EPA-600/2-75-048
September 1975
Environmental Protection Technology Series
                       PROTOCOL TO CHARACTERIZE
                                 GASEOUS  EMISSIONS
                                  AS A  FUNCTION OF
                  FUEL AND  ADDITIVE  COMPOSITION
                           Environmental Sciences Research Laboratory
                                    Office of Research and Development
                                    U.S. Environmental Protection Agency
                               Research Trisnsle Park  N C. 27711

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                     RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. Environmental Protection Agency, have been grouped into
five series.  These five broad categories were established to
facilitate further development and application of environmental
technology.  Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields.  The five series are:

          1.  Environmental Health Effects Research
          2.  Environmental Protection Technology
          3.  Ecological Research
          4.  Environmental Monitoring
          5.  Socioeconomic Environmental Studies
                               i       / ..
                              r
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series.  This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation from point and non-
point sources of pollution.  This work provides the new or improved
technology required for the control and treatment of pollution
sources to meet environmental quality standards.
This document is available to the public through the National
Technical Information Service, Springfield, Virginia  22151.

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                                        EPA-600/2-75-048
                                        September 1975
     PROTOCOL TO CHARACTERIZE GASEOUS EMISSIONS
     AS A FUNCTION OF FUEL-ADDITIVE COMPOSITION
                        by

                Harry E. Dietzmann
           Southwest Research Institute
             Post Office Drawer 28510
                 8500 Culebra Road
             San Antonio, Texas 78284
              Contract No. 68-02-1275
                  Project Officer

                 Ronald L. Bradow
Emissions Measurement and Characterization Division
    Environmental Sciences Research Laboratory
   Research Triangle Park, North Carolina 27711
       U.S. ENVIRONMENTAL PROTECTION AGENCY
        OFFICE OF RESEARCH AND DEVELOPMENT
    ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
   RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711

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                            DISCLAIMER
     This report has been reviewed by the Environmental Sciences
Research Laboratory, U.S. Environmental Protection Agency, and
approved for publication.  Approval does not signify that the
contents necessarily reflect the views and policies of the U.S.
Environmental Protection Agency, nor does mention of trade names
or commercial products constitute endorsement or recommendation
for use.
                                ii

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                             ABSTRACT

       Analytical techniques  and equipment were developed and applied
to characterize gaseous emissions as a function of fuel/additive compo-
sition from two versions of a high production automotive engine.  A
number of potentially-harmful gaseous emissions were measured at
specific .mileage  intervals on a 1972 and 1975 350 CID Chevrolet engine.
Mileage accumulation was accomplished using repetitive 23 minute long
driving L.A-4 cycles featured in the current Federal light-duty emissions
test procedure.  The operation of the  engine was by  means of special
stationary dynamometers with an automatic tape-controlled servo-driver.
Emission tests were conducted at 0, 1000, and 2000 mile intervals with
four fuel/additive packages with each engine using a hot start version of
the 1975 light-duty Federal Test Procedure.

       In addition to the regulated emissions of unburned hydrocarbons,
carbon monoxide, and oxides of nitrogen,  a number  of additional gaseous
and particulate emissions were determined at each emissions inspection
on both engines with all four fuel/additive combinations.  Sulfur compounds
measured included-sulfur dioxide,  sulfate, hydrogen sulfide,  carbonyl
sulfide, methyl mercaptan, and ethyl mercaptan.  Nitrogen compounds
measured were ammonia,  dimethylnitrosamine, and nitromethane.   In
addition,  particulate emission rates were determined using a 8 inch  di-
lution tunnel at all engine-fuel combinations at the three emission inspections.

       One important aspect  of this program was the statistical relia-
bility of the emissions testing.  Several types of engine starts (i.e.,  cold,
forced cold, hot) were evaluated,  and hot  starts were selected for full
scale emissions inspection testing.  Comparison of emission rate vari-
ability of  hot starts on engine dynamometers with the standard certification
test indicated that hot start dynamometer  was a more repeatable test pro-
cedure.  A limited amount of statistical analysis of the data has also been
included.   The  two engines operating on the short cycle mileage accumu-
lation driving schedule  were not found to produce any increase in regulated
emissions which  could be specifically attributed to the fuel additive packages.
The inherent test procedure variability coupled with engine emissions de-
terioration generally explained any  changes in emission rates.
                                  111

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                            FOREWORD

       The work described in this report was performed by Southwest
Research institute for the U.S. Environmental Protection Agency under
Contract No. 68-02-1275,  "Protocol to Characterize Gaseous Emissions
as a Function of Fuel Additive Composition",  This research effort was
a result of Request for Proposal No. DU-74-B349 and Southwest Research
Institute's responding Proposal No. 11-9865,  dated November 9,  1973.
This project was initiated on February 13,  1974, and the technical effort
was  completed on April 23, 1975.  It was identified within SwRI as Project
No.  11-3902.

       Project Leader for SwRI was Harry E. Dietzmann,  Senior Research
Chemist,  Department of Emissions Research. Overall supervision has
been provided by Karl J. Springer, Director, Department of Emissions
Research.  Project Officer for the Environmental Protection Agency has
been Dr.  Ronald L. Bradow, Chief,  Emissions Testing and Characterization
Section,  Chemistry and Physics Laboratory.
                                  IV

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                       TABLE OF CONTENTS

                                                               Page

ABSTRACT                                                    iii

FOREWORD                                                   iv

LIST OF FIGURES                                              vii

LIST OF TABLES                                              ix

I.      INTRODUCTION                                          1

       A.  Approach                                            1
       B.  Scope                                                2

II.     TEST PROCEDURES                                     5

       A.  Chemical Analysis                                    5
       B,  Engine Dynamometer Test Stands                      8
       C.  Test Plan                                           14
       D.  Engine Qualification                                  16

III.    RESULTS                                               21

       A.  1972 350 CID Chevrolet Engine                       21
       B.  1975 350 CID Chevrolet Engine                       37
       C.  Documentation of Engine Deposits                     52
       D.  Statistical Analysis                                  56

IV.    SUMMARY AND CONCLUSIONS                           63

LIST OF REFERENCES                                         67

APPENDIXES

       A.  Methods of Chemical Analysis
       B.  Individual Hydrocarbon Distribution
       C.  Individual Sulfur and Nitrogen Compound Distribution
       D.  Sulfur Distribution

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                         LIST OF FIGURES

Figure                                                         Page

  1        Several Views of 350 CID Chevrolet Test Stands        9

  2        Sulfate Sampling Flow Schematic with Dilution
           Tunnel Dimensions                                  13.

  3        HC Emission Rates of 1972 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     26

  4        CO Emission Rates of 1972 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     27

  5        NOV Emission Rates of 1972 350 CID Chevrolet
              Jt
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     28

  6        SO2 Emission Rates of 1972 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     29

  7        SO4= Emission Rates of 1972 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     30

  8        Particulate Emission Rates of 1972 350 CID
           Chevrolet Engine at Several Mileage Intervals
           with the Four Test Fuels                             31

  9        HC Emission Rates of 1975 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     41

 10        CO Emission Rates of 1975 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     42

 11        NOX Emission Rates of 1975 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     43

 12        SO2 Emission Rates of 1975 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                     44
                                 vn

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                     LIST OF FIGURES (Cont'd)

Figure                                                        Pag

 13        SO4= Emission Rates of 1975 350 CID Chevrolet
           Engine at Several Mileage Intervals with the
           Four Test Fuels                                    45

 14        Particulate Emission Rates of 1975 350 CID
           Chevrolet Engine at Several Mileage Intervals
           with the Four Test Fuels                         .   46

 15        Typically Cleaned Piston Heads and Cylinder
           Heads, 1972 Chevrolet 350 Engine                   53

 16        Typical Piston Deposits from 1972 350 CID
           Chevrolet Engine Operating on the Four Test
           Fuels After 2000 Miles of LA-4 Cycles              54

 17        Cylinder Head Deposits of 1972 350 CID Chev-
           rolet Engine Operating the Four Test Fuels at
           2000 Miles of LA-4 Cycles                          55

 18        Typically Cleaned Valves  and Valve Deposits
           From 1972 350 CID Chevrolet Engine Operating
           on Three Test Fuels with 2000 Miles of LA-4
           Cycles                                             57
                                  Vlll

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                         LIST OF TABLES

Table

  1        Federal Light Duty Emission Standards               14

  2        List of Fuel/Additive Combinations                   15

  3        Mileage Accumulation and Emission Testing
           Fuel Inspection Data                                17

  4        1972 and 1975 350 CID Chevrolet Engine Emis-
           sion Qualification Results                            19

  5        Qualification Test Emissions Variability              22

  6        Summary of Exhaust Emissions of 1972 Chev-
           rolet 350 CID Engine,  EM-214-F (Base Fuel
           at 0.1% S)                                          23

  7        Summary of 1972 350 CID Chevrolet Engine
           Emission Rates                                     24

  8        Summary of Exhaust Emissions of 1972 Chev-
           rolet 350 CID Engine,  EM-215-F (Base Fuel
           at 0.1% S + 0.378 g/gal Lubrizol 8101)                32

  9        Summary of Exhaust Emissions of 1972 Chev-
           rolet 350 CID Engine,  EM-216-F (Base Fuel at
           0.1% S + 0. 486 g/gal Paradyne 506)                   34

 10        Summary of Exhaust Emissions of 1972 Chev-
           rolet 350 CID Engine,  EM-231-F (Base Fuel
           at 0.1% S + 0. 05 g Pb/gal + 0. 378 g/gal Lubri-
           zol 8101)                                           36

 11        Summary of Exhaust Emissions of 1975 Chev-
           rolet 350 CID Engine,  EM-214-F (Base Fuel
           at 0.1% S)                                          39

 12        Summary of 1975 350 CID Chevrolet Engine
           Emission Rates                                     40

 13        Summary of Exhaust Emissions of 1975 Chev-
           rolet 350 CID Engine,  EM-215-F (Base Fuel
           at 0.1% S + 0.378 g/gal Lubrizol 8101)                48

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                     LIST OF TABLES (Cont'd)

Table

 14        Summary of Exhaust Emissions of 1975 Chev-
           rolet 350 CID Engine, EM-216-F (Base Fuel
           at 0.1% S + 0. 486 g/gal Paradyne 506)                50

 15        Summary of Exhaust Emissions of 1975 Chev-
           rolet 350 CID Engine, EM-218-F (High Aro-
           matic Fuel at 0.1% S + 0.378 g/gal Lubriaol
           8101)                                               51

 16        Standard Deviation (Sx) and Standard Deviation
           in Percent of Mean Value (% Sx) for 1972 350
           CID Chevrolet Engine with All Four Test Fuele       58

 17        Standard Deviation (Sx) and Standard Deviation
           in Percent of Mean Value (% Sx) for 1975 350
           CID Chevrolet Engine with All Four Test Fuels       59

 18        Comparison of Standard Deviation in Percent  of
           Mean Value (% Sx) of Standard Cold Start FTP,
           Hot Start Qualification Testing and Fuel Scale
           Hot Start Emission Testing                          6l

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                         I.  INTRODUCTION

       The Administrator of the Environmental Protection Agency (EPA)
is required by Section 211 of the Clean Air Act^1)* to register all fuels
and additives used in interstate commerce.  The Administrator is further
required that the additive, manufacturers document additive effects on
gaseous and particulate emissions,  control system performance,  and
visibility.  This project was initiated by EPA to develop analytical methods
for the sampling and analysis of gasoline exhaust emissions.  An  additional
purpose was to further evaluate the success of a test procedure, selected
by EPA and required by the  contract, in the detection of effects of fuel
additives on the gaseous,  particulate, and sulfate emissions from cars.
These methods were used to determine  if the effects of fuel and additive
composition could be observed using the 1975 light-duty (LD) Federal Test
Procedure (FTP)(2).  Research and development efforts were centered
on major areas,  namely:

       development of sampling and measurement procedures for the
           characterization  of automotive exhaust for a wide  variety of
           potentially-harmful exhaust products and

       establish the validity of the 1975 LD FTP as  a test procedure
           for determining the effects of fuel/additive combinations on
           gaseous emissions.

