run  at a

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nominal 315 scfm.   A cooling  fan  of  5,000 cfm capacity was used in front  of the
vehicles  during  all  tests.   Vehicle hoods were maintained fully  open during the
testing and were closed during the soak periods.

     Partial views of the chassis dynamometer, the dilution tunnel, and the  intake
to the CVS can be  seen in  Figure 2.  Both  the dynamometer  and  the CVS were
calibrated,  maintained,  and  operated  in accordance  with  the manufacturer's
instructions and the  appropriate  sections of  the Code  of  Federal  Regulations
applicable to light-duty vehicles.'*
      FIGURE 2. PARTIAL VIEWS OF THE CHASSIS DYNAMOMETER, THE
              DILUTION TUNNEL, AND THE INTAKE TO THE CVS
D.   Instrumentation for Regulated Emissions

     Bagged samples of the dilute exhaust were evaluated for HC, CO, NOX, and
CO2 using SwRI Bag  Cart No.  2.  This bag cart  was designed, calibrated, and
operated  in  accordance  with the  appropriate  sections  of  the  Code  of  Federal
Regulations applicable to light-duty vehicles.

E.   Vehicle Test Procedure

     The test procedure utilized in this project was the Federal Test Procedure^)
(FTP).  The FTP uses the Urban Dynamometer  Driving  Schedule (UDDS)  which is
1372 seconds in duration. The UDDS, in turn, is  divided into two segments; the first
having 505 seconds and the  second  having 867 seconds. The FTP  consists of a cold-
start  505 and a stabilized 867 followed by a ten-minute  soak  and then a hot-start
505. The FTP schedule is illustrated in Figure 3.


* Numbers in parentheses designate references at the end of the report.

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1
100


 80

 60

 40

 20

  0
                   200
                              400
                                        600        800
                                            TIME,  sec
                                                            1000
                                                                      1200
                                                                                1371
               FIGURE 3.  FTP DRIVING CYCLE VS TIME TRACE
F.    1,3-Butadiene Analytical Procedure

      The analytical procedure used to measure  1,3-butadiene and several other €4
hydrocarbons is summarized in this section. A detailed description of the procedure
has been included as Attachment A of this report.

      The procedure  was  developed to  measure  1,3-butadiene in dilute vehicle
exhaust. In addition to 1,3-butadiene, the procedure provides separation and exhaust
concentrations for six other C4 hydrocarbons  including:  isobutane,  butane,  1-
butene, isobutylene, cis-2-butene,  and trans-2-butene.  Standard CVS bag samples
are analyzed for 1,3-butadiene  using a  gas chromatograph equipped with  a flame
ionization detector (FID).  The gas chromatograph system utilizes a Perkin-Elmer
Model 3920B  gas chromatograph  with  an FID, two  pneumatically-operated and
electrically-controlled  Seiscor valves,  and an analytical column.   The  analytical
column is a 9' x 1/8" stainless steel column  containing 80/100  Carbopack C  with
0.19% picric acid.  The carrier  gas is helium, which flows through  the column at  a
rate of 27  ml/min.  The column temperature is maintained at  40°C  for analysis.
External 1,3-butadiene standards  in  zero air  are  used  to quantify the results.
Detection limits for the procedure  are on the order of 0.03 ppmC in dilute exhaust
for 1,3-butadiene (0.5 mg/mile for the FTP).

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                 PROCEDURE DEVELOPMENT AND VALIDATION
     A selective measurement technique for  1,3-butadiene in dilute  exhaust  was
necessary,  because  previous  methods  utilized in exhaust measurements did  not
permit the determination of 1,3-butadiene separately from butane^),  and because
1,3-butadiene  had been determined  to have  a high carcinogenic potency.  This
section describes the development and validation of a gas chromatography procedure
to accurately separate and quantify 1,3-butadiene emissions in vehicle exhaust.

     A  review  of  the  literature  and of  currently  in-use  methods  for  the
determination  of 1,3-butadiene in complex hydrocarbon mixtures revealed that a
number of gas chromatograph columns to separate 1,3-butadiene  from butane  and
other 04 hydrocarbons were  commercially available.  A Perkin-Elmer 3920B  Gas
Chromatograph equipped with a flame ionization  detector (FID)  and  a gas phase
injection system was utilized  in the evaluation of these columns.  The gas phase
injection system allowed the analysis of standard CVS sample bags.  The GC columns
were  either purchased  from  commercial distributors or prepared  in-house using
commercially  available packing materials. A 6' x 1/8" SS column packed with 0.19
percent  picric acid  on  80/100 mesh Graphpac-GC  gave promising  results in the
initial portion of the program.  Figure 4 illustrates the separation obtained with the
Graphpac Column.   GC parameters for  the analysis included an isothermal GC oven
temperature of 30°C, an injection loop of 10 ml, an amplifier  attenuation setting of
x8, and a carrier gas (helium) flow rate of 40 ml/min. The GC parameters were then
varied  to optimize the GC response for 1,3-butadiene. The 2.6 ppmC 1,3-butadiene
peak in Figure 5 was obtained by increasing the sample loop to 20 ml, increasing the
oven temperature to 35°C, and changing the amplifier attenuation to x4.

     A CVS bag sample (Bag  1) from the FTP testing of a 1987 Plymouth Reliant
was analyzed for 1,3-butadiene. This analysis gave a 1,3-butadiene concentration in
the dilute exhaust sample of 1.4 ppmC (Figure  6).  This 1,3-butadiene concentration
represented approximately 1 percent of the  "cold-start 505" total hydrocarbons (147
ppmC).  A second vehicle,  a  1986 Chevrolet Celebrity (2.8 liter V-6  engine) gave
approximately  0.2 ppmC in  a Bag 1 FTP dilute exhaust sample.  This concentration
represented approximately  0.4 percent of the total  hydrocarbons (46  ppmC).  Mr.
Craig A. Harvey, the EPA Project Officer for this program, was present during the
Celebrity testing.

     Mr. Frank Black of EPA-RTP was then contacted as to their approach for the
analysis  of 1,3-butadiene.   The RTP laboratory also uses a stainless steel column
packed with  0.19 percent  picric  acid  on  80/100 mesh  Graphpac-GC  for  the GC
analysis of 1,3-butadiene. Differences in the SwRI and RTP procedures at this point
included: 1) cryogenic concentration of the hydrocarbon sample at RTP as opposed
to a 20cc  sample loop  at  SwRI; 2)   a  longer analytical column at  RTP,  9-foot
compared to  6-foot at  SwRI; and 3) naming  of a 1,3-butadiene  standard against
propane on a total hydrocarbon FID at SwRI as opposed to naming the 1,3-butadiene
on  the GC-FID at RTP  (differences  in response factors  for different hydrocarbons
are greater on  a total hydrocarbon FID than on  a GC-FID). At this  point, a certified
low concentration 1,3-butadiene standard (2.0 ± 0.04 ppmC) was purchased from
Scott Specialty Gases and  utilized  as  a standard in subsequent  test work.  This
standard also  contained  8.04 ± 0.16 ppmC butane.  To achieve additional separation
of the C4 hydrocarbons, a  9-foot x 1/8 inch SS column packed with  0.19  percent

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                                            laobutyleite •—j
                                            CiBM2~Buttene
                                            Trans -2-S utene
                                            l,3-BaLa(ken
                         6        3      "" 0
                   Retention time, Minutes
FIGURE 4. GAS CHROMATOGRAM OF C4 HYDROCARBONS,
            ~25 PPMC EACH HYDROCARBON
                       8

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                         Retention time, Minutes
FIGURE 5. CHROMATOGRAM OF ~Z.6 PPMC, 1,3-BUTADIENE STANDARD

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                      9630
                        Retention time, minutes

FIGURE 6. CHROMATOGRAM OF FTP - BAG 1 SAMPLE FROM
                1987 PLYMOUTH RELIANT

                   10

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picric acid on 80/100 mesh Carbopack C was prepared and installed into the GC to
replace the existing six-foot column.  With a carrier flow of 35 ml/min and an oven
temperature  of 35°C, this column provided a minimum separation of one minute
between any two of the C± hydrocarbons. Figure  7 illustrates the separation of 1,3-
butadiene and butane using the 9-foot column.  A gas divider was used to dilute  the
standard to various levels in order to determine the linearity of the FID detector
over the range of expected concentrations of both 1,3-butadiene (0-2.0 ppmC) and
butane (0-8.04 ppmC)  in dilute exhaust.  The detector was found to be linear  for
both 1,3-butadiene and butane with r2 values of 1.00 for both compounds.  The data
used to determine detector linearity can be found in Table 3.   Figure  8 shows a
chromatogram of a dilute exhaust  sample (sample taken during the first 140 seconds
of an  FTP-bag  1).   Seven €4  compounds were  separated  and identified  in  the
chromatogram.   The identities  of the  butane and  1,3-butadiene peaks  were
confirmed by spiking the exhaust  sample with the Scott standard.  The remaining
five C^ compounds were identified by relative retention times.