A.     Approach

       The approach used in this research program resulted from the
collective experience of EPA,  Southwest Research Institute (SwRI), and
others involved in air pollution studies with gasoline additives(3-7)^  ^
particular  test procedure, called out in the EPA work statement,  was
to be  evaluated with respect to its ability to detect harmful effects of
fuel additives  on both currently-regulated and non-regulated gaseous
emissions.  The 1975 Federal light-duty vehicle emissions test procedure
was used as the basic method of examining both regulated and non-regulated
gaseous exhaust components and sulfuric acid for both  catalyst-equipped
and non-catalyst engines  mounted on engine dynamometer stands.  The
test facility used Clayton hydraulic dynamometers and fixed inertia fly-
wheels to correct engine  dynamometer load simulation  problems found
in previous EPA programs.

       The EPA-selected procedure involved emissions testing by a hot
start  31 minute modification of the 1975 Federal Test Procedure after
* Superscript numbers in parentheses designate List of References at
  the end of this report.

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preliminary preconditioning with base fuel,  mileage accumulation to
2000 miles  using repetitive Federal Urban driving cycles using both ad-
ditive and base fuels followed by retesting using the modified hot start
1975 FTP.

       Final and initial emissions data would be then statistically com-
pared to (a) determine whether or  not a significant additive influence
was detectable with commercial additive packages and (b) determine on
the basis of statistical considerations the magnitude of an effect which
would be detectable by this procedure.

       Finally, considerations involved in setting up, calibrating,  and
operating the EPA procedure provided a background of experience  in
the practicality of the test itself as a fuel additive protocol.  A quali-
tative discussion of the problems incurred at SwRI with this schedule
is included  in a later portion of this report as 'a guide for future protocol
development work.

       The  main thrust of this effort was to  develop methods to measure
both presently regulated and unregulated, potentially harmful gaseous
products; however,  particulate sampling and sulfate analysis was con-
ducted as well.  A variety of analytical methods were used during the
course of the study.

       Several of the instrumental methods of analysis used in the char-
acterization of automotive exhaust were developed at EPA prior to project
initiation.   These methods  included non-reactive hydrocarbons (NRHC)
by gas chromatography and sulfate analysis using the barium chloranilate
(BCA) procedure.  Measurement of additional compounds for the charac-
terization of emissions was accomplished by SwRI during a procedural
phase of the program. Sulfur compounds measured include sulfur dioxide
(SO2), carbonyl sulfide (COS), hydrogen sulfide (I^S), methyl mercaptan
(CH3SH), and ethyl mercaptan (C2H5SH).  Ammonia (NI^), nitromethane
(CH^NC^).  and dimethylnitrosamine (DMNA) were nitrogen compounds
measured to characterize the exhaust as a function of fuel and additive
composition.  Particulate emission rates were calculated from weight
gain on small filters used to collect sulfate using an 8 inch dilution tun-
nel.  Tunnel size  selection was based on direct  experience of EPA per-
sonnel.  Regulated emission rates for unburned hydrocarbons (HC),
carbon monoxide (CO), and oxides of nitrogen (NOX) were obtained using
the accepted procedure.

B.     Scope

       Two versions of a current high production engine were employed
in this research effort. The engine selected for this study was a 350  CID
Chevrolet engine, a 1975 version complete with EGR,  air pump, and GM

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oxidation catalyst,  and a 1972 version.  The fuel was supplied by EPA,
and additive selection was made by SwRI with the advice and consent of
the EPA Project Officer and included Paradyne 506 and Lubrizol 8101.
Engines were mounted on a stationary dynamometer test stand designed
to simulate vehicle operation.  An automatic tape-controlled servo-
driver system was  incorporated into the two test stands and was used
for mileage accumulation.  Characterization emission tests were con-
ducted at specific mileage intervals; namely,  0, 1000, and 2000 miles.

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                           II.  TEST PROCEDURES

            The characterization of exhaust from the 1972 and 1975 350 CID
     Chevrolet engines was accomplished using a number of analytical pro-
     cedures.  These  methods were available from EPA-RTP or were developed
     by SwRI during the procedural development phase of the program.  Emis-
     sion tests were conducted at specific intervals on a mileage accumulation
     schedule.  Engine mileage was obtained using an automatic driver on a
     24-hour basis using  a repetitive driving cycle.  The driving cycle  speci-
     fied was  the urban dynamometer driving schedule of the 1975 light duty
     Federal Test Procedure, commonly called the LA-4 driving cycle.  Four
     fuel/additive packages were tested on both engines.  Two commercially-
     available fuel additives were selected for this program and were run
     using the supplier's  suggested fuel treatment  concentrations.
     A.
Chemical Analysis
            In addition to the regulated emissions of unburned hydrocarbons,
     carbon monoxide, and oxides of nitrogen, five additional groups of com-
     pounds were measured in the characterization of emissions from the two
     engines as a function of fuel and additive composition.  These groups in-
     cluded a series of non-reactive hydrocarbons, sulfur dioxide, sulfate
     (804"), nitrogen  compounds and sulfur compounds.

            Nitrogen  compounds which were determined included ammonia,
     nitromethane,  and dimethylnitrosamine. Hydrogen sulfide,  carbonyl
     sulfide, methyl mercaptan, and ethyl mercaptan were sulfur  compounds
     of interest.  The following summarizes the compounds measured to char-
     acterize emissions along with the methods of detection.

              TABLE X.  SUMMARY OF ANALYTICAL METHODS
   Chemical Analyses

1.  non-reactive hydro-
   carbons (NRHC)

2.  sulfur dioxide

3.  sulfate
4.  nitrogen compounds
5.  sulfur compounds
                Compounds Detected

             CH4, C2H6, C2H4, C2H2,
             C3H8,  C3H6, C6H6, C?H8

             S02

             S04= (S03)
             ammonia, dimethylriitro 
             samine, nitromethane

             H2S, COS, CH3SH,
             C2H5SH
 Instrument
Varian 1740
TECO Model 40

Beckman
Model 25

gas chroma-
tog raph

gas chroma-
tograph
Detection
 System

  FID
  PF

  UV


  ECD


  FPD

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       1.  Non-reactive Hydrocarbons (NRHC|

       Non-reactive hydrocarbons were measured using a gas chromato-
graph procedure^ developed by EPA. This procedure employs a 4-
column arrangement coupled with dual gas sampling valves, pneumatically
operated valves programmed electrically.  In  essence,  this procedure
allows baseline separation of all Cj to 3 hydrocarbons, including air and
CH4.  In addition, benzene and toluene are  also baseline separated during
the same analysis.

       Hydrocarbons considered to be non- reactive were methane,  ethane,
acetylene,  propane and benzene.  Non-reactive hydrocarbon emission
rates were determined by adding the individual NRHC ppmC values  for
each bag and computing the NRHC emission rates using these values in
lieu of the  bag cart HC concentrations.  The samples were also back-
ground corrected, and  calculated emission  rates were  expressed in
accord with the usual bag weighting factors.

       The NRHC emission rate for a given part of the test was the sum
of the  individual non-reactive hydrocarbons in ppmC  with the appropriate
bag weighting factor applied.  All bags were analyzed using the procedure
specified in the Federal Register'  ' to obtain HC emission rates.  The
NRHC/HC  is the fraction of non-reactive hydrocarbons in the total hydro-
carbons  determined by the bag cart, expressed on weighed basis.

       In addition to hydrocarbons considered non-reactive (CH^, C^H^,
C^HT, C-jHg,  and C^H^), several other compounds were measured.
These compounds included C^H ,, C^H^, and C-^Hg; and consequently,
when individual non-reactive hydrocarbon concentrations are presented,
these three reactive hydrocarbons  are also included.  The NRHC sam-
ples were obtained from the bag  samples obtained during the hot start
1975 L,D FTP.  Calibration standards were obtained and named using
EPA golden standards.  Emission rates of reactive and non-reactive
hydrocarbons were determined on both engines with all four test fuels,
The ratio of NRHC to HC were calculated for all tests where NRHC values
were obtained.

       2.  Sulfur Dioxide
       Sulfur dioxide was measured using a TECO Model 40 pulsed
fluorescent (PF) SO2 analyzer.  Measurements were obtained using the
1975 LD FTP bag samples as well as continuous on-line monitoring.  An
integrator  was included an an integral part of the CVS to provide the
average SC>2 concentrations during these tests.

       By  obtaining bag and continuous SO2 values,  it was possible to
establish the relationship between continuous and bag sampling.  Sulf
                                                              Sulfur

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balances were calculated on all tests  utilizing the SC>2 a-nd sulfatc  emis-
sion rates.  In general, the bag SO2 values were less than the continuous
SO^;  and both were in excess of 100 percent sulfur recovery most of the
time.  A complete description of the measurement of SO_, using the  I LCO
Model 40 pulsed fluorescent SO2 analyzer is presented in Appendix A.

       3.  Sulfate (SO4=)

       The measurement of sulfate in the exhaust was measured using
the barium chloranilate procedure.  This method involves collecting
under quasi-isokinetic  conditions, a sample of exhaust sulfate on a
47mm 0.5 micron fluoropore (FH) filter,  extraction with 60 percent iso-
propyl alcohol (IPA) and analysis using  a recording UV colorimeter  at
3lOnm.  Sulfuric acid standards  were used to calibrate the system and
determine sulfate filter concentrations.

       Prior  to obtaining a sulfate sample, each filter was weighed  on
a microgram  balance under a controlled environment and then again
after each sample was  obtained and before the extraction step.   The con-
trolled environment for the microgram  balance was maintained at  72
 IF (dry) and 57  1F  (wet),  providing an absolute humidity of 46
 2 grains F^O per pound dry air and a relative humidity of 39 percent.
By obtaining the particulate weight, it was possible to determine what
fraction was sulfate of  the total particulate as well as the particulate
emission rates.

       Both sulfate and particulate weights were obtained using a  single
filter for the entire 31  minute 1975 LD FTP.  The 31 minute duration
consisted of the hot start 23 minute LA-4 driving cycle plus the first
505 seconds of the next LA-4 test following a 10 minute soak.  The sul-
fate  and particulate emission rates are  not weighted in accordance with
the 1975  FTP, since only one sample was obtained and,  therefore, must
be viewed accordingly.  The SO^ and particulate weights were simply
divided by the kilometers driven to obtain g/km for the engines, fuels, and
additives tested.

       The barium chloranilate detection method was used throughout the
program for sulfate collected samples and proved to  be a precise, re-
liable analytical tool.   A number  of standards were exchanged between
EPA (Ann Arbor),  EPA (RTP),  and SwRI; and the correlation between
laboratories was satisfactory.  A thorough description of the sampling
system interface, dilution tunnel,  and the analytical instrumentation is
presented in Appendix A.

       4.  Nitrogen Compounds

       Nitrogen compounds measured included ammonia, dimethylnitro-
samine,  and nitromethane.  Samples  were analyzed from the 1975 LD FTP

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bags,  and the concentration of individual compounds was determined.
Individual standards were prepared for the quantitative determination
of each of the nitrogen compounds.  The NH^, CH^NC^,  and DMNA
were measured using a gas chromatograph system equipped with an
electrocoulometric detector (ECD).  Of all three compounds,  only
CH3NC>2  was observed in the majority of bag samples.  This procedure
is described more thoroughly in Appendix A.