            TABLE 3. DETERMINATION OF DETECTOR LINEARITY

                	Butane	
                 Gas Concentration
                      in ppmC
                  by Gas Divider(x)          GC Peak Area(y)

                          8.04                    69716
                          6.83                    56045
                          4.02                    33086
                          0.80                     6821
                          0.0                         0
                          8.04                    69411
                          6.83                    58070
                                r2 = 1.00
                                a = -426
                                b = 8569

                                1,3-Butadiene
2.0
1.7
1.0
0.2
0.0
2.0
1.7
16532
13117
7528
1792
0
16346
13539
                                r2 = 1.00
                                a = -89
                                b = 8080
      To determine 1,3-butadiene stability in exhaust, a cold-start 505 (bag 1) dilute
 exhaust sample  from the FTP testing of  a 1986 Chevrolet Celebrity  (2.8 liter V-6
 engine) was spiked with 1,3-butadiene. The sample bag was then analyzed for 1,3-
 butadiene immediately  after the spike (time 0) and at 30,  60, 120, and 240 minutes
                                     11

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      24   22   20  18  16  14   12   10   8    6    4  2    0
                          Retention time,  minutes

FIGURE 7. CHROMATOGRAM OF 1,3-BUTADIENE AND N-BUTANE STANDARD

                              12

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32
28
 20        16
Retention time, minutes
    FIGURE 8.  CHROMATOGRAM OF DILUTE EXHAUST SAMPLE
                            13

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after the spike.  Figure 9 displays the result of this experiment.  The initial spiked
concentration of 1,3-butadiene was on the order of 3 ppmC.  After 4 hours, the 1,3-
butadiene decreased  to  63 percent  of the original  concentration.  A  1,3-butadiene
standard (
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27
                                      Time, minutes
  FIGURE 9. DECAY OF 1,3-BUTADIENE IN A DILUTE EXHAUST SAMPLE BAG (COLD-START 505
SAMPLE BAG FROM FTP TESTING OF 1986 CHEVROLET CELEBRITY) SPIKED WITH 1,3-BUTADEENE

-------
                                IV.  RESULTS
     This section describes the results of the regulated and 1,3-butadiene emission
tests conducted on two vehicles. In addition to 1,3-butadiene, analyses for six other
€4  hydrocarbons  were   conducted,  including:    butane,  isobutane,  1-butene,
isobutylene, cis-2-butene, and trans-2-butene.

A.   Regulated Emissions and Fuel Economy

     Duplicate FTP tests were conducted on each of the two test  vehicles.   A
summary of the individual and average regulated emission and fuel economy results
is  presented in  Table 4  along  with  the Federal Emission Standards.  Computer
printouts for the regulated emissions and  fuel economy are included in Appendix B.

   TABLE 4. REGULATED EMISSIONS AND FUEL ECONOMY TEST RESULTS

                      	FTP Emissions, g/mi, except as noted	
                             Camaro
                             Taurus
Test   Test
                                              Test
                                                1
                              Test
                                2
Hydrocarbons
Carbon Monoxide
Oxides of Nitrogen
0.28
3.88
0.34
        0.28
        5.16
        0.43
0.28
4.52
0.39
0.25   0.25    0.25
2.91   2.95    2.93
0.44   0.44    0.44
Federal
Standard

  0.41
   3.4
   1.0
Fuel Economy, mi/gal  23.72   22.91  23.32   23.69  23.14  23.42
     With the exception of one voided test on the Taurus, the operation of the test
vehicles was consistent during testing. During the voided test, the Ford Taurus died
repeatedly in the initial stages of the hot-start portion of the FTP (Bag 3).  Because
of these problems, the results of this test (Test 2, Run 1, 1/25/88) were not included
in Table 4.  Regulated emissions and fuel economy were recorded for the  test (HC,
0.38 g/mi; CO.  3.36  g/mi; NOX, 0.38 g/mi, and fuel  economy, 22.72 mi/gal), and a
copy of the computer printout  for the  regulated emissions has been  included in
Appendix  C.  The C±  emissions were also recorded for this test and will be discussed
in the  following section.  One additional test  was also  conducted on the Camaro
(Test 1, Run 1, 1/19/88), however, problems with the 1,3-butadiene analysis system
prevented the sampling of a complete set of C± data.  The Bag 1, 1,3-butadiene
emissions  were recorded and the results will be included in the following section.
The regulated emissions for the entire test were recorded (HC, 0.30  g/mi; CO,  5.48
g/mi; NOX, 0.35 g/mi; and fuel economy, 23.67  mi/gal) with a copy of the computer
printout included in Appendix C.  These data  were not included  in Table 4  since
comparable  1,3-butadiene data were not available.

B.   1,3-Butadiene Test Results

     Emission measurements for  1,3-butadiene were  conducted in duplicate for
each of the test  vehicles operated  over the FTP  cycle.  The  results  of  these
measurements are reported in Table 5.  The Camaro (port fuel injection) had higher
1,3-butadiene  emission rates than the Taurus (throttle body injection), 1.7  mg/mi
                                    16

-------
versus 0.9 rag/mi.  The 1,3-butadiene  for the Camaro also accounted for a higher
percentage of the  total hydrocarbons than the Taurus, 0.61 percent  versus 0.36
percent.   The average total mass of 1,3-butadiene generated during the FTP test
(unweighted) was 29.93 mg for the Camaro and 15.80 mg for the Taurus.  The voided
test on the Taurus  gave a slightly higher 1,3-butadiene emission rate than the two
tests listed in Table  5  (1.5 nag/mi versus 0.8  and 1.0  nag/mi), however,  the  1,3-
butadiene percentage of the total hydrocarbons was similar to the other tests (0.40
percent versus 0.32  and 0.40 percent).

                TABLE 5.  1,3-BUTADIENE EMISSION RESULTS

                             FTP Emissions, nag/mi, except as noted	
                      	Camaro	     	Taurus
                       Test    Test              Test     Test
                        1        2      Avg        1       2

Total Hydrocarbons      280      280     280       250     250
1,3-Butadiene           1.8      1.6     1.7       0.8     1.0

1,3-Butadiene Percent   0.64     0.57    0.61      0.32    0.40     0.36
of Total Hydrocarbons

Total mg 1,3-Butadiene 31.65    28.20   29.93     14.13   17.46    15.80
per test (not weighted)


      The 1,3-butadiene emission results for each FTP segment are given in Table 6
for the two test vehicles.  As can be seen in the table, virtually all (> 98%)  of  the
1,3-butadiene is generated  in Bag  1, the first 505-second segment of the cold-start
UDDS cycle.  The 1,3-butadiene accounted for  0.70  percent  of the  Bag  1 Taurus
emissions and 0.95 percent of  the  Bag 1 Camaro emissions.  The  1,3-butadiene
emission rate for  Bag 1 of the incomplete  Camaro  test was 8.6 rag/mi and  the
percentage of the  total hydrocarbons was  1.1 percent. The voided Taurus test (hot-
start problems)  had lower Bag 1 1,3-butadiene emissions than the recorded tests (3.3
nag/mi versus 4.0 and 4.9 mg/mi), however, the Bag 3  emissions were significant, 2.8
rag/mi, and accounted for 0.35 percent of the total hydrocarbons.