B.     Engine Dynamometer Test Stands

       Two engine dynamometer stands were constructed using water
brake absorbers  removed from Clayton CT-200  chassis dynamometers.
The  shaft used to connect the automatic transmission output and the ab-
sorber also held  an inertia wheel and a hydraulic disc brake.  The  rpm
signal obtained from the tach generator of the Clayton unit was calibrated
in miles  per hour, permitting a  standard driving aid to be used as a speed
readout;  and the entire torque arm-load cell-readout system from the
Clayton was  retained intact for  setting  road loads.  Several views of the
engine dynamometer stands and  control systems are shown in Figure 1.

       One  major advantage of  this system is that the power absorption
curve is  intrinsically similar to that of the water-brake chassis dyna-
mometer systems commonly used for LA-4 vehicle tests.  The proper
simulation of road load (as  it varies with speed) by electric dynamometers
is a  complex and expensive process, and often the accuracy of the simu-
lation is  not  as good as expected.  Once calibrated, the water brake sys-
tem  essentially reprodur.ss the  chassis dynamometer results faithfully.
In addition,  since the w.ter absorber "loads  up" by itself as speed  in-
creases, no  control loop is required for that purpose; and  engine control
becomes simply a matter of throttle or brake application as required to
follow the LA-4 trace.

       The  system controls simulate those in an automobile,  permitting
throttle and brake application by an operator for system checkouts,  pro-
cedural development, or in the  event of equipment failure to prevent ex-
cessive downtime during repairs.  For mileage  accumulation,  an auto-
matic control loop utilizing the  HYTRESS (Highway Test Recorder and
Simulator System), manufactured by Dynamic Precision Controls Corp-
oration,  was used. This unit was mounted under the operator's seat and
could be  readily disconnected when not in use.  With the exception of a
slight delay and then a slight overshoot on rapid accelerations and decel-
erations, the driving trace  using the automatic control system was essen-
tially identical to driving traces obtained during manual driving.

       The  ratio of tire  diameter to Clayton  dynamometer roller diameter
has been determined to be 3. 07  for the  standard 1972 and 1973 Chevrolet
Bel Air and Impala automobiles.  Therefore, the rotational speed of the
                                  8

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FIGURE 1.  SEVERAL VIEWS OF 350 CID CHEVROLET TEST STANDS

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Clayton dynamometer would equal the rotational speed of the trans mission
output shaft if the rear axle ratio was 3.07.  The Chevrolet  Bel Air and
Impala standard rear axle ratios were 3.08 in 1972 and  2.73 in 1973.  For
this project, it was decided to use a single axle ratio for both of the  two
engines; and the 3.08 ratio was selected. Therefore,  in the test stands
constructed, the dynamometer to transmission output  speed relationship
for the test stand versus the vehicle with standard  axle ratio was identical
for the 1972 model and varied a  little more than 10 percent for the 1973
model.

       The inertia wheel was a solid mild steel disc with an OD/ID 75.
The general formulas used to determine the inertia wheel dimensions
are:

                 30,000                        A                         7
       D(max)=TvT^	       I   = 0.0003986TD4        Ww ft* 0. 006l45TD^
         v     '   1N(max)                                w

       D = diameter of inertia wheel, cm
       N = speed,  rad/sec
       T = thickness of inertia wheel,  cm
           = inertia of wheel, kg - m2
         w = weight of wheel, kg (disregarding center hole)

In the  dynamometer test stands,  the dynamometer  speed is equal to the
transmission  output speed.  Therefore,  the following equations were
derived and used to establish the relationship between the test stand  dyna-
mometer speed and the chassis dynamometer speed.

stationary test stand dynamometer speed _       /	axle ratio	\
     chassis dynamometer speed              '   \effective tire diameter/

                         /effective tire diameter \
       I   =0. 000025 W  I	;	.	)
        w              v \      axle ratio       /
                Effective Tire Diameter in Centimeters

       Several methods were evaluated for determining the proper dyna-
mometer horsepower to be set on the test stand dynamometer.  The test
stand does not have a differential,  rear axle  bearings,  tire to dynamo-
meter roll friction, etc.; and therefore, these must be accounted for
in the horsepower set into the dynamometer.  For determination of the
horsepower setting, a 1972 Chevrolet Impala with a 350 CID engine and
automatic transmission was used.   This automobile and the test stands
were essentially identical with respect to the engine and the automatic
transmission.

       The simulation  of the automobile on a test stand can be accom-
plished by simulating the total inertia and horsepower from the transmission
                                 10

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onward through the drive system and the dynamometer.  This horse-
power was determined with the transmission in neutral using the method
in Appendix II of the Federal Register for the Control of Air Pollution -
New Motor Vehicles and New Motor Vehicle Engines.  Initially,  the  road
load horsepower and inertia prescribed in the Federal Register  (12. 7
and 4500 respectively) were set into the chassis dynamometer.  Coast
down times were determined on the 1972 Chevrolet and also on an avail-
able 1973 Ford.  The times  were essentially the same for both vehicles
indicating that the  horsepower absorbed in the drive systems was essen-
tially the same.  The total horsepower was calculated from the cost down
times using the method in the Federal Register.  This test was conducted
with the transmission in neutral with a 12. 7 hp road load and 4500 Ib inertia.
This calculated horsepower  value was then used for setting up the horse-
power on the test stand, and coast downs were determined on the test
stand. The coast down times obtained on the test stands were essentially
the same as those  obtained with the vehicle on the chassis dynamometer.
These and other data are summarized below:

       Horsepower Calculated From 55 to 45 mph Coast Downs
                                        Coast Down   Calculated
    	Vehicle	   Operation    Time, sec        hp
    1972 Chevrolet Impala
    1972 Chevrolet Impala
    1972 Chevrolet Impala
    1973 Ford LTD
           Test Stand
           Engine No.  1
           Engine No.  2
   dyno
   dyno
   road
   dyno
Total Load, hp

      18
      18
15
16
16
15
18
17

18
 Coast Down
 Time, sec.

      15
      15
       Other determinations included:  the coast down times for the
vehicles on level roadway, the vacuum  at constant 50 mph on level
roadway and on the chassis dynamometer, and the fuel consumption
rate with the vehicle held at 50 mph on  the chassis dynamometer.   These
results are summarized below:

                    Data at 50 mph Constant Speed


Vehicle on Dynamometer
Vehicle on Road
Engine No. 1
Engine No. 2
Set Road
Load, hp
12.7
	
12.7
12.7
Manifold
Vacuum, " Hg
18.5
18.1
17.9
18.1
Fuel Rate,
Ib/min
0.24
_ _ - -
0.25
0.24
                                 11

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In addition, engine backing at cut-throttle was determined to be approxi-
mately 15 hp at 50 mph using the coast down procedure.   All of these
evaluations indicated that the horsepower set into the test stand dynamo-
meter was reasonably indicative of road-load horsepower at an equivalent
speed.

       It is recognized that friction horsepower essentially increases
linearly  with speed and aerodynamics; horsepower increases essentially
as the cube of the speed.   Therefore, the resultant horsepower as the
speed decreases is dependent on the ratio of the friction to aerodynamic
horsepower.  Just as some difference occurs between horsepower on the
road  and the chassis dynamometer over a wide speed range, some differ-
ence will occur between these test stands,  the chassis dynamometer,  and
the road.  In a cycle such as the LA-4,  however, where fairly rapid accel-
erations and decelerations are the dominant feature,  inertia (not road-
load horsepower) is the dominant factor affecting emissions.  At slower
vehicle speeds, the road-load horsepower  is a relatively small portion
of the total horsepower generated during a rapid acceleration;  and rapid
decelerations are controlled by braking, with road-load horsepower being
of essentially no significance.  At higher speeds, where road-load horse-
power is more significant, all systems  have been calibrated to  essentially
the same equivalent horsepower.  Therefore,  both the chassis dynamo-
meter and these test stands adequately simulate road operation for cyclic
tests  such as the LA-4.

       Mileage accumulation was obtained using an automatic driver
system on both engine stands   Repetitive LA-4 cycles were used as the
mileage  accumulation cycle throughout the program.   The automatic drivers
were  used on a 24-hour basis to obtain the mileage in as short a time  as
possible.  Emission tests were conducted using a manual driver and hot
start  LA-4 tests of 31 minute duration.   A 2.54 km (10 foot) long by 21.3 cm
(8.4 inch) ID stainless steel dilution tunnel was used to obtain "isokinetic"
fluoropore filter samples for sulfate and particulate analysis.   This sys-
tem was designed basically for  the analysis of sulfate, since the 803
initially  formed acts as both a gas and a particle.  The construction of
the tunnel was  for SO4= measurements.  However,  it was possible to
weigh the filters before and after each test to obtain an indication of
particulate emission rates.  A flow schematic of the "mini tunnel" along
with the  critical dimensions is presented in Figure 2.  This research
effort was  not intended to be a particulate study, and no  correlation with
the EPA standard 45. 7 cm (18 inch) dilution tunnel was performed.

       The contractual requirement to report all data and results in mod-
ernized metric units (SI) requires a statement of equivalent emission
standards for 1973 and later model  year light-duty cars  in grams per
kilometers (g/km) for understanding. Table 1 lists the HC,  CO, and NOX
limits in g/km with those published in appropriate Federal Registers in
                                 12

-------
t  X  IO  !IJl,M!  -.                "*
      KIlUFf <-l.  a ES-.ER CO.

-------
g/mile in parentheses.  The conversion was based on 1.609 km equal to
1 mile and were rounded to the same number of decimals as the published
limit.  The metric equivalent levels are approximately 62 percent of the
mixed metric-English units.

       As previously mentioned,  emission rates  calculated during this
research effort were on the basis of a hot.start 1975 LD  FTP.  The  gas-
eous emission  rates, particularly HC and CO, were affected by hot start
testing; and comparisons between emission rates reported in this report
and those standards presented in Table 1 should be  made with extreme
caution.

       Table 1 is  merely included as a frame of reference.  Please keep
in mind,  as mentioned earlier, that even though gaseous emissions of
HC,  CO,  NOX,  and SO2 were taken on a three bag 1975 LD FTP (from a
hot start), only one sample for SO^= was collected during the entire 31
minutes  (23 minutes plus 505 seconds).

     TABLE 1. FEDERAL LIGHT DUTY EMISSION STANDARDS

      Year          Units            HC          CO        NO
                                                                 if
1973-1974      g/km (g/mile)   2.1(3.4)      24(39)     1.9(3.0)

1975 Interim     g/km (g/mile)   0.9(1.5)      9.3(15)    1.9(3.1)

Original
1975 Statutory   g/km (C/mile)   0.25(0.41)    2.1(3.4)   1.9(3.1)
1977 Statutory*   g/km (g/mile)   0.25(0.41)    2.1(3.4)   1.3(2.0)

1978 Statutory*   g/km (g/mile)   0.25(0.41)    2.1(3.4)   0.25(0.40)
 * suggested by the Administrator on March 6,  1975 but not yet enacted
  into law

C.     Test Plan

       The basic test plan of this program involved the use of the two
aforementioned  Chevrolet engines on a mileage accumulation engine
dynamometer system.  Each engine was run using a total of four fuel/
additive packages.  Two additives were selected from a number of can-
didate additives as the fuel/additive combinations for evaluation.  The
additives  were selected based on application to the fuel, and engine model
years used in this research  effort.