C.    04 Emission Results

      In addition to 1,3-butadiene, the emission  rates of six other C±  hydrocarbons
were determined in this program.  The emission  rates for  these six C±  hydrocarbons
(butane,  isobutane,  1-butene,  isobutylene,  cis-2-butene,  and trans-2-butene)  are
listed in Table 7  along with 1,3-butadiene  and total hydrocarbon emission rates.
Figure 10 illustrates the separation of the C± hydrocarbons obtained during the gas
chromatography analysis. In general, the Camaro had  higher emission rates than the
Taurus for the  unsaturated C± hydrocarbons (1,3-butadiene, 1-butene, isobutylene,
and trans-2-butene) while the reverse was noted for the  saturated C±  hydrocarbons
(butane, isobutane).  1,3-Butadiene was found to be 13.1 percent of the "butane plus
1,3-butadiene" emissions for the Camaro, and 4.6 percent for the Taurus.
                                    17

-------
                TABLE 6.  1,3-BUTADIENE EMISSION RESULTS
                         FOR EACH FTP SEGMENT
Total Hydrocarbons
1,3-Butadiene
1,3-Butadiene
 (detection limit)

Total rag 1,3-Butadiene 31.Z
per test

1,3-Butadiene Percent  0.95
of Total Hydrocarbons

Test
1
920
8.7
--
31.2
0.95
Bael
Test
2
830
7.9
—
28.2
0.95


Avg
875
8.3
0.4C
29.7
0.95

Test
1
60
NDa
—
ND
0
Bag 2
Test
2
90
ND
—
ND
0


Avg
75
ND
0.6C
ND
0

Test
1
230
jb
«*
0.4
0.04
Bag 3
Test
2
240
ND
~*~
ND
0


Avg
235
T
0.4
0,4
0.04
Total Hydrocarbons
1,3-Butadiene
1,3-Butadiene
  (detection limit)
Total mg 1,3-Butadiene 14.1
per test

1,3-Butadiene Percent  0.61
of Total Hydrocarbons
                                  Taurus Emissions, nag/mi, except as noted

Test
1
660
4.0
—
Bag 1
Test
2
620
4.9
—


Avg
640
4.5
0.4

Test
1
80
ND
—
Bag 2
Test
2
100
ND
—


Avg
90
ND
0.6

Test
1
250
ND
—
Bag 3
Test
2
270
ND
_


Avg
260
ND
0.4
17.5


0.79
15.8
0.70
ND
ND
ND
ND
ND
ND
aNone Detected
bTrace, detected but below the level of quantification. Estimated to be in the order
of 0.1 nag/mile.
cDetection limits for bags 1 and 2 are not equivalent due to differences in CVS volumes
and miles driven for the two FTP segments.
                                    18

-------
                      TABLE 7. C4 EMISSION RESULTS

                            FTP Emissions, mg/roi, except as noted
Total Hydrocarbons
1,3 -Butadiene
Butane
Isobutane
1-Butene
Isobutylene
cis-2-Butene
trans-2-Butene

1,3-Butadiene Percent
of Butane plus
1,3-Butadiene

Test
1
280
1.8
11.0
2.1
1.9
3.4
1.0
1.4
14.1
Camaro
Test
2
280
1.6
11.6
2.0
1.9
3.7
1.1
1.4
12.1


AZ&.
280
1.7
11.3
2.1
1.9
3.6
1.1
1.4
13.1

Test
1
250
0.8
19.8
3.9
1.6
2.5
1.1
1.3
3.9
Taurus
Test
2
250
1.0
17.5
3.0
1.3
2.4
1.1
1.2
5.4


Avg
250
0.9
18.7
3.5
1.5
2.5
1.1
1.3
4.6
                                   19

-------
                 Camaro Bag 1 Sample
 Injection
 Air, Cl, C2
 C3
 0.37 ppmC Isobutane
 0.58 ppmC 1-Butene
 2.36 ppmC Butane
 0.95 ppmC Isobutylene
 0.26 ppmC cis-2-butene
 0.36 ppmC trans-2-butene
 0.73 ppmC 1,3-Butadiene
 Unknown
 Backflush
                        Time, minutes
36
32
     FIGURE 10. SEPARATION OF C4 HYDROCARBONS
                      20

-------
                          V. QUALITY ASSURANCE


     The Quality Assurance (QA) guidelines addressed in the QA plan for this Work
Assignment  were  followed in performing the work for  the  program.   Chassis
dynamometer, CVS, and bag cart calibrations were performed using procedures and
equipment  specified  in  the Federal Register, and are available  for  inspection.
Quality assurance  associated  with  1,3-butadiene  analyses  is described  in  the
following paragraphs.

     Tedlar sample bags routinely used with the  CVS to collect  diluted  vehicle
exhaust gas for  analyses  of HC, CO, and  NOX regulated emissions were  also
employed  for  1,3-butadiene analyses utilizing an FID-equipped  gas  chromatograph.
All sample bags  were analyzed within one hour of collection  to  avoid long-term
degradation of 1,3-butadiene experienced in the validation experiments.  Sample Bag
1 was typically analyzed within 5  minutes of collection, while sample bags 2 and 3
were analyzed within 30 and 60 minutes of collection, respectively.  One background
bag, background bag 2, was run during  the analyses. This background bag was run
after all sample bags had been analyzed and within 2 hours of collection.  After all
sample and background bags had been analyzed, Bag 1  was spiked with the standard
sample (containing both butane and 1,3-butadiene) to confirm the presence of 1,3-
butadiene in the diluted exhaust.

     A series of six consecutive injections of the  standard containing 1,3-butadiene
and  butane during the analysis phase of the program gave average peak areas and
standard deviations of 17,180 ± 313 for 1,3-butadiene and 77,339 - 463  for  butane.
The  precision  of these injections as percent standard deviation  was 1.8  percent for
1,3-butadiene  and 0.6 percent for butane.  A  more reasonable assessment of the
precision  of the  analytical method may be determined by using peak  areas from
standards actually used to bracket samples run.  The precision  determination using
the results for the 20 standard injections carried out during this program to  bracket
samples is shown below:
                                                             Percent
                                                             Deviation
Hydrocarbon
Standard
Number of
Analyses
Average
Area
Standard
Deviation
in Area
 1,3-butadiene        20          18,277         795             4.4

 Butane              20          78,513         3,530            4.5


 Precision determinations  by repetitive injections  of  actual  samples  were  not
 practical due to the decay of 1,3-butadiene with time.

      The program objectives for precision (5.0 percent), accuracy (5.4 percent), and
 completeness (95  percent)  for  the analysis  of 1,3-butadiene were  met with  a
 precision of 4.4 percent, accuracy of 4.8 percent, and completeness of 100 percent.
 Accuracy was determined employing a certified standard of 1,3-butadiene purchased
 from Scott Specialty Gases.  The analytical accuracy  of the purchased gas was ±2
 percent as determined by Scott.
                                     21

-------
     The detection limit of 0.03 ppmC for  1,3-butadiene, as used in this report, is
the level above which the Hewlett-Packard Model 3353 gas chromatograph computer
system can consistently detect and integrate the 1,3-butadiene signal from the GC-
FID. Levels between 0.01 and 0.03 ppmC  can be detected by the GC-FID, however,
quantification by the computer system is variable.  These levels have been referred
to as trace amounts in this report.
                                    2.2

-------
                               REFERENCES
1.    Code of Federal Regulations, Title 40, Chapter 1, Part 85, Subpart H, Sections
     applicable to Light-Duty Vehicles.

2.    (a)  F.M. Black and R.L.  Bradow, "Patterns  of  Hydrocarbon Emissions from
     1975  Production Cars."  SAE  750681  presented at Fuels  and  Lubricants
     Meeting, Houston, Texas, June 1975.
     (b)  F.M. Black, "The Impact of Emission Control Technology on Passenger Car
     Hydrocarbon Emission  Rates and Patterns.11 Proceedings of the  International
     Conference  on Photochemical Oxidant Pollution and Its Control, EPA-600/3-
     77-OOlb, January 1977.
     (c)  F.M. Black and L.E. High, "Automotive Hydrocarbon  Emission Patterns and
     the Measurement of Nonmethane Emission Rates." SAE 770144  presented  at
     SAE Congress, Detroit, Michigan, February 1977.
     (d)  F.M. Black and  L.E. High, "Methodology for Determining Particulate and
     Gaseous Diesel Hydrocarbon Emissions."   SAE  790422  presented  at  SAE
     Congress and Exposition, Detroit, Michigan, February 1979.
     (e)  J.E.  Sigsby, S. Tejada, et al. "Volatile Organic Compound Emissions from
     46 In-Use Passenger Cars." Environmental Science and Technology, Vol. 21, p.
     466, May 1987.
                                    23

-------
       APPENDIX A




1,3-BUTADIENE PROCEDURE

-------
               MEASUREMENT OF 1,3-BUTADIENE IN EXHAUST


     This procedure  was  developed to  measure  1,3-butadiene  in  dilute vehicle
exhaust.  In addition to 1,3-butadiene, the procedure provides separation and relative
exhaust concentrations for six other 04 hydrocarbons including:  isobutane, butane,
1-butene, isobutylene,  cis-2-butene, and trans-Z-butene. Standard CVS bag samples
are analyzed for 1,3-butadiene using a gas chromatograph equipped with a  flame
ionization detector (FID).  External 1,3-butadiene standards  in zero air are used to
quantify  the results.  Detection limits for this procedure  are on the order of 0.03
ppmC in  dilute exhaust for 1,3-butadiene.