       Enjay  Paradyne 506 and Lubrizol 8101  were the two additive
formulations selected.  Paradyne 506 is an  amine type carburetor
                                 14

-------
detergent with multifunctional additives to reduce rust, engine sludge,
and water miscibility.  The Lubrizol 8101 additive is also a nitrogen con-
taining additive typically employed as a carburetor detergent.  Anti-rust
and anti-icing additives are also included in the Lubrizol 8101  additive
package.  Enjay Paradyne 506 was added to the fuel in the manufacturer's
recommended treatment level of 45 PTB (0.486 g/gal).  The supplier's
recommended treatment level for  Lubrizol 8101 was 35 PTB (0.378 g/gal),
A list of the fuel/additive combinations used for each of the engines is
presented in Table 2.

       TABLE 2.   LIST OF FUEL/ADDITIVE COMBINATIONS
  Engine Description    Fuel Code

  1972 350 CID Chevy   EM-214-F

  1972 350 CID Chevy   EM-215-F


  1972 350 CID Chevy   EM-216-F


  1972 350 CID Chevy   EM-231-F


  1975 350 CID Chevy   EM-214-F

  1975 350 CID Chevy   EM-215-F
	Fuel Additive Description

Base fuel at 0.1% S

Base fuel at 0.1% S + 0. 378 g/gal
Lubrizol 8101

Base fuel at 0.1% S + 0. 486 g/gal
Paradyne 506

Base fuel at 0.1% S + 0.378 g/gal
Lubrizol 8101 + 0.05 g/gal Pb

Base fuel at 0.1% S

Base fuel at 0.1% S + 0. 378 g/gal
Lubrizol 8101
  1975 350 CID Chevy   EM-216-F   Base fuel at 0.1% S -I-0.486 g/gal
                                   Paradyne 506

  1975 350 CID Chevy   EM-218-F   High aromatic fuel at 0.1% S +
                                   0.378 g/gal Lubrizol 8101

       The first three additive combinations were identical for both en-
gines. These included base fuel, base fuel with Lubrizol 8101, and base
fuel with Paradyne 506.  The fourth fuel/additive combination utilized
Lubrizol 8101 at 0.1 percent sulfur level but with two different base
fuels.  Tests with the 1975 350 CID engine were conducted using a high
aromatic fuel with the Lubrizol 8101 at a 0.1 percent sulfur  level.  Tests
with the 1972 350 CID Chevrolet engine were conducted using the original
base fuel with Lubrizol  8101 at 0.1 percent S but with 0.05 g/gal Pb added.

       The base fuel was supplied by EPA and was used for  both mileage
accumulation and emission testing.  The high aromatic fuel was obtained
                                 15

-------
from the American Oil Company and the fuel inspection data for both
fuels is presented in Table 3.  The fuels were supplied in 55-gal drums
and each drum was blended individually.  Both fuels were doped with thio-
phene to obtain the desired 0. 1 percent sulfur level.  Emission tests for
a given fuel/additive combination were conducted on fuel from a given drum
at the three mileage accumulation test intervals.

       During the procedural development phase of the program, the catalyst
had sufficient hours of repetitive  LA-4 operation to insure catalyst break-
in.  Once the emission testing was initiated  for record, it was felt  that the
catalyst had in excess of 600 miles of LA-4 'operation.  Prior to  testing a
given fuel/additive combination the cylinder heads were removed and cleaned.
Valves were cleaned and lapped.  The exhaust system was cleaned  or re-
placed, the only portion remaining unchanged was the catalyst in the 1975
350 CID Chevrolet engine.

       A minor tune-up was also performed, which included points,  plugs,
condenser  prior to testing each fuel/additive combination.  After re-
assembling the engine and performing the necessary tune-up steps,  the
engine went through a short conditioning period to burn-out any residual
oils in the  new exhaust system and to allow  seating of engine components.

       Due to the nature of the objectives of this program, it was decided
to use a hot start 1975 LD FTP as the test procedure in this study.  Each
test  that is reported in this report is based  on a hot start LA-4.  Each test
was preceded by a 23 -minute LA-4 and then a 10 -minute soak.  After the
10-minute  soak, the engin ; was started and  the three bag 1975 LD FTP was
run from that point.  The first two bags were obtained during the first 23
minutes and  the third bag obtained during the first 505 seconds for  the second
23 minute  run.  Although the mileage accumulation was obtained  using an
automatic  driver, the emission tests were performed using a manual driver.

        The emission test intervals were at  0, 1000 and 2000 miles.  In
most cases,  three 1975 LD FTP tests were  conducted on both engines with
each fuel/additive combination.  When emissions data was repeatable only
two tests were conducted.   As part of the characterization portion of the
program,  measurement of NRHC, sulfur and nitrogen compounds were con-
ducted only on the first two runs.
       Generally, if a given test was repeated,  SO2 SO^" and particulate
were also obtained.   After the final test for a given  fuel/additive combination
at 2000 miles, then  the engine was disassembled,  cleaned and readied
for the next fuel/additive package.

D.     Engine Qualification

       Engine qualification tests were conducted on  both engines during
the initial phase of the program.  Emission specifications were pre-

                                   16

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TABLE 3.  MILEAGE ACCUMULATION AND EMISSION TESTING
                 FUEL INSPECTION t)ATA
                              Base Fuel          High Aromatic Fuel
       Analysis	      (EM-214-F)           (EM-217-F)
Distillation, ASTM D-86, F
10%
50%
90%
. EP
Gum, ASTD D-381, mg
Sulfur , ppm
Stability, D-525, hrs
Phosphorous, ppm
Research Octane Number
Motor Octane Number
Lead, g/gal
FIA Analysis, D-1319
Aroma tics, %
Olefins, %
Paraffins, %

123
199
325
383
4.8
190
24+
1
93.2
84.7
nil

24.0
8.3
67.7

125
205
340
390
5.
40
24+
-
-
-
nil

52.'
4.
43.


2







0
3
7
                             17

-------
sented by EPA for the engines to be accepted for mileage accumulation.
Since the type of start was not specified, a number of emission tests
were conducted using three different types of starts on both test stands.
They were cold starts, force-cooled starts and hot starts.

       The force cooled starts -were conducted using a given set of.pre-
determined conditions to insure  repeatable test conditions.  After the
initial cold start had been completed, the engine was shut off and cooling
water was forced through the engine.  A fan was used to force  lab air
over the engine and once the engine had been cooled down and remained
stable at not more than 3F above ambient temperature, the engine was
ready for 1975 LD FTP testing.  Similar force cooling procedures have
been used quite satisfactory in other projects.

       An alternative  procedure for conducting the mileage accumulation
emission testing was to use a hot start rather than force cooled or cold
starts.  A procedure was readily devised for obtaining repeatable hot
start emission data.  One advantage of using hot starts  was to  enable the
tunnel to be pre-heated to a consistent temperature.  This aided in the
preservation of sample integrity, especially for the reactive sulfur con-
taining compounds during the start-up and initial warm-up period  of the
tunnel prior to the CVS.  It was uncertain as to the fate of SO and 803
if the tunnel wall temperature changes significantly during the  first 505
seconds of the  1975 LD FTP.  This uncertainty was eliminated by employing
hot starts exclusively  during  the mileage accumulation emission testing.
Further,  sulfate testing required an initially preheated  engine  exhaust
system to avoid losses fro^n condensing water, which normally occurs
in cold start testing.

       The EPA emission specifications, along with the emission results
for both test stands for the three types of starts are presented in Table 4.
Investigation of the effect of type of start on emission rates provided data
which proved to be useful in the  selection of type of  start.  When summarizing
the emission results,  it became apparent that the hot start produced  some-
what more consistent results.  The data in Table 4 illustrate that the engines
do and do not fall within the contract specifications, depending on the type of
start used in conducting the tests.

       Since the emission rates were definitely influenced by type of en-
gine start,  and more consistent results were obtained using hot starts, all
emission testing during the mileage accumulation phase was conducted
using hot starts.  This decision was in concurrence with the Project Officer
and engines were deemed acceptable for fuel/additive testing.
                                   18

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       TABLE 4.   1972 AND 1975 350 CID CHEVROLET ENGINE
               EMISSION QUALIFICATION RESULTS
                             EPA             S-wRI Emission Results
 1975 LD FTP            Specifications*
 Emission Rates          Max      Min

 HC, g/km       1972    2.5       1.5
HC, g/km       1975    0.3      0.2
CO, g/km       1972    22        12
CO,  g/km        1975    2.1       1.7
NOX,  g/km       1972    2.5      1.9
NOX,  g/km       1975     1.9      1.6

Run
1
2
3
Avg.
1
2
3
4
Avg.
1
2
3
Avg.
1
2
3
4
Avg.
1
2
3
Avg.
1
2
3
4
Avg.

Cold
2.06
2.05
-
2.06
0.34
0.46
0. 28
0.39
0.37
28.16
26.43
-
27.30
4.09
4.98
4.09
4.70
4.47
1.74
1.60
-
1.67
1.14
1.26
1.17
1.26
1.21
Force
Cold
1.82
1.79
2.00
1.87
0.23
0. 18
0.21
0.27
0.22
21.99
23.54
21.84
22.46
2.71
2.70
2.56
2.99
2.74
1.58
1.71
1.84
1.71
1.24
1. 12
1.08
1.24
1. 17
Hot
Start
1.56
1.43
1.45
1.48
0. 13
0. 14
0. 14
0.14
0. 14
20. 13
18.34
20.99
19.82
1.16
1. 13
1.61
1.87
1.44
1.70
1.73
1.61
1.68
1. 16
1.19
1.12
1.12
1. 15
*EPA Specifications did not state type of start
                                 19

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                           HI.  RESULTS

       The nature of the test matrix for the characterization of emissions
as a function of fuel/additive  combinations necessitates comparisons be-
tween these test fuels on each engine separately.  Comparisons of emis-
sion rates  between engines for a given fuel/additive package are not pre-
sented; although, data is included if comparisons are desired.

       The question of test repeatability is significant in the potential
conclusions from this research effort. For example,  historic values
of standard deviations in FTP testing in percent of mean value are  13.0
percent for HC, 18. 2 percent for CO, and 9.1 percent for NOX.  In the
cold, forced cold, and hot start qualification tests, emission variability
is presented in Table 5.   Based on results of these experiments, it was
felt that hot starts would give the best overall test repeatability.

       One of the primary objectives of this program was to establish
whether the 1975 LD FTP would be sufficiently sensitive to  detect
changes in emissions as a function of fuel/additive packages.   With
this  in mind, a number of curves were determined for six different
emissions  to establish the fuel/additive packages as  a function of LA-4
mileage accumulation.

       These curves must be viewed in the proper perspective with re-
gard to emission test variability when looking for fuel additive effects.
In a  number of cases,  emission trends were observed but careful anal-
ysis  of test variability indicated that these trends were actually within
the test variability itself.

A.     1972  350 CID  Chevrolet Engine

       For the purposes of this  report,  the results from the 1972 engine
will  be discussed first.  This engine was used in evaluation of the four
fuel/additive packages.  These test fuels were coded EM-214-F, EM-215-F,
EM-216-F and EM-231-F.