Analytical Procedure

     The analysis of 1,3-butadiene is accomplished by collecting 1,3-butadiene  in
Tedlar bags and analyzing the samples with a gas chromatograph equipped  with  a
flame  ionization detector  (FID).   The analysis flow schematic  for 1,3-butadiene is
shown  in Figure  A-l.  A detailed description of the procedure follows.

     The gas chromatograph system for the analysis  of 1,3-butadiene  utilizes  a
Perkin-Elmer  Model 39ZOB gas chromatograph  with  an  FID,  two  pneumatically-
operated and electrically-controlled Seiscor valves, and an analytical column.  The
analytical column  is a 9' x 1/8" stainless steel column containing 80/100  Carbopack
C with 0.19% picric acid.  The carrier gas is helium, which flows through the column
at a rate of 27 ml/min. The column temperature is maintained at 40°C for analysis.
A chromatogram  of a Z.O ppmC  1,3-butadiene  and 8.04  ppmC butane standard is
shown  in Figure  A-Z.  A chromatogram of an exhaust sample  is shown in Figure A-3.
To quantify the results,  the sample peak areas  are compared to the peak area of a
standard, which  was run before and after each set of sample bags. Figure  A-4 shows
the  analytical system with gas chromatograph,  detector, sample injection system,
and recorder.

     The analytical column, sampling loop, and  Seiscor valves are all housed in the
GC  oven and  are  operated with the aid of a specially fabricated  control system.
Figure A-5  (Step  1) illustrates the gas chromatograph flow  schematic with the gas
sampling valve in the purge position and the backflush valve in the foreflush position
for the analytical column.  Figure A-6 (Step  Z) illustrates the flow schematic when
the gas sampling valve is actuated and the backflushed valve is still in the foreflush
position.  Once  the 1,3-butadiene peak has eluted, the backflush valve is activated
and the  €5 and heavier molecular weight  hydrocarbons  are backflushed from  the
analytical column (Figure A-7).   Under normal conditions, it is not necessary to
backflush the calibration standards since they are free of contaminants  that would
interfere with the analytical column.

Control System

     The control of the  two Seiscor valves is accomplished by ATC  timers  and
ASCO electric  solenoid valves.   The  electric  schematic  for  the  control  of the
Seiscor valves using these timers and electric solenoid valves is shown in Figure A-8.
The flow schematics for vacuum and pressure lines to  the  Seiscor  valves  are
presented in Figures A-9, A-10, and A-ll.
                                  A-Z

-------
    Vehicle
        I
     CVS
 Tedlar Bags
      Gas
Chromatograph
   Recorder
A/D Converter
   HP 3353
Computer System
                                            I
                                        Computer
                                        Printout
 FIGURE A-l. THE ANALYSIS FLOW SCHEMATIC FOR 1,3-BUTADIENE
                            A-3

-------
   24   22   20   18  16  14    12   10   8    6    42    0
                         Retention time, minutes
FIGURE A-2. CHROMATOGRAM OF 1,3-BUTADffiNE AND N-BUTANE STANDARD

                               A-4

-------
                20        16       12
               Retention time, minutes

FIGURE A-3. CHROMATOGRAM OF DILUTE EXHAUST SAMPLES

                      A-5

-------
FIGURE A-4.  ANALYTICAL SYSTEM
             A-6

-------
     Analytical Column
(9'xl/8"  SS, 0.19% Picric Acid
 on 80/100 Carbopack C)
                                           Seiscor Valve
                                       (Normal Configuration)
                                                           PE  3920B
                                                        Gas Chromatograph
                                                           with  FID
                                 Seiscor Valve
                                 (Gas  Sampling Configuration)
10 ml
sample
loop
                   •••••••••••••••••»•••••••••••%
                   A	o
                                                                Carrier Gas
 Vent
                                                Regulating
                                                  Valve
                                   Pump
                                                                 Sample or
                                                                 Calibration
                                                                   gas  in
                                                          Female
                                                        quick-connect
      FIGURE A-5. FLOW SCHEMATIC OF 1,3-BUTADIENE ANALYTICAL SYSTEM
                        (STEP 1 - PURGE OF SAMPLE LOOP)
                                   A-7

-------
    Analytical Column
(9'xl/8" SS, 0.19 Picric Acid
  on 80/100 £arbopack C)
                                         Seiscor Valve
                                              Configuration)
                                      ./
                                                         PE 3920B
                                                      Gas Chromatograph
                                                         with FID
                               Seiscor Valve
                            (Sanple Inject Configuration)
                                                             Carrier Gas
Vent
                                                              Sample or
                                                              Calibration
                                                                gas  in
                                                        Female
                                                     quick-connect
    FIGURE A-6. FLOW SCHEMATIC OF 1,3-BUTADIENE ANALYTICAL SYSTEM
         (STEP Z - INJECT SAMPLE OR CALIBRATION GAS INTO SYSTEM)
                                  A-8

-------
    Analytical Column
(9'xl/8"  SS, 0.19 Picric Acid
  on 80/100 Carbopack C)
       Seiscor Valve
(backflush configuration)
Vent
                                                          PE 3920B
                                                       Gas Chromatograph
                                                          with FID
                               Seiscor Valve
                               (Purging Configuration)
                                                              Carrier Gas
 10 ml
 Sample
 Loop
                                               Regulating
                                                 Valve
                                  Pump
                                                               Sample or
                                                               Calibration
                                                                 gas in
                                                         Female
                                                      quick-connec t
   FIGURE A-7.  FLOW SCHEMATIC OF 1,3-BUTADffiNE ANALYSIS SYSTEM
              (STEP 3 - BACKFLUSH ANALYTICAL COLUMN)
                                  A-9

-------
                       AC (-)
>

(-»
o
                         FIGURE A-8. ELECTRICAL SCHEMATIC OF 1,3-BUTADIENE ANALYSIS SYSTEM

-------
Vacuum
                                                          n
      cap
Air Pressure  (30 psi)
                                   cac
                                      P   V
                                       CSV
                                      Seiscor
                                   :	i
                                     CSV off
Vacuum
                     n.
      cap
                                   cap
Air Pressure (30 psi)
y
                                      P  V
                                     Backflush
                                      Seiscor
Backflush  off
       FIGURE A-9. FLOW SCHEMATIC IN ELECTRIC SOLENOID VALVES
                     (BOTH VALVES DE-ENERGIZED)
                               A-ll

-------
Vacuum
                    n
                     E2
      cap
Air Pressure (30 psi)

                                    caP
 Vacuum

                                                             P   V

                                                           Backflush

                                                            Seiscor
 Air Pressure  (30 psi)
Backflush off
        FIGURE A-10. FLOW SCHEMATIC IN ELECTRIC SOLENOID VALVES

                (GSV ENERGIZED, BACKFLUSH DE-ENERGIZED)
                                 A-12

-------
Vacuum
                    ri
Air Pressure  (30 psi)
si)   |
                                         3
                                          P   V
                                           CSV
                                          Seiscor
:...............!

   CSV  on
Vacuum
      C3P
                     n
Air Pressure  (30 psi)
                     u
                                          P  V

                                         Backflush
                                          Seiscor
                                        Backflush on
      FIGURE A-ll. FLOW SCHEMATIC IN ELECTRIC SOLENOID VALVES
                      (BOTH VALVES ENERGIZED)
                               A-13

-------
Sample Calculations

     The quantification of 1,3-butadiene is based on a direct comparison of the 1,3-
butadiene  in   exhaust  with  a  calibration  blend   of  a  known  1,3-butadiene
concentration.  Two basic assumptions are made in the calculations that should be
considered when conducting 1,3-butadiene analyses. The first assumption is that the
exhaust samples are analyzed as quickly as possible after  collection and that  the
measurements are made within the working range of the system. Exhaust  samples
spiked with  1,3-butadiene have  indicated  a  loss  of   1,3-butadiene with  time.
Calculations  for this system are based on the assumption that the analyses  are
conducted  within  one hour of  sample collection  and minimal sample decay  has
occurred. The use of a gas divider and a 2.0 ppmC  1,3-butadiene standard has shown
that the FID  response  of 1,3-butadiene is  linear in the 0.05  to 2.0  ppmC range.
Procedural development work  has  found that  1,3-butadiene levels are generally
below 2.0 ppmC in dilute exhaust.   The other C± hydrocarbons are quantified by
direct comparisons of  the hydrocarbons in exhaust  with  a calibration blend of
butane.  If the above assumptions are followed, then the  following relationships are
valid.

Let   Csam= ppmC concentration of 1,3-butadiene in sample
      ^std = PPmC concentration of 1,3-butadiene in standard
      Asam= area of 1,3-butadiene peak in sample
      Astd ~ area °* l»3-butadiene peak in standard
      csam


      If a 2.0 ppmC 1,3-butadiene (in air) calibration blend gives 8000  area counts
 for the 1,3-butadiene peak and an exhaust sample gives 1000 area counts for the 1,3-
 butadiene peak, then the 1,3-butadiene in the exhaust is calculated as follows:

      CSam = Asam * Cstd
Csam= 1,000 x 2.0
                 Astd

                00 x 2
                 8,000
      csam= °-2

      The 1,3-butadiene concentration in ppmC can be multiplied by the per carbon
 density of 1,3-butadiene at 68°F and 29.92" Hg (562 fig/ml) to give a mass per unit
 volume of 1,3-butadiene in dilute exhaust (fig/m3) for subsequent mass calculations.

 Equipment

      The  analyses  for 1,3-butadiene  are performed using a  gas chromatograph
 equipped with  a flame ionization detector.  The detector, electrometer, recorder,
                                    A-14

-------
and GC integrator are the major electronic components in the detection system.  A
control console was  fabricated to house the mechanical hardware items that are
necessary for the proper operation of the 1,3-butadiene analysis system.   Major
items in the analysis system are listed below:

Gas Chromatograph

      1.    Perkin-Elmer Model  39ZO  gas  chromatograph   equipped  with  flame
           ionization detector
     2.    Soltec Model B-281 1 mv recorder
     3.    Hewlett-Packard Model  3353  gas chromatograph computer system with
           remote printer
     4.    Hewlett-Packard Model 1865A A/D Converter
     5.    Analytical column, 9' x 1/8"  SS, 0.19 picric on 80/100 mesh Graphpac GC
     6.    Seiscor valve - gas sampling configuration
     7.    Seiscor valve - back flush configuration

Control Console System

     1.    ATC timers,  Model 3Z5A346A10PX (2 ea)
     2.    ASCO solenoid valve, Model 834501 {2 ea)
     3.    Brook  flowmeter, R-2-15-A  w/ss float; 0-150 scale
     4.    Metal  Bellows MD-155 pump
     5.    Female quick-connect, stainless steel
     6.    Nupro Model 2M stainless  steel, copper and Teflon  tubing (1/8" and
           1/16")
     7.    Miscellaneous stainless steel and brass unions, tees, etc.
     8.    Bud Classic n control console cabinet
     9.    Miscellaneous electrical  on-off switches
                                  A-15

-------
                  APPENDIX B

          COMPUTER PRINTOUTS OF THE
    REGULATED EMISSIONS AND FUEL ECONOMY
                 TEST RESULTS
Table B-     Vehicle     Test No.     Run No.

   1        Camaro         1           2
   2        Camaro         2           1
   3        Taurus         1           1
   4        Taurus         2           2

-------
                                SOUTHWEST RESEARCH INSTITUTE - DEPORTMENT OF EMISSIONS RESEARCH
                                  TABLE B-l.  FTP   - VEHICLE EMISSIONS RESULTS -
                                                         PROJECT 08-1567-001
  TEST NO.    1            RUN
  VEHICLE XODEL   86 CftMftRO
  ENGINE 2.8  L(171. CID) L-6
  3A33*TER  746.00 MM H6(29.37 IN H6)
  RELATIVE HUMIDITY  16. PCT
  BAG  RESULTS
    BA6 NUMBER
    DESCRIPTION

    BL.OWER  DIP ? MM. H20UN. H20>
    BLOWER  INLET * MM. H20UN. .-120)
    BLOWER  INLET TEMP. DEB. CIDE6. F)
    ROWER  REVOLUTIONS
    TOT FLOW STD. CU.  METRES(SCF)
    TKC SAMPLE METER/RANGE/PPW
    THC 3CKGRD METER/RAN6E/PPX
    CO  SAMPLE .1ETER/RAN6E/PPN
    CO  BCKGRD METES/RANSE/PPM
    COc SflRPLE «ETER/RftNGE/PCT
    OK BCKSRD METER/RflNGE/PCT
    W» SAMPLE METER/RANGE/PPM
    NDX FCK6RD METER/RAN6E/PPM
    DILUTION FACTOR
    THC CONCENTRATION PP«
    CO  CONCENTRATION PPM
    COS CONCENTRATION PCT
    NCX CONCENTRflTION PPM
    THC MASS GRAMS
    CC  MASS GRAMS
    Cue MASS SRAMS
    N0< MASS GRANS

    THC  SRWS/MI
    CO   GRAMS/MI
    C02  BRAMS/KI
    NOX  QRAMS/MI
    FUEL ECONOMY IN MP6
    RUN TINE             SECONDS
    MEASURED DISTANCE    MI
    SCF,  DM

COMPOSITE RESULTS
    TEST NUMBER        1
    BAROMETER    MM HG  746.0
    HUMIDITY     G/KG     3.0
    TEMPERATURE  DE6 C   23.9
  VEHICLE NO.i
  DATE    1/20/flfl
  BAB CART NO.   2
  DYNO NO.       3
  CVS NO.    Z

  DRY BULB TEMP.  23.9 D£6 C(75,0 DE6 F)
  ABS.  HUMIDITY  3.0 6M/K8
                   TEST WEIGH;  ises.
                   ACTUAL ROAD LOAD
                   GASOLINE  EM-7B1-F
                   ODOMETER 55260.  KM(33094.  MILES)
                    KG( 3500.  IBS)
                    6.3 KU(  3.4 HP)
       1
COLD
STABILIZE
                   NOX HUMIDITY CORRECTION FACTOR   .30
HOT TRANSlcNT
762.0 (30.0)
762.0 (30.0)
45.6 (114.0)
40637.
76.1 ( £686.)
79. 7/ Zl BO.
5.4/ Zl 6.
81. if 14/ 386.
.9/14/ 4.
15.2/14/1.0032
14.1/14/ .0502
98. 4/ I/ 24.5
i.9/ I/ .5
12.77
75.
374.
.9570
24.0
3.23
33.10
1332.9
2.79
.92
9.27
373.2
.78
22.70
505.
3.57
.986
762.0 (30.0)
762.0 (30.0)
41.1 (106.0)
69667.
131.0 ( 4626.)
8.2/ £/ B.
S.3/ 2/ 5.
37.7/12/ 38.
1.7/12/ 2.
Bl.3/14/ .6848
13.8/iV .0489
15. 1/ I/ 3.9
1.5/ I/ .4
19.44
3.
35.
.6385
3.5
.24
5.41
1531.4
.70
.06
1.39
392.4
.18
22.46
867.
3.90
.988
762.0 (30.0)
762.0 (30.0)
44.4 (112.0)
40572.
75.8 ( 2577.;
32. */ 2/ 23.
4.5/ 2/ 5.
44.4/14/ 191.
.4/14, 2.
89.t/;4- .£.437
13.3/14/ .0468
41. 2/ I/ 10.3
.fl/ I/ .2
15.41
18.
186.
.8049
10.1
.81
16.40
1117.3
:.i?
.23
4.60
313.3
.33
£7.50
505,
3.57
.987
                              CARBON DIOXIDE      6/MI
                              FUEL ECONOMY        MP6
                              HYDROCARBONS  (THC)  6/KI
                              CARBON MONOXIDE     6/MI
                              OXIDES OF  NITROGEN  6/XI
                                      3-BA6
                                      366.3
                                      23.72
                                        .28
                                       3.88
                                        .34
                               (4-BA6)
                                   .0)
                                  .00!
                                  .00!
                                  .00}
                                  .00)
                                                              B-2

-------
                                SOUTHWEST RESEARCH INSTITUTE - DEPARTMENT OF EMISSIONS RESEARCH
                                   TABLE B-2.FTP   - VEHICLE EMISSIONS RESULTS -
                                                         PROJECT 06-1X7-001
 TEST NO.   a            RUN   1
 VEHICLE MODEL   66 CAMARO
 ENGINE c.8 L(i71. CID) L-6
 TRPNSK.S3ION ft4
 BAROMETER 747.27 HI HGI29.42 IN HE)
 RELATIVE HUMIDITY  18.  PCT
 8% RESULTS
    BAG NUMBER
    DESCRIPTION