       1.   EM-214-F Base Fuel at 0. 1 Percent Sulfur

            The first fuel tested was the base  fuel at 0. 1 percent sulfur
(EM-214-F)  and the results of each individual test are shown in Table  6.
A summary of these test  results is presented  in Table  7. The HC  emis-
sion rates  were essentially constant over  the 2000 mileage accumulation
schedule.  The CO emission rates increased slightly,  from 18. 16 to 21. 14
g/km, although within the test variability.  The NOX emission rates de-
creased from 2.04 to 1.59 g/km over the  additional miles.  The SO?
(bag) emission rates  decreased from 0.30 to 0.23 g/km, and the SO?
(continuous)  decreased from 0.41 to 0.34  g/km.  The  sulfate emission
                                 21

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TABLE 5.  QUALIFICATION TEST EMISSIONS VARIABILITY




 Cold Start                    Forced Cold                   Hot Start
72
Emission 
-------
                              TABLE 6 .  SUMMARY OF EXHAUST EMISSIONS OF 1972 CHEVROLET 350 CID ENGINE
                                                         EM-214-F (BASE FUEL at 0.1% S)
t\>
Co
Mileage
Interval Date
0 miles 12/16/74


1000 miles 12/23/74


2000 miles 12/31/74


Run
No.
1
2
Avg.
1
2
Avg.
1
2
Avg.
1975 LD FTP
HC
1.74
1.44
1.59
1.56
1.43
1.50
1.45
1,41
1.43
NRHC
0.25
0.22
0.24
0.25
0.20
0.23
0.31
0.30
0.31
CO
18.87
17.45
18.16
20.13
18.34
19.23
20.99
21.29
21.14
NOV
2.02
2.06
2.04
1.70
1.73
1.72
1.61
1.56
1.59
Emission
S0,(b)*
0.28
0.31
0.30
0.26
0.28
0.27
0.23
0.23
0.23
Rate, g/km***
SOz(c)**
0.42
0.40
0.41
0.35
0.32
0.34
0.35
0.33
0.34
504 =
0.0004
0.0004
0.0004
0.0002
0.0003
0.0003
0.0004
0.0003
0.0004
Part.
0. 0094
0.0049
0.0072
0.0146
0.0085
0.0116
0.0112
0. 0085
0.0099
NRHC*1'
HC
0.14
0.15
0.15
0.16
0.14
0.15
0.21
0.21
0.21
S07(b)^'
S02(c)
0.67
0.78
0.73
0.74
0.88
0.81
0.66
0.70
0.68
S04 =
Part.
0.04
0.08
0.06
0.02
0.03
0.03
0.03
0.04
0.04
            SO2(b) indicates SO2 values obtained using CVS bag samples
         ** SO(c) indicates SOg values obtained using continuous on-line sampling with TECO
        *** All 1975 LD FTP emission tests are conducted using hot starts
        (1) NRHC/HC indicates the ratio of NRHC to HC emission rates
        (2) SOgfbJ/SOgfc) indicates the ratio of bag SO2 to continuous 803 values
        (3) SC>4=/particulate indicates the fraction of SO* = in the particulate

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                  TABLE  7.  SUMMARY OF 1972 350 CID CHEVROLET ENGINE EMISSION RATES




                                              1975 LD FTP (Hot Start) Emission Rate, g/km
Exhaust
. Species
HC
NRHC
NRHC/HC
CO
NOX
S02(b)
S02(c)
S02(b)/S02{c)
SO4=*
Part. *
SO4=/Part.
EM-214-F
0
1.59
0.24
6.15
18.16
2.04
0.30
0.41
0.73
0,4
7.2
Ok06
1000
1.50
0.23
Q.15
19.23
1/72
0;27
0.3,4
0.81
0.3
11.6
0.03
2000
1.43
0.31
0.21
21.14
1.59
0..23
or 34
0.68
0.4
9.9
0.04
EM-215-F
0
 0.99
0.15
0.15
12.96
1.39
0.30
0.39
0.77
0.4
3.5
O.U.
1000
0.75
0.12
0,16,
11.60
1.56
0.^0.
0.37
0.81
0.3
4.1
0^
2000
0.77
0.14
0.18
13.14
1.51
0 . 30_
0.37
0.81
0.3
5.3
0.06
EM-216-F
0
1.35
0*25
23.62
1.81
0.31
0.40
0.78
0.2
5.1
0.01
1000
0.96
0.12
0.12
11.85
1.48
0.27
0.34
0.81
0.2
6.6
0.03
2000
0.83
0.15
0.18
13.30
1.60.
Q.,29
0.33
0.88
0.2
5.2
0.04
EM-231-F
0
1.02
0.19
0.19
t
1.32
0.25
0.39
0.64
0.2
3.3
6.05
1000
0.89
0.16
0.18
16.63
1.55
0.33
0.41
0.80
0.2
6.2
0.03
2000
0.88
0.18
0.19
16.36
1.38
0.22
0.36
0.61
0.4
5.1
0.08
* mg/krn

-------
rates remained relatively constant at 0.4 mg/km, while the particulate
emission rates ranged between 7.2 to 11.6 mg/km.

           The effect of mileage accumulation on HC,  CO and NOX emis-
sion rates is presented in Figures 3,4, and 5 respectively.  Figures 6, 7'-,
and 8 illustrate the effect of mileage accumulation on the emission rates  of
SOo  SO "and particulate respectively.

           The ratio of NRHC/HC ranged from 0. 15 to 0. 21; whereas
the SO2 (b)/SO2 (c) ratio ranged from 0. 68 to 0. 81 and the SO4~/particulate
varied from 0.03 to 0. 06.  The sulfur recoveries based on bag SO values
ranged from 60-96 percent while the continuous SO2 sulfur recoveries
ranged from 110-135 percent.  The bag SO emission rates averaged about
0. 74 of the continuous  SO concentrations.  Of the fuel  sulfur, less than 0. 1
percent appears as sulfate, and of the particulate the sulfate was about 4 per:
cent of the total weight.

           Characterization of the exhaust of the 1972  350 CID Chevrolet
engine operating on EM-214-F for sulfur and nitrogen compounds is pre-
sented in Table C-l of Appendix C.  Of all of the compounds to be deter-
mined,  only one was found on a routine basis.  Only trace quantities of COS
and HS were detected upon occasion and under no tests was CH^SH and
C2-H5SH detected.   The analysis for ammonia and dimethylnitrosamine
indicated that neither of these compounds were present in any of  the bag
samples at any of the mileage test intervals.   Of all the nitrogen and  sulfur
compounds included in the analysis,  only nitromethane  was  detected on a
regular basis.  First and third bag values were typically 0. 15-0. 20 ppm and
the second bag ranged from 0.05-0. 12 ppm.  Individual non-reactive and
several reactive hydrocarbons were measured during each test and the raw
data is presented in Table B-l of Appendix B.

       2.   EM-215-F Base Fuel, 0. 1 Percent Sulfur with 0. 378 g/gal
           Lubrizol 8101

           This fuel/additive package involved the use of the base fuel
doped with thiophene to achieve a 0. 1 percent sulfur level.  In addition,
0. 378 g/gal of Lubrizol 8101 was added.  The emission rates of all tests
conducted on the 1972 350 CID Chevrolet engine with EM-215-F is  presented
in Table 8.  A summary of all the emission rates is included in Table 7
for comparison to other fuel/additive packages.

           The HC emission  rates decreased from 0. 99 to  about 0.76 g/km
from the 0-mile to the 1000-and 2000-mile emissions inspection.  Figure 3
(hexagon shaped points) illustrates the effect of mileage accumulation  on the
HC emission rates using EM-215-F in the 1972 engine.  The CO  emission
rates ranged from 11. 60 to 13. 14 g/km and can be  seen as a function of
mileage accumulation in Figure 4.  Only a slight increase in NOX emission
                                  25

-------
c
o
.1-1
CO
to
|H
6
w
u
   0.4
       0
           1000
LA-4 Mileage Accumulation
2000
     FIGURE 3 .  HC EMISSION RATES OF 1972 350 CID
 CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS
               WITH THE FOUR TEST FUELS

-------
(U
o
H

(0

(0
w

o
u
    12
     8
     0
                                 1000

                        LA-4 Mileage Accumulation
2000
    FIGURE  4.  CO EMISSION RATES OF 1972 350 CID

CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS

              WITH THE FOUR TEST FUELS
                           27

-------
    2.8
a
o
m
CD
w
 X
o
z
    2.4r-
                                                  ':|  iluOlli''-I-.'H' ^.il !
    0.8
    0.4
      0 -
                                   1000
                        LA-4 Mileage Accumulation
2000
      FIGURE  5 .  NOX EMISSION RATES OF 1972 350 CID
  CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS
                WITH  THE FOUR TEST FUELS
                              28

-------
    0.7 :
    0.6
    0.5
S

-------
X

g
C

O
H
co

CO
w

II
^
o
CO
      0
         1000

LA-4 Mileage Accumulation
                                                           2000
    FIGURE 7 .  S04= EMISSION RATES OF 1972 350 CID

 CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS

               WITH THE FOUR TEST FUELS
                            30

-------
    2.8
X


I

00
 G
 O
i-i
 (0
 CO
|H

 s

w
t-4

at
    2.4 -r
    0.8
    0.4
      0
                                    1000


                          LA-4 Mileage Accumulation
2000
 FIGURE 8 .  PARTICULATE EMISSION RATES OF 1972 350 CID


    CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS

                 WITH THE FOUR TEST FUELS
                              31

-------
                               TABLE 8 .  SUMMARY OF EXHAUST EMISSIONS OF 1972 CHEVROLET 350 CID ENGINE
                                           EM-215-F (BASE FUEL at 0.1% S + 0.378 g/gal LUBRIZOL 8101)
to
Mileage
Interval Date
0 miles 2/10/75



1000 miles 2/13/75


2000 miles 2/18/75



Run
No.
1
2
3
Avg.
1
2
Avg.
1
2
3
Avg.
1975 LD FTP
HC
1.12
0.94
0.92
0.99
0.73
0.77
0.75
0.78
0.75
0.78
0.77
NRHC
0.16
0.14
	
0.15
0.12
0.12
0.12
0.15
0.12
	
0.14
CO
15.01
11.66
12.22
12.96
11.29
11.90
11.60
14.68
12.02
12.71
13.14
NOV
1.44
1.47
1.26
1.39
1.67
1.45
1.56
1.52
1.52
1.48
1.51
Emission
S0?(b)*
0.30
0.30
0.31
0.30
0.30
0.30
0.30
0.30
0.27
0.33
0.30
Rate, g/km*** NRHC^
SOj.{c)**
0.-42
0.38
0.38
0.39
0.38
0.36
0.37
0.38
0.36
0.37
0.37
S04 -
0.0004
0.0004
0. 0004
0.0004
0.0003
0.0002
0.0003
0.0003
0.0003
0.0003
0. 0003
Part.
0.0041
0. 0036
0.0029
0.0035
0.0062
0.0021
0.0041
0.0072
0.0048
0.0038
0.0053
HC
0.14
0.15
	
0.15
0.16
0.16
0.16
0.19
0.16
--.--
0.18
S0?(b)<2)
S0?(c)
0.71
0.79
0.82
0.77
0.79
0.83
0.81
0.79
0.75
0.89
0.81
SOa =<3>
Part.
0.10
0. 12
0.12
0.11
0.06
O.H
0.08
0.05
0.06
0.08
0.06
           * SO2(b) indicates SOg values obtained using CVS bag samples
          ** SO2(c) indicates SOg values obtained using continuous on-line sampling with TECO
         *** All 1975 LD FTP emission tests are conducted using hot starts
         (1) NRHC/HC indicates the ratio of NRHC to HC emission rates
         (2) SO2(b)/SQ2(c) indicates the ratio of bag SO2 to continuous SO2 values
         (3) SO4=/particulate indicates the  fraction'of SO^= in the particulate

-------
rates was observed,  from 1. 39 to 1. 51 g/km, with increasing mileage accu-
mulation, as illustrated in Figure 5.