    BLOWER DIF P MM.  rfc'OUN.  H20J
    BLOWER INLET P MM.  H2QUN.  H20)
    SLOPES INLET TEMP,  DEE.  Ci&ES.  F>
    BLOWER REVOLUTIONS
    TOT FLOW STD, CU.  METRES (SCF)
    THC SAMPLE METER/RANGE/PPM
    THC BCK6RD METER/RAN6E/PPM
    CO  SAMPLE METER/RANQE/PPM
    CO  BCKBRD NETER/RAN6E/PPM
    COc SAMPLE METER/flflNGE/PCT
    002 BCh&RD METER/RAN6E/PCT
    N3X SAMPLE METER 'fiftySE /PR
    MX BCK6RD METER/RANGE/PPM
    DILUTION FACTOR
    THC CONCENTRATION PP«
    CO  CGNCEOPT10N PPW
    C0£ CC1CENTRATION PCT
    NO* CI3NCENTRATION PPM
    THC KASSSRAKS
    CQ  KfiSS GRAMS
    CD£ MASS 3RAHS
    NuK «SS C-RAMS
    THC  GRAKS/MI
    C5   5HAMS/KI
    C0£  GRftMS/Ki
SECONDS
MI
    FUEL ECONOMY IK MP&
    ^UN TINE
    •MEASURED DISTANCE
    SCF,  DRV
CWPCSITE RESULTS
    TEST NUHBER        £
    BAROMETER    MM HG  747.3
    HUNIDITV     6/K6     3.6
    TEMPERflTURE  DEB C   25.0
                             VEHICLE NO.1
                             DATE    1/21/68
                             BAG CART NO.   £
                             DYNOND.       3
                             CVS NO.    £

                             DRY BULB TEMP.  25.0 DE6 Cm.O DEG F)
                             ABS.  HUMIDITY  3.6 GM/K6
                   TEST UEI8KT  1588.
                   ACTUAL ROM LOAD
                   8ASOLINE  EM-Tfll-F
                   ODONETER 53277.  KN(33105.  MILES)
                    KGi 3500.  LB3)
                    6.3 HU!  6.4 HP)
                                  1
                           COLO TRANSIENT
STABILIZED
                   NOX HUMIDITY CORRECTION FACTOR   .81
HOT TRANSIENT
762.0 (30.0)
762.0 (30.0)
43.3 (110.0)
40501.
76.0 ( 26B3.)
72. 6/ 2/ 73,
6. I/ 11 6.
92.7/14/ 457.
2.1/14/ 8.
%. 3/14/1. 0352
15.8/14/ .0574
23. 9/ 2/ 2S.O
.&/ 2/ .6
12.33
67.
438.
.9824
28.4
2. 94
38.72
1366.5
3.34
.83
10.91
385.0
.94
21.31
505.
3.55
.985
762.0 (30.0)
762.0 \30.0)
40.6 (105.0)
69600.
131.2 ( 4634.)
10.1/2/ 10.
6.0/ 2/ 6.
67.0/12/ 67.
6.3/12/ 6.
82.0/14/ .6979
15.4/14/ .0557
20. 2/ I/ 5.2
1.2/ I/ .3
18.99
5.
60.
.6452
4.9
.34
9.14
1550.0
.99
.09
2.39
405.0
.26
21.68
867.
3.83
.968
7K.O (30.0)
762.0 130.0)
41.7 (107.0)
40442.
76.1 ( 2687.)
24. 7/ 2/ 25.
5.5/ 11 6.
56.9/14/ 253.
1.2/14/ 5.
9C.1/14/ .8700
15.1/14/ .0544
44.7/ I/ 11.2
1.7/ I/ .4
14.93
20.
243.
.8192
10.6
.87
21.56
1141.2
1.27
.24
6.08
321.7
.36
26.70
504.
3.55
.986
                                                         CARBON 3IQXIDE     S/Ml
                                                         FUEL ECONOMY       MP6
                                                         HYDROCfiRBONS (THC)  G/M1
                                                         CARBON MONOXIDE    G/MI
                                                         OXIDES OF NITROGEN  6/MI
                                      3-BAG
                                      373.1
                                      22.91
                                        .28
                                       5.16
                                        .43
                                (4-BftS»
                              •    .0)
                              (   .00)
                              i   .00,
                              (   .00)
                              t   .00;
                                                              B-3

-------
                                 SOUTHWEST  RESEARCH  INSTITUTE - DEPARTMENT OF EMISSIONS RESEARCH
                                  TABLE  B-3. FTP   - VEHICLE EMISSIONS RESULTS -
                                                         PROJECT 08-1567-001
  TEST NO.    1            RUN   1
  VEHICLE MODEL   87 FORD TAURU
  EN6INE 2.5 U150.  CID)  L-4
  TRANSMISSION A3
  BAROMETER 749.05 MM HG129.49 IN HG)
  RELATIVE HUMIDITY  14.  PCT
  BAG RESULTS
     BAG NUMBER
     DESCRIPTION

     BLOWER DIF P MM.  H20UN.  H2Q)
     BLOUER INLET P MM. H20UN. H20)
     BLOWER INLET TEMP. DEB. CIDEB. F)
     BLOUER REVOLUTIONS
     TOT FLOW STD.  CU. METRES(SCF)
     THC SAMPLE METER/RANGE/PPM
     THC BCK6RD METER/RANBE/PPM
     CO  SAMPLE METER/RANBE/PPM
     CO  BCK6RD METER/RANBE/PPM
     C02 SAMPLE METER/RANBE/PCT
     C02 BCK6RD METER/RANBE/PCT
     NOX SAMPLE METER/RANBE/PPM
     NOX BCK6RD METER/RANGE/PPM
     DILUTION FACTOR
     THC CONCENTRATION PPM
     CO  CONCENTRATION PPM
     COS CONCENTRATION PCT
     NOX CONCENTRATION PPM
     THC MASS GRAMS
     CO  MASS GRAMS
     COS. MASS GRAMS
     NOX  MASS GRAMS

     THC GRAMS/MI
    CO  GRANS/MI
    COS  GRAMS/MI
    NOX  GRAMS/MI
    FUEL ECONOMY  IN MP6
    RUNTIME             SECONDS
    MEASURED DISTANCE    MI
    SCF, DRY

COMPOSITE RESULTS
    TEST NUMBER        1
    BAROMETER    MM HG  749.0
    HUMIDITY     6/K6     8.8
    TEMPERATURE  DEC C   25.6
  VEHICLE N0.2
  DATE    1/22/88
  BAB CART NO.  2
  DYNONO.      3
  CVS NO.   2

  DRY BULB TEMP. 25.6 DE6 C(78.0 DE6 F)
  ABS.  HUMIDITY  2.8 6M/K6
       1
COLD TRANSIENT

 762.0 (30.0)
 762.0 (30.0)
  43.3 (110.0)
    40611.
  76.4 ( 2697.)
 57.6/ 2/  SB.
  4.9/ 2/   5.
 75.4/14/ 353.
   .8/14/   3.
 95.3/14/1.0061
 12.7/14/ .0444
 73.87 I/ 20.0
   .9/ I/   .2
     12.81
      53.
     342.
     .9651
     19.8
      2.35
     30.43
    1349.8
      2.29

       .66
      8.56
     379.8
       .64
     22.43
     505.
     3.55
     .986
TEST HEIGHT  1361. KGI 3000. IBS)
ACTUAL ROAD LOAD   5.5 KU(  7.4 HP)
GASOLINE  EM-781-F
ODOMETER 45997. KM(2B5B1. MILES)
NOX HUMIDITY CORRECTION FACTOR   .79
2
STABILIZED
762.0 (30.0)
762.0 (30.0)
42.2 (108.0)
69615.
131.2 ( 4632.)
9.S/ 2/ 10.
5.6X 21 6.
13.4/12/ 14.
1.9/12/ 2.
79.57 IV .6523
12.7/14/ .0444
24. 3/ I/ 6.2
,5/ I/ .1
20.47
4.
12.
.6101
6.0
.32
1.76
1465.5
1.20
.08
.46
385.1
.32
22.97
867.
3.81
.990
3
HOT TRANSIENT
762.0 (30.0)
762.0 (30.0)
43.3 (110.0)
40556.
76.3 ( 2693.)
24.S/2/ 25.
5.1/2/ 5.
56.6/137 134.
.6/13/ 2.
50.67147 .8821
12.7/14/ .0444
65.27 I/ 16.3
.3/ I/ .0
14.93
20.
130.
.8406
16.3
.88
11.54
1174.0
1.88
.25
3.25
330.3
.53
26.38
505.
3.55
.987
                              CARBON DIOXIDE      G7HI
                              FUELECONOMY        MP6
                              HYDROCARBONS (THC)   6/NI
                              CARBON MONOXIDE     6/NI
                              OXIDES OF NITROGEN  6/MI
                   3-BAG
                   368.9
                   23.69
                     .25
                    2.91
                     .44
(4-BA6)
    .0)
   .00)
   .00)
   .00)
   .00)
                                                              B-4