            SO2 (bag) emission rates remained constant at 0. 30 g/km while
the SOz continuous emission rates were about 0. 38 g/km for all the test
intervals.  The sulfate emission rates ranged from 0. 3-0. 4 mg/km while
the particulate emission rates increased from an initial level of 3. 5 to 5. 3
mg/km at 2000 miles.  Sulfur dioxide,  sulfate and particulate emission
rates as a function of mileage inspection interval is presented in Figures 6,
7, and 8 respectively.

            The characterization of the exhaust for various sulfur and nitrogen
compounds of interest is presented in Table C-2 of Appendix C.  As in the
previous test,  the only sulfur or nitrogen compound of interest that was de-
tected on a routine basis was nitromethane.  The CH3NO2 concentration in
the first and third bags ranged from 0. 18 to 0. 31 ppm while the  second bag
ranged from 0. 12 to 0. 15 ppm. No ammonia, dimethylnitrosamine, hydrogen
sulfide,  carbonyl sulfide, methyl or ethyl mercaptan was detected.  Individual
non-reactive and several reactive hydrocarbons were measured during
these tests, and these results are presented in Table B-2 of Appendix B.

            The  ratio of NRHC/HC  ranged  from 0. 15 to  0. 18 over the
three emission inspections.  The ratio of SO2 (bag)/SOo  (continuous) varied
between  0. 77 and 0. 81 for the three test intervals.  The  fraction of SO^"
in the total particulate decreased from 0. 11 to 0. 06 from the 0 to  2000 mile
inspection.

            The sulfur distribution in the exhaust for the 1972 engine using
EM-215-F is presented in Table D-2.  Sulfur balances using  the SC^ values
obtained from the bag samples averaged  108 percent-recovery,  while using
continuous SC>2 values, the sulfur recoveries averaged 134 percent.  Less
than 0. 1 percent of the fuel sulfur appeared as sulfate in the exhaust.

       3.   EM-216-F Base Fuel, 0. 1 Percent Sulfur with 0.486 g/gal
            Paradyne 506

            The third fuel/additive package had 0.486 g/gal Paradyne  506
added to the base fuel doped to 0. 1 percent  sulfur with thiophene.  The
results of the individual emission tests are found in Table 9 and these  results
are summarized in Table 7.

           As with the previous tests,  the  HC emission  rates decreased
with increasing mileage accumulation, from 1.35 to 0.83 g/km.   There was
a significant decrease in the CO emission rates, from 23. 62  at the initial
test to 11. 85 and 13.30 g/km at the 1000- and 2000-mile emissions  inspec-
tion.  The effect of mileage accumulation on HC and CO emission  rates is
presented in Figures 3 and 4.  The NOX emission rate varied between 1.81
and 1.48 g/km over the three test intervals,  as illustrated in Figure 5.


                                  33  "

-------
                      TABLK  V   SUMMARY OF EXHAUST EMISSIONS OF 1972 CHEVROLET 350 CID ENGINE
                                  EM-216-F (BASE FUEL at 0.1% S + 0.486 g/gal PARADYNE 506)
Mileage
Interval Date
0 miles 1/10/75


1000 miles 1/13/75


2000 miles 1/20/75



Run
No.
1
2
Avg.
1
2
Avg.
1
2
3
Avg.
1975 LD FTP Emission Rate, g/km*** NRHC*1' SO^b)^'
HC
1.37
1.33
1.35
0.97
0.95
0.96
0.84
0.81
0.83
0.83
NRHC
0.25
0.24
0.25
0.12
0.11
0.12
0.16
0.13
	
0.15
CO
24.31
22.91
23.62
12.80
10.89
11.85
13.71
12.60
13.60
13.30
NOV SO,(b)*
1.63
1.98
1.81
1.50
1.45
1.48
1.53
1.69
1.58
1.60
0.29
0.33
0.31
0.26
0.28
0.27
0.28
0.29
0.30
0.29
SO?(c)**
0.38
0.42
0.40
0.35
0.32
0.34
0.30
0.33
0.36
0.33
S04 =
0.0002
0.0002
0.0002
0.0002
0.0001
0.0002
0.0002
0.0002
0.0002
0.0002
Part.
0.0050
0.0051
0.0051
0.0072
0.0059
0.0066
0.0050
0.0039
0.0067
0.0052
HC
0. 18
0.18
0.18
0.12
0.12
0.12
0.19
0.16
	
0.18
SOz(c)
0.76
0.79
0.78
0.74
0.88
0.81
0.93
0.88
0.83
0.8S
SO4 =W
Part.
0.01
0.01
0.01
0.03
0.02
0.03
0.04
0.05
0.03
0.04
  * SOg(b) indicates SO2 values obtained using CVS bag samples
 ** SOgCc) indicates SO2 values obtained using continuous on-line sampling with TECO
*#* All 1975 LD FTP emissions tests are conducted using hot starts
(1) NRHC/HC indicates the ratio of NRHC to HC emission rates
(2) SO2(b)/SO2
-------
            The SO2 (bag) emission rates ranged from 0.27 to 0.31 g/km
while the SO2 (continuous) emission rate ranged from 0.40 at the 0-mile
test to 0.33 g/km at the 2000-mile inspection,  as shown in Figure  6.  The
sulfate emission rate remained at 0.2 mg/km  for all three mileage interval
tests, as illustrated in Figure 7-  The particulate emission rate for
EM-216-F ranged only from 5. 1 to 6. 6 mg/km at the  three mileage emis-
sion inspections and is shown in Figure 8.

            The fraction of NRHC in the total HC ranged from 0. 12 to 0. 18
at the three test intervals.  The fraction of SO4~ in the total particulate of
the 1972 engine operating on EM-216-F  increased from 0.01 to 0.04.  The
SO2 (bag)/SO2  (continuous) ratio ranged from 0.78 to  0. 88.

            As with the two  previous tests,  CHoNOo was  the only sulfur or
nitrogen compound consistently detected, although trace quantities  of H2S
and COS were observed upon occasion.  The CH^NO,  concentrations were
slightly higher at the 0- and 2000-mile tests than the two previous fuel/addi-
tive tests.   The individual bag analysis for  all sulfur and nitrogen compounds
is presented in Table C-3 of Appendix C.

            Sulfur recoveries based on SO- bag values were more encour-
aging than with the two previous fuels.   The overall sulfur recovery averaged
95 percent using the SO2 bag values compared to 115 percent recovery  using
the continuous  SO2 concentrations.  Again,  the fraction of fuel sulfur
appearing as sulfate in the non-catalyst 1972 engine was less than 0. 1 per-
cent.  The sulfur distribution for each individual run on the 1972 350 CID
Chevrolet engine operating on EM-216-F is presented in Table D-3 of
Appendix D.

       4.    EM-231-F  Base Fuel. 0. 1 Percent Sulfur. 0.378 g/gal Lub-
            rizol 8101, and 0.05 g/gal TEL

            The final fuel additive package evaluated using the 1972 engine
was EM-231-F.  This was the EPA supplied base fuel doped to a 0. 1 per-
cent sulfur  level with thiophene.   Also added to the fuel was Lubrizol 8101
at 0. 378 g/gal and tetra ethyl lead (TEL) motor mix at 0. 05 g/gal.  As with
the previous tests, emission inspections were conducted at the 0-,  1000-,
and 2000-mile  intervals.

            The results of the individual emission tests are presented in
Table 10 and are summarized in Table 7.  There was only a  slight decrease
in the HC  emission rates over the three inspections as illustrated in Figure 3.
The CO emission rates had an insignificant decrease from 18.40 g/km  at
the initial inspection to about 16.5 g/km at the 1000- and 2000-mile emission
tests.  There was no definite trend in the NOX emission rate as  a function  of
mileage accumulation using fuel EM-231-F, as shown in Figure 5.
                                  35

-------
                      TABLE 10.  SUMMARY OF EXHAUST EMISSIONS OF 1972 CHEVROLET 350 CID ENGINE
                           EM-231-F (BASE FUEL at 0.1% S + 0. 05 g Pb/gal + 0.378 g/gal LUBRIZOL 8101)
Mileage
Interval Date
0 miles 3/11/75


1000 miles 3/14/75



2000 miles 3/21/75



Run
No.
1
2
Avg.
1
2
3
Avg.
1
2
3
Avg.
1975 LD FTP
HC
1.02
1.01
1.02
0.88
0.91
0.87
0.89
0.88
0.93
0.82
0.88
NRHC
0.18
0.19
0.19
0.16
0.16
	
0.16
0.17
0.18
	
0.18
CO
17.91
18.89
18.40
16.71
17.24
15.93
16.63
16.41
16.80
15.87
16.36
NOX
1.34
1.29
1.32
1.41
1.71
1.53
1.55
1.34
1.47
1.32
1.38
Emission
SO?(b)*
0.25
0.25
0.25
0.30
0.35
0.34
0.33
0.21
0.23
0.23
0.22
Rate, g/km***
SO?(c)**
0.39
0.39
0.39
0.41
0.41
0.40
0.41
0.35
0.36
0.38
0.36
SO4 =
0.0001
0.0002
0.0002
0.0002
0.0001
0.0002
0.0002
0.0002
0.0004
0.0007
0.0004
Part.
0.0033
0.0032
0.0033
0.0087
0.0056
0.0044
0.0062
0.0045
0.0058
0.0050
0.0051
NRHC(1)
HC
0.18
0.19
0.19
0.18
0.18
	
0.18
0.19
0.19
	
0.19
SO,(b)<2>
S02(c)
0.64
0.64
0.64
0.73
0.85
0.85
0.80
0.60
0.64
0.61
0.61
S04 = <3>
Part.
0.03
0.06
0.05
0.02
0.02
0.05
0.03
0.04
0.07
0.14
a. 08
  * SO2(b) indicates SOg values obtained using CVS bag samples
 ** SO^tc) indicates SO values obtained using continuous on-line sampling with TECO
*** All 1975  LD FTP emission tests are conducted using hot starts
(1) NRHC/HC indicates the ratio of NRHC to HC emission rates
(2) SO2
-------
            The SC>2 continuous values ranged from 0.36 to 0.41 g/km.  The
SC>2 continuous emission rates as a function of mileage accumulation is
shown in Figure 6.  The SO^= emission rates increased from 0. 2 mg/km at
the initial and 1000-mile emissions inspection to 0.4 mg/km at the final
inspection.   Particulate emission rates at the three  emissions inspections
are presented in Figure 8.

            The fraction of NRHC/HC ranged from 0. 18-0. 19 at all three
mileage intervals. The ratio of SC^ (b) / SO2 (c) was observed to be 0. 80
at the  1000-mile emissions inspection compared to about 0. 6 at the initial
and final tests.  The fraction of sulfate in the total particulate ranged from
0. 03 at the 1000-mile test to 0. 08 at the final inspection.

            Individual non-reactive and several reactive hydrocarbon con-
centrations  are presented in Table B-4 of Appendix B to supplement char-
acterization  data.  Individual sulfur and nitrogen concentrations are
presented in Table C-4 of Appendix C.  The first and third bag concentra-
tions ranged from 0. 23 to 0.40 ppm CH,NO_ for all tests with the second
bag CH^NOo  values ranging between 0. 11 and 6.  16 ppm. No other sulfur
or nitrogen compounds were detected using EM-231-F.

           The  sulfur distribution for  all runs at the three emissions
inspections are presented in Table D-4 of Appendix D.  This was first fuel/
additive package where the  sulfur recoveries were less than 85 percent using
SC>2 bag values.   When using SO? continuous concentrations,  the sulfur
recoveries were higher than the  three previous test fuels.  Sulfur recoveries
at the three  inspections ranged from 133  to 142 percent. As with  the three
previous tests, the fuel sulfur appearing  as SO^~ was less  than 0. 1 percent
on this non-catalyst equipped 1972 Chevrolet 350 engine.

B.      1975 350 CID Chevrolet Engine

       The second test stand was a 1975  350 CID Chevrolet engine, equipped
with EGR, air pump and GM (AC) pelleted type oxidation catalyst.  As with
the 1972 engine discussed earlier, emission inspection tests were conducted
at 0, 1000, and 2000 miles.  The first  three fuel/additive packages were
identical to those tested on the 1972 version of the 350 CID Chevrolet engine.
The final fuel was a high aromatic fuel at the same 0. 1  percent sulfur level
with Lubrizol 8101. Documentation photos  of piston  crown and cylinder head
deposits were obtained for all fuel/additive combinations.  Due to the simi-
larity in appearance of engine deposits, only the 1972 engine deposits are
presented.

        1.  EM-214-F Base Fuel with 0.  1 Percent Sulfur

            The initial test on the 1975 engine was with the base fuel,  EM-
214-F.  The hot start 1975 LD FTP emission rates  for each test  at the
                                   37

-------
three mileage emissions inspection is presented in Table 11 and summarized
in Table 12.  The HC emission rate increased from about 0. 10 g/km at the
initial test to 0. 26 g/km at the final 2000-mile emissions inspection.  The
effect of mileage accumulation on the HC emission rates is presented in
Figure 9.  The CO emission rates increased from 1.75 to 3. 12 g/km, as
shown in Figure  10.  The NOX emission rates remained relatively constant  
over the three emission test intervals, as  illustrated in Figure 11.

            The SO^  continuous emission rates increased from an  initial
value of 0. 19 to about 0. 25 g/km at the 1000- and 2000-mile tests.  The
effect of mileage accumulation of the  SOo continuous emission rates of the
1975 engine operating on EM-214-F is presented in Figure 12.. The sulfate
emission rates are plotted  as a function of mileage test interval and are
presented in Figure  13.  The sulfate  emission rates ranged from 6-14 mg/km
over the three inspections.  Particulate emission rates at the three mileage
accumulation test intervals are shown in Figure  14.  The particulate emission
rate almost doubled between the 1000- and 2000-mile tests.

            The substantial increase in HC emission rates at the 2000-mile
test was also apparent in the NRHC/HC ratio.  The initial and 1000-mile
emission tests had NRHC/HC ratios in excess of 0.7,  whereas at 2000 miles
this dropped to 0.4,  which  was more  consistent with data obtained later in
the program. The SC>2 (bag) emission rates were about 70 percent of the
SC2 emission rates obtained using continuous measurement.  Typical sul-
fur recoveries from  the fuel sulfur (based on continuous SO? and SO4=)
ranged from 78 to 96 percent.   It is expected that the lower sulfur  recov-
eries on the  catalyst engine were due  to sulfate and SOo storage in the cata-
lyst.  The fraction of SC4=  in the total particulate varied from about 0. 3 to
0.4.

           In addition to the regulated emissions of HC,  CO, and NO ,  and
the species of specific interest,  i.e.,  SO2 SO^,  and particulate,  character-
ization of exhaust samples was also obtained for  a number of nitrogen and
sulfur compounds.  Of these compounds, only CH3NO2 was found to be
present on a consistent basis.   Concentrations in the first and third bags
ranged from 0. 05 to  0. 14 ppm while the second bag values ranged from  unde-
tected to 0. 04.  Individual run results for sulfur  and nitrogen compounds are
presented in Table C-5 of Appendix C.

           No ammonia, dimethylnttrosamine,  carbonyl sulfide,  hydrogen
sulfide, or mercaptans were detected in any of the  samples.  During the
measurement of NRHC, a number  of individual non-reactive and reactive
hydrocarbons "were obtained and the results for these runs are presented
as additional characterization  information as Table B-5 of Appendix B.

           It became apparent that sulfate storage would be an important
factor in establishing sulfur balances  using a catalyst equipped engine.
                                   38

-------
                              TABLE 11.  SUMMARY OF EXHAUST EMISSIONS OF 1975 CHEVROLET 350 CID ENGINE
                                                         EM-214-F (BASE FUEL at 0.1% S)
sO
Mileage
Interval
0 miles


1000 miles


2000 miles


Run
Date No.
12/17/74 1
2
Avg.
12/20/74 1
2
Avg.
12/30/74 1
2
Avg.
1975 LD FTP
HC
0. 10
0.09
0. 10
0.09
0.07
0.08
0.26
0.27
0.26
NRHC
0.08
0.06
0.07
0.06
0.08
0.07
0.11
0.10
0.11
CO
1.67
1.82
1.75
2.03
2.26
2.15
3.11
3.12
3.12
NOX
1.08
1.25
1.17
1.37
1.30
1.34
1.33
1.22
1.28
Emission
S02(b)*
0. 14
0.14
0.14
0. 15
0. 19
0.17
0.15
0.17
0.16
Rate, g/krn*** NRHC*1' SO>(br ' SO4 =
-------
                  TABLE 12. SUMMARY OF 1975 350 CID CHEVROLET ENGINE EMISSION RATES




                                              1975 LD FTP (Hot Start) Emission Rate, g/km
Exhaust
Species
HC
NRHC
NRHC/HC
CO
NOX
S02(b)
S02(c)
so2(b)/so2(c)
804=*
Part. *
804= /Part.
EM-E14-F
0
0.10
0.07
0.73
1.75
1.17
0.14
0.19
0.75
9.7
24.6
0.40
1000
0.08
0.07
0.91
2.15
1.34
0.17
0.25
0.70
6.4
22.6
0.29
2000
0.26
0.11
0.40
3.12
1.28
0.16
0.24
0.68
14.1
39.5
0.36
EM-215-F
0
0.12
0.05
0.46
1.97
0.97
0.26
0.31
0.84
9.7
29.7
0.32
1000
0.10
0.06
0.43
1.68
1.18
0.19
0.29
0.67
14.1
41.3
0.34
2000
0.09
0.05
0.49
1.34
1.31
0.23
0.30
0.77
21.8
35.2
0.38
EM-216-F
0
0.17
0.05
0.31
4.64
1.03
0.20
0.32
0.61
2.8
17.2
0.18
1000
0.18
0.06
0.31
2.41
1.35
0.23
0.30
0.76
8.0
25.7
0.30
2000
0.15
0.05
0.34
2.39
1.62
0.18
0.26
0.68
10.1
21.4
0.45
EM-218-F
0
0.11
0.05
0.44
1.46
0.87
0.21
0.25
0.85
22.0
57.8
0.38
1000
0.09
0.05
0.48
1.41
1.16
0.22
0.24
0.91
22.3
58.7
0.38
2000
0.11
0.04
0.37
1.01
1.26
0.17
0.20
0.88
30.0
76.7
0.39
* mg/km

-------
   0.28 -Hh
   0.24^
   0.20
GO
CO
8
CD
CO
w
u
ffi
0.16
0.12
                                1000
                     LA- 4 Mileage Accumulation
                                                              2000
         FIGURE 9 .  HC EMISSION RATES OF 1975 350 CID
      CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS
                   WITH THE FOUR TEST FUELS
                                41

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00
G
O
H
(0
la
w
o
u
                                                                 JlOl)
   0.8
                                                              2000
                        LA-4 Mileage Accumulation
       FIGURE 10.  CO EMISSION RATES OF 1975 350 CID
    CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS
                 WITH THE FOUR TEST FUELS
                               42

-------
a
4S

too


Q)  1 :

%

rt

a

.2
co
CO
i-t

a  o,
H


o*
2
                                                                  rizol 8101)
   0.4^rES
      0-
                                  100

                       LA-4 Mileage  Accumulation
        FIGURE 11. NOX EMISSION RATES OF 1975 350 CID

    CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS

                  WITH THE FOUR TEST FUELS
                                43

-------
   0.36
   0.32
   0.28
I
"So
 fl
 o
H
 CD
 1C
w
 oj
O
   0.24
    0.20
    0.16
    0.12
       0 
                                                                   101)
                          LA-
       1000

4 Mileage Accumulation
         FIGURE 12. SO2 EMISSION RATES OF 1975 350 CID

      CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS

                    WITH THE FOUR TEST FUELS
                                 44

-------
    30. 0
CO
 i
 o
 .I

 X


 6
 x

 00


 
-------
    70
    60
CO
 i
 o
50
 00
 flfc
 O
 r+-
 (0
 09
 W

 0)
 n)
 0,
    40  :r
    30
    20
    10
      0
                                   1000

                          LA-4 Mileage Accumulation
                                                           2000
  FIGURE  14.  PARTICULATE EMISSION RATES OF 1975 350 CID

    CHEVROLET ENGINE AT SEVERAL MILEAGE INTERVALS

                  WITH THE FOUR TEST FUELS
                               46

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Sulfur recoveries based on SO? continuous readings ranged from 78 to 96
percent.  The percent of fuel sulfur appearing as sulfate was 2-4 percent.
Individual run results  are presented in Table D-5 of Appendix D.

       2.  EM-215-F Base  Fuel,  0. 1 Percent S, 0. 378 g/gal Lubrizol 8 10 1

           Another fuel/additive package used in the  characterization of
emissions of the  1975  350 CID Chevrolet engine was Lubrizol 8101.  The
base fuel at a 0. 1 percent sulfur level had Lubrizol 8101 added at 0. 378
g/gal.   The results of each individual run at all three of the emissions
inspections is presented in Table 13 and  summarized  in Table 12.

           The HC emission rates decreased from 0. 12 g/km at the initial
test to 0.09 g/km at the 2000-mile emissions inspection.  The CO emission
rates decreased with increasing mileage accumulation as illustrated in
Figure  10.  An increase in the NO   emission rate was observed, from 0.97
g/km at the 0-mile test to 1.31 g/km at the  final 2000 mileage inspection.
The effect of mileage accumulation on the NOV emission rates of the 1975
                    _                        Jt
engine operating on FM-215-F is shown in Figure 11.

            The SO2 (continuous) emission rates remained essentially con-
stant at about 0. 30 g/km over the three test inspections.  The sulfate emis-
sion rates as  a function of mileage accumulation are shown in Figure 13.
As observed, there was a gradual  increase  in the SO^~ emission rates
over the mileage accumulation schedule.  The particulate emission rates
ranged from 30 to 41 mg/km, and  the emission rates as a function of mile-
age accumulation are  illustrated in Figure  14. The SO2 (bag) emission
rates were  67 to 84 percent of the  continuous  SO2 emission rates.   The
NRHC/HC ratio  remained relatively constant ranging between 0.43  and
0.49.   The  ratio of sulfate fraction in the total particulate mass also
remained stable ranging only from 0.32 to 0.38,  slightly increasing with
mileage.