-------
                                 SOUTHWEST  RESEARCH  INSTITUTE - DEPARTMENT OF EMISSIONS  RESEARCH
                                 TABLE B-4.   FTP   - VEHICLE EMISSIONS RESULTS -
                                                         PROJECT 08-1567-001
  TEST NO.    2            RUN   2
  VEHICLE MODEL   87  FORD  TAURU
  EN6INE 2.5 LU50. CID) L-4
  TRANSMISSION A3
  BAROMETER 750.82 MM H6(29.56  IN H6)
  RELATIVE  HUMIDITY  14. PCT
  BAG RESULTS
     BA6 NUMBER
     DESCRIPTION

     BLOUER DIF P  MM. H2DUN. H20)
     BLOWER INLET  P MM. H20(IN. H20)
     BLOUER INLET  TEMP. DE6. C(DE6. F)
     BLOUER REVOLUTIONS
     TOT FLOW STD. CU. METRES(SCF)
     THC SAMPLE METER/RANGE/PPM
     THC BCKGRD KETER/RAN6E/PPM
     CO   SAMPLE METER/RANGE/PPM
     CO   BCKBRD METER/RflNGE/PPM
     C02 SAMPLE METER/RANGE/PCT
     C02 BCKGRD METER/RANGE/PCT
     NOX SAMPLE METER/RANGE/PPM
     NOX BCKGRD METER/RANGE/PPM
     DILUTION FACTOR
     THC CONCENTRATION PPM
     CO   CONCENTRATION PPM
     C02 CONCENTRATION PCT
     NOX  CONCENTRATION PPM
     THC MASS GRAMS
     CO   MASS 6RAMS
     C02  NABS GRAMS
     NQX  MASS GRAMS

     THC  GRAMS/MI
     CO   GRAMS/MI
     C02  GRAMS/MI
    NOX  GRAMS/MI
    FUEL ECONOMY  IN MP6
    RUN TINE            SECONDS
    MEASURED DISTANCE    MI
    SCF, DRY

COMPOSITE RESULTS
    TEST NUMBER        2
    BAROMETER    MM HG  750.8
    HUMIDITY     6/K6     2.3
    TEMPERATURE  DEC C   21.7
  VEHICLE NO.2
  DATE    1/26/88
  BAG CART NO.  2
  DYNONO.       3
  CVS NO.   2

  DRY BULB TEMP. 21.7 DEG CI71.0 DEC F)
  ABS. HUMIDITY  2.3 GM/KG
       1
COLD TRANSIENT
STABILIZED
                   TEST WEIGHT  1361. KG( 3000. LBS)
                   ACTUAL ROAD LOAD   5.5 KU(  7.4 HP)
                   GASOLINE  EM-781-F
                   ODOMETER 46043. KM(28610. MILES)
                   NOX HUMIDITY CORRECTION FACTOR
HOT TRANSIENT
787.4 (31.0)
787.4 (31.0)
44.4 (112.0)
40495.
75.9 ( 2682.)
53. 8/ 2/ 54.
4.1/2/ 4.
BO.2/14/ 361.
.3/14/ 1.
97.3/14/1.0654
12.1/14/ .0420
93. 0/ t/ 23.2
1.6/ I/ .4
12.09
50.
371.
1.0269
22.8
2.20
32.76
1427.9
2.60
.62
9.19
400.8
.73
21.26
504.
3.56
.986
787.4 (31.0)
787.4 (31.0)
41.7 (107.0)
69677.
131.3 ( 4637.)
8.77 2/ 9.
4.1/2/ 4.
10.6/12/ 11.
.9/12/ 1.
80.0/14/ .6612
12.1/14/ .0420
25. 4/ I/ 6.4
l.B/ I/ .5
20.21
5.
10.
.6213
6.0
.37
1.48
1493.7
1.18
.10
.38
386.5
.30
22.89
868.
3.86
.989
787.4 (31.0)
787.4 (31.0)
43.3 (110.0)
40551.
76.2 ( 2690.)
25. 1/ 2/ 25.
3.8/ 2/ 4.
54.6/13/ 129.
.4/13/ 1.
92.2/14/ .9221
12.1/14/ .0420
61.0/ I/ 15.3
1.5/ I/ .4
14.30
22.
125.
.8830
14.9
.96
11.12
1231.8
1.70
.27
3.11
344.2
.48
25.34
505.
3.58
.987
                              CARBON DIOXIDE      6/MI
                              FUEL ECONOMY        MPG
                              HYDROCARBONS (THC)  6/MI
                              CARBON MONOXIDE     6/MI
                              OXIDES OF NITROGEN  G/MI
                                      3-BA6
                                      377.9
                                      23.14
                                        .25
                                       2.95
                                        .44
                               (4-BA6)
                                   .0)
                                  .00)
                                  .00)
                                  .00)
                                  .00)
                                                              B-5

-------
                        APPENDIX C

                  COMPUTER PRINTOUTS OF
         REGULATED EMISSIONS AND FUEL ECONOMY
                    VOIDED TEST RESULTS
Table C-    Vehicle   Test No.    Run No.          Test Problem
   1      Taurus        2          1      vehicle died during hot-start
   2      Camaro       1          1      incomplete 1,3-butadiene data

-------
                                 SOUTHWEST  RESEARCH  INSTITUTE - DEPftRTNENT OF EMISSIONS RESEARCH
                                  TABLE  C-l. FTP   - VEHICLE EMISSIONS RESULTS -
                                                         PROJECT 08-1567-001
  TEST NO.    2            RUN   1
  VEHICLE MODEL   87 FORD TAURU
  ENGINE 2.5 LI150.  CID)  L-4
  TRANSMISSION A3
  BAROMETER 755.14 MM  H6<29.73  IN H6)
  RELATIVE HUMIDITY 13.  PCT
  BAG RESULTS
     BAG NUMBER
     DESCRIPTION

     BLOWER DIF P  MM.  H20(IN. H20)
     BLOWER INLET  P MM. H20UN. H20)
     BLOWER INLET  TEMP. DE6. CtDES. F)
     BLOWER REVOLUTIONS
     TOT aOW STD.  CU. METRES(SCF)
     THC SAMPLE METER/RANGE/PPM
     THC BCK6RD METER/RANGE/PPM
     CO   SAMPLE METER/RANGE/PPM
     CO   BCK6RD NETER/RANBE/PPM
     C02 SAMPLE NETER/RANGE/PCT
     C02 BCKGRD METER/RAN6E/PCT
     NOX SAMPLE METER/RANGE/PPM
     NOX BCKGRD METER/RANGE/PPM
     DILUTION FACTOR
     THC CONCENTRATION PPM
     CO   CONCENTRATION PPM
     C02 CONCENTRATION PCT
     NOX CONCENTRATION PPM
     THC MASS GRAMS
     CO   MASS GRAMS
     COS MASS GRAMS
     NDX  MASS GRAMS

     THC  GRANS/MI
     CO   GRAMS/MI
     C02  GRAMS/MI
     NOX  GRAMS/MI
     FUR ECONOMY  IN MP6
     RUNTIME            SECONDS
    MEASURED DISTANCE    MI
    SCF, DRY

COMPOSITE RESULTS
    TEST NUMBER        2
    BAROMETER    MM H6  755.1
    HUMIDITY     G/K6     2.4
     TEMPERATURE  DE6 C   23.9
  VEHICLE NO.2
  DATE    1/25/BB
  BAG CART NO.  2
  DYNONO.      3
  CVS NO.   2

  DRY BULB TEMP. 23.9 DE6 C(75.0 DE6 F)
  ABS. HUMIDITY  2.4 6M/K6
       1
COLD TRANSIENT
STABILIZED
                   TEST WEIGHT  1361. K6( 3000. LBS)
                   ACTUAL ROAD LOAD   5.5 KW(  7.4 HP)
                   GASOLINE  EM-7B1-F
                   ODOMETER 46026. KM (28599. MILES)
                   NOX HUMIDITY CORRECTION FACTOR   .7fl
HOT TRANSIENT
762.0 (30.0)
762.0 (30.0)
45.6 (114.0)
40697.
77.2 ( 2727.)
45. 11 ^l 46.
3.3/ 2/ 3.
65.6/14/ 299.
.0/14/ 0.
96.9/14/1.0532
11.4/14/ .0392
68. 8/ I/ 17.2
.4/ I/ .1
12.33
43.
292.
1.0172
17.1
1.91
26.24
1438.1
1.99
.54
7.42
406.8
.56
21.11
506.
3.54
.986
762.0 (30.0)
762.0 (30.0)
42.2 (108.0)
69669.
132.5 ( 4678.)
7.9/ 2/ 8.
3.6/ 2/ 4.
12.0/12/ 12.
.0/12/ 0.
80.2/14/ .6648
11.6/14/ .0400
22.2/ I/ 5.7
.&/ I/ .2
20.10
5.
12.
.6268
5.5
.35
1.85
1520.3
1.09
.09
.48
398.5
.29
22.19
868.
3.81
.990
762.0 (30.0)
762.0 (30.0)
43.3 (110.0)
40604.
77.1 ( 2721.)
66.27 2/ 67.
3.9/ 2/ 4.
52.5/14/ 231.
.0/14/ 0.
90.9/14/ .8894
11.6/14/ .0400
53. 11 \l 13.5
.6/ I/ .2
14.59
63.
226.
.8522
13.3
2.79
20.29
1202.2
1.54
.79
5.72
339.0
.43
25.30
506.
3.55
.966
                              CARBON DIOXIDE      6/MI
                              FUEL ECONOMY        HP6
                              HYDROCARBONS (THC)   G/NI
                              CARBON MONOXIDE     6/MI
                              OXIDES OF NITROGEN  6/MI
                                      3-BA6
                                      383.9
                                      22.72
                                        .38
                                       3.36
                                        .38
                               (4-BA6)
                              (    .0)
                              (   .00)
                              (   .00)
                              (   .00)
                              (   .00)
                                                            02

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                               SOUTHWEST  RESEARCH  INSTITUTE - DEPARTMENT OF EMISSIONS RESEARCH
                                 TABLE  C-2. FTP   - VEHICLE EMISSIONS RESULTS -
                                                        PROJECT 08-1567-001
 TEST NO.    1             RUN   1
 v^:Cj£ MCDEi.   86 CAMMO
 ENGINE 2.3 LU71.  CID)  L-6
 TRANSMISSION  A4
 BfiRO«tTER 735.33 MM KG(28.95 IN  HG)
 SLftTIVE HUMIDITY  28.  PCT
 BAG RESULTS
    BAG NUMBER
    DESCRIPTION

    SLOWER DIF P m.  H20(IN.  H20)
    BLOWER INLET P MM.  H20UN.  H20)
    BLOWER INLET TEMP.  DEG.  C(DE6.  F)
    BLOWER REVOLUTIONS
    TOT FLOW 3TD. C'J. METRES(SCF)
    THE SAMPLE METER/RAN6E/PPM
    THC BCKGRD NETER/RANGE/PPM
    CO  SAMPLE METER/RANGE/PPM
    CO  BCKGRD METER/RANGE/PPM
    COS SAMPLE NETER/RAN6E/PCT
    C02 BCKGRD METER'.RANGE/PCI
    NOX SAMPLE METER/RANGE/PPW
    NOX BCKGRD METER/RANGE/PPM
    DILUTION FACTOR
    THC CONCENTRATION PPM
    CO  CONCENTRATION PPM
    COS CONCENTRATION PCT
    NOX CONCENTRATION PPM
    THC MASS GRAMS
    CO  MfiSS GRAMS
    CCc ;'Hoi SRAMS
    WX MASS GRAMS

    THC  SRH«S/WI
    CO   SRAMS/Mi
    CQ2  SRAMS/KI
    NOX  GRAMS/HI
    FUEL ECONOMY IN WPG
    RUNTIME             SECONDS
    MEASURED DISTANCE    MI
    SCF,  DRY

CO*:-;-.  = RESULTS
    r£ST NUMBER        1
    BAR01CTER    MM HB   735.3
    HUMIDITY     G/KG     5.4
    TEMPERATURE  DEG C    23.9
  VEHICLE NO. i
  DATE    1/19/B8
  BAG CART NO.  2
  DYNO NO.       3
  CVS NO.    c

  DRY BULB TEMP.  23.9 DEB Ci75.0 DEG F5
  ABS. HUMIDITY  5.4 6M/KG
                   TEST WEIGHT  1588.
                   ACTUAL ROAD LOAD
                   GASOLINE  EM-781-F
                   ODOMETER 53242.  KM(33083.  MILES)
                    KGi 3500.  LBS)
                    6.3 KW(  8,4 HP)
                       HUMIDITY CORRECTION FACTOR   .85
       1
COLD TRANSIENT
STABILIZED
HOT TRANSIENT
774.7 (30.5)
774.7 (30.5)
44.4 (112.0)
40573.
74.5 t £630.)
71. 5/ 2J 72.
6.2/ 2/ 6.
66.9/14/ 421.
1. 1/14/ 4.
94.1/H/ .9725
13.3/14/ .0468
66. 11 \l 21.7
2.6/ I/ .7
13.13
66.
405.
.9232
£1.1
2.83
35.16
1267. 1
2.55
.79
9.85
354.9
.71
23.78
505.
3.57
.382
"74.7 (30.5;
774.7 (30.5)
40.6 (105.0)
69655.
128.8 ( 4546.)
10. 1/ 2/ 10.
5.7/ 2/ 6.
64.6/12/ 65.
2.8/12/ 3.
81.6/14/ .6904
13. 3/1 W .0468
16. 0/ I/ 4.1
1.3/ I/ .3
19.20
5.
61.
.6460
3.8
.36
9.12
1522.9
.79
.09
2.36
394.7
.21
22.24
868.
3,86
.984
7 -i. 7 i2C>.5)
774.7 (30.5/
42.2 (109.0)
40523.
74.7 ( 2637.)
31. 5/ 2/ 32.
5.0/ 2/ 5.
73.5/14/ 343.
.8/14/ 3.
89.9/14/ .8652
13.1/14/ .0460
40. 1/ I/ 10.1
,8/ I/ .2
14.86
27.
331.
.8223
9.9
1.17
£8.77
1124.2
1.20
.33
8.09
316.1
.34
26.88
505.
3.56
.983
                              CARBON DIOXIDE      6/MI
                              FUEL ECONOMY        MP6
                              HYDROCARBONS  (THC)  6/MI
                              CARBON MONOXIDE     6/KI
                              OXIDES OF NITROGEN  G/MI
3-BA6
365.0
23.67
.30
5.48
.35
(4-BA6)
( .0)
( .00)
( .00)
( .00)
( .00)
                                                             C-3

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                                    TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 ^. REPORT NO.
 EPA 460/3-83-005
                                             3. RECIPIENT'S ACCESSION-NO.
 4. TITLE AND SUBTITLE

      BUTADIENE MEASUREMENT METHODOLOGY
                                             5. REPORT DATE
                                               August 1988
                                                            6. PERFORMING ORGANIZATION CODE
 7. AUTHOH(S)
     Lawrence
R. Smith
                                             8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
   Southwest  Research Institute
   6220 Culebra Road
   San Antonio, Texas  78284
                                             10. PROGRAM ELEMENT NO.
                                               Work Assignment  B-l
                                             11. CONTRACT7GRANT NO.

                                                 68-03-4044
 12. SPONSORING AGENCY NAME AND ADDRESS
   Environmental Protection Agency
   2565 Plymouth Road
   Ann Arbor,  Michigan  48105
                                             13. TYPE OF REPORT AND PERIOD COVERED
                                             Final Report  (6-11-87/2-88)
                                             14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT
  This program involved the development and validation  of a gas chromatography
  procedure  to measure 1,3-butadiene levels in vehicle  exhaust.  After development
  and validation,  the procedure was  used to measure  1,3-butadiene emissions from
  each of  two  gasoline-fueled  light-duty test vehicles  over duplicate cold-start
  FTP tests.   The  1,3-butadiene emissions are reported  in mg/mile and as  total
  grams for  each FTP test.  In addition to the 1,3-butadiene measurements,  regulated
  exhaust  emissions (HC, CO, and  NOX in g/raile), other  C^ hydrocarbon (n-butane,
  isobutane, etc.  in mg/mile), and fuel economy  (in  mi/gallon) measurements were
  conducted  for each FTP test.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                               b.lDENTIFIERS/OPEN ENDED TERMS
                                                              COS AT I Field/Group
     Air Pollution
     Exhaust Emission
     Motor Vehicles
                                  Emission Characterizati( n
                                  Emission Test  Procedures
                                  Light-Duty Vehicles
                                  1,3-Butadiene  Emissions
       IBUTION STATEMENT


         Release Unlimited
                                19. SECURITY CLASS (This Report)
                                  Unclassified
21. NO. OF PAGES
     53
                                20. SECURITY CLASS (This page)
                                  Unclassified
                                                                          22. PRICE
EPA Form 2220-1 (»-73)

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