            The  individual results  of sulfur  and nitrogen compound are
presented in Table D-6 of Appendix D.  As with the previous tests on the
 1975 engine,  the only species present during the emission testing was the
nitromethane.  The first and third bag concentration  ranged from 0.09
to 0. 32 ppm,  with no apparent trend as a function of mileage accumulation.
Individual non-reactive and  several reactive hydrocarbon concentration  are
presented in Table B-6 of Appendix B for characterization data for  the three
bags at the  three emission inspection intervals.  Sulfur distribution in the
exhaust for all runs using EM-215-F in the  1975 engine is presented in  Table
D-6 of Appendix D. Sulfur recoveries based on continuous SO2 concentra-
tions averaged 109 percent for the three emissions inspections.
                                   47

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                            TABLE 13.  SUMMARY OF EXHAUST EMISSIONS OF 1975 CHEVROLET 350 CID ENGINE
                                        EM-215-F (BASE FUEL at 0.1% S + 0.378 g/gal LUBRIZOL 8101)
00
Mileage
Interval Date
0 miles 2/7/75



1000 miles 2/14/75



2000 miles 2/17/75




Run
No.
1
2
3
Avg.
1
2
3
Avg.
1
2
3
4
Avg.
1975 LD FTP
HC
0.12
0.10
0.14
0.12
0.14
0.12
0.14
0.10
0.09
0.12
0.10
0.06
0.09
NRHC
0.05
0.05
-___
0.05
0.06
0.05
	
0.06
0.05
0.05
-__ _

0.05
CO
1.70
1.96
2.26
1.97
1.43
1.61
2.00
1'.68
1.45
1.41
0.96
1.52
1.34
NO
0.99
0.98
0.^4
0.97
1.30
1.07
1.18
1.18
1.51
1.26
1.26
1.21
1.31
Emission Rate, g/k.m*** NRHC1 ' SO,(b)1 '
SO?(b)*
0.28
0.23
0.28
0.26'
0.18
0.19
0.21
0.19
0.20
0.24
0.25
0.24
0.23
SOgic)**'
0.28
0.31
0,35
0.31
0.28
0.28
0.30
0.29
0.29
0.30
0.30
0.32
0.30
SO4 =
0.0125
0.0058
0.0107
0.009?
0.0155
0.0160
0.0108
0.0141
0.0210
0.0324
0.0220
0.0116
0.0218
Part.
0.0399
0.0196
0.0297
0.0297
0.0504
0.0424
0.0312
0.0413
0.0515
0.0807
0.0591
0.0352
0.0566
HC
0.42
0.50
----
0.46
0.43
0.42
	
0.43
0.56
0.42
	
	
0.49
S02(c)
1.00
0.74
0.80
0.84
0.64
0.68
0.70
0.67
0.69
0.80
0.83
0.75
0.77
S04 =^
Part.
0.31
0.29
0.36
0.32
0.31
0.38
0.35
0.34
0.41
0.40
0.37
0.33
0.38
         * SO^fb) indicates SO2 values obtained using' CVS bag samples
        ** SO^tc) indicates SO^ values obtained using continuous on-line sampling with TECO
       *** All 1975 LD FTP emission tests are conducted using hot starts
       (1) NRHC/HC indicates the ratio of NRHC to HC emission rates
       (2) SO2(b)/SO2(c) indicates the ratio of bag SO2 to  continuous SO2 values
       (3) SO4=/particulate indie at s the fraction of SO^- in the particulate

-------
       3.   EM-216-F,  0. 1 Percent Sulfur with 0.468 g/gal Paradyne 506

            Another fuel/additive package contained 0. 468 g/gal Paradyne
506 in the base fuel at a 0. 1 percent sulfur level.  The individual emission
rates for all runs at the three inspections are presented in Table 14 and
summarized in Table 12.  The HC emission rates changed only slightly
with increasing mileage, as  shown in  Figure 9.  The  CO emission  rate
at the initial inspection was 4. 64 g/km and decreased to 2. 4 g/km  at the
1000- and 2000-mile tests, as shown  in Figure 10. The NOX emission
rates increased from 1.03 g/km at the 0-mile inspection to 1. 62 g/km at
the final emission test.

            The SO_ (continuous) emission rates decreased from 0.32 g/km
to 0. 26 over the three test intervals.  The effect of mileage accumulation
on the SO (continuous) emission rates is shown in Figure 12.  The sulfate
emission rates increased from 2.8 to 10. 1 mg/km, as shown in Figure 13.
The particulate emission rates ranged from 17. 2 to 25. 7 g/km.

            The fraction of SO? (bag)  / SO? (continuous)  ranged from 0. 61
at the initial inspection to 0. 76 at the  1000-mile tests.  The NRHC/HC  ratio
varied only  slightly during the 2000 miles of operation, ranging between
0.31 and 0.34. The fraction of sulfate in the total particulate increased with
increasing mileage accumulation.  At the initial inspection, the fraction was
only 0. 18 and increased to 0.30 and 0.45 at the  1000- and 2000-mile  inspec-
tions,  respectively.

            The measurement of individual nitrogen and sulfur compounds
was conducted on all three bags at the three emissions inspection intervals.
The results of these tests are presented in Table  C-7 of Appendix  C  to
assist in the characterization of the exhaust.  In addition, individual non-
reactive and several reactive hydrocarbons measured during these same
tests are presented in Table  B-7 of Appendix B.

            The sulfur  distribution for the 1975 engine operating on EM-
216-F is presented in Table D-7 of Appendix D for all tests.  The  percent
fuel sulfur appearing as SO2  (continuous) varied from 90-110 percent.  The
percent  fuel sulfur appearing as sulfate increased from  1. 1 to 2. 5  with
increasing mileage accumulation.

       4.   EM-218-F  High Aromatic, 0. 1 Percent Sulfur, 0.378 g/gal
            Lubrizol 8101

            The final fuel/additive package contained 0.378 g/gal Lubrizol
8101  in a high aromatic fuel doped with thiophene  to a 0. 1 percent  sulfur
level. The emission rates for each run  at the three inspections is found
in Table 15  and summarized  in Table 12.  The HC emission rates  remained
essentially  constant at 0. 1 g/km at the three test intervals, as  shown in
Figure 9.

                                   49

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                      TABLE 14.  SUMMARY OF EXHAUST EMISSIONS OF 1975 CHEVROLET 350 CID ENGINE
                                   EM-Z16-F (BASE FUEL at 0.1% S + 0.486 g/gal PARADYNE 506)
Mileage
Interval Date
0 miles 1/9/75



1000 miles 1/14/75


2000 miles 1/17/75


Run
No.
1
2
3
Avg.
1
2
Avg.
1
2
Avg.
1975 LD FTP
HC
0.14
0.17
0.19
0.17
0.18
0.17
0.18
0.16
0.14
0.15
NRHC
0.05
0.05
	
0.. 05
0.06
0.05
0.06
0.05
0.05
0.05
CO
6.23
3.53
4.15
4.64
2.70
2.13
2.41
2.57
2.20
2.39
NO,
1.17
0.88
1.05
1.03
1.29
1.41
1.35
1.63
1.61
1.62
Emission
SO7(b)*
0.22
0.18
0.19
0.20
0.21
0.24
0.23
0.18
0.17
0.18
Rate, g/km***
SO?(c)**
0.33
0.31
0.32
0.32
0.29
0.30
0.30
0.25
0.27
0.26
so4-
0.0013
0.0015
0.0055
0.0028
0.0051
0.0109
0.0080
0.0087
0.0115
0.0101
Part.
0.0146
0.0129
0.0242
0.0172
0.0181
0.0333
0.0257
0.0187
0.0240
0.0214
NRHC(1)
HC
0.36
0.26 
	 _
0.31
0.33
0.29
0.31
0.31
0.36
0.34
S02(b)(2)
S07(c)
0.67
0.58
0.59
0.61
0.72
0.80
0.76
0.72
0.63
0.68
SO/ <3
Part.
0,09
0.12
0.33
0.18
0.27
0.33
0.30
0.41
0.48
0.45
  * SO2(b) indicates SO2 values obtained using CVS bag samples
 ** SO2(c) indicates SO2 values obtained using continuous on-line sampling with TECO
*** All 1975 LD FTP emission tests are conducted using hot starts
(1) NRHC/HC indicates the ratio of NRHC to HC emission rates
(2) SO2(b)/SO2(c) indicates the ratio of bag SO2 to continuous SO2 values
(3) SO^=/particulate indicates the weight fraction of SO4= in the particulate

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                      TABLE 15.  SUMMARY OF EXHAUST EMISSIONS OF 1975 CHEVROLET 350 CID ENGINE
                             EM-218-F (HIGH AROMATIC FUEL at 0.1% S + 0.378 g/gal LUBRIZOL 8101)
Mileage
Interval Date
0 miles 3/10/75



1000 miles 3/17/75



2000 miles 3/20/75



Run
No.
1
2
3
Avg.
1
2
3
Avg.
1
2
3
Avg.
1975 LD FTP
HC
0.12
0.11
0.10
0.11
0.10
0.09
0.09
0.09
0.12
0.10
0.11
0.11
NRHC
0.05
0.05
	
0.05
0.04
0.05
	
0.05
0.04
0.04
	
0.04
CO
1.47
1.57
1.35
1.46
1.52
1.30
1.41
1.41
1.04
1.02
0.98
1.01
NOV
0.82
0.85
0.94
0.87
1.16
1.15
1.16
1.16
1.29
1.26
1.24
1.26
Emission
SO2(b)*
0.23
0.23
0.17
0.21
0.22
0.21
0.22
0.22
0.18
0.16
0.18
0.17
Rate, g/km*** NRHC11' SO?(b)<2' SO4= (3)
SO?(c)**
0.25
0.27
0.22
0.25
0.23
0.25
0.24
0.24
0.20
0. 18
0.21
0.20
SO4=
0.0187
0.0261
0.0213
0.0220
0.0178
0.0274
0.0216
0.0223
0.0258
0.0316
0.0327
0. 0300
Part.
0.0512
0.0666
0.0558
0.0578
0.0476
0.0730
0.0556
0.0587
0.0670
0.0800
0.0831
0.0767
HC
0.42
0.45
	
0.44
0.40
0.55
	
0.48
0.33
0.40
	
0.37
S02(c)
0.92
0.85
0. 77
0.85
0.96
0.84
0.92
0.91
0.90
0.89
0.86
0.88
Part.
0.37
0.39
0.38
0.38
0.37
0.38
0.39
0.38
0.39
0.40
0.39
0.39
  * SO2(b) indicates SO2 values obtained using CVS bag samples
 ** SO(c) indicates SO2 values obtained using continuous on-line sampling with TECO
*#* All 1975 LD FTP emissions tests are  conducted using hot starts
(1) NRHC/HC indicates the ratio of NRHC  to HC emission rates
(2) SO2(b)/SO2(c) indicates the ratio of bag SO2 to continuous SO2 values
(3) SO4=/particulate indicates the  fraction' of SO^= in the particulate

-------
            The CO emission rates were about 1.4 g/km for the first two
inspections and decreased to 1. 0 g/km at the final test interval.  The
effect of mileage accumulation on the NOV emission rates of the 1^75
                                        X
engine operating on EM-218-F is presented in Figure 11.  As illustrated,
the NOX emission rates increased from 0. 87 g/km at the 0-mile test to
1. 26 g/km at the final 2000-mile test.

            The SO., continuous emission rates decreased from 0. 25 g/km
at the initial test to 0. 20 g/km at the 2000-mile emissions inspection.   The
effect of mileage accumulation on the SO^  continuous emission rates is illus-
trated in Figure  12.  Sulfate emission rates  remained at 22 mg/km for the
first two emissions inspection (0 and 1000 miles)  and increased to 30 mg/km
at 2000  miles, as shown in Figure 13.  Similar results were  observed for
particulate emission rates in that the first two emission  test  intervals pro-
duced about 58 mg/km while the final test  resulted in a particulate emission
rate of 77 mg/km.   Figure 14 illustrates the effect of mileage accumulation
on particulate emissions.

            The fraction of NRHC in the total hydrocarbons varied between
0.37 and 0.48 for the three  emission inspections. The  ratio of SC>2 (bag)/
SC>2 (continuous) at a nominal 0. 88 for the same tests.  The sulfate  fraction
of the total particulate remained essentially constant at 0. 38.  The sulfur
distribution  for each run is  presented in Table D-8 of Appendix D.   Sulfur
recoveries from this high aromatic fuel were the best of all fuel/additive
 combinations.  This was the only test fuel where the SO^ continuous
 recoveries were less than 100 percent.

 C.     Documentation  of Engine Deposits

        During the initial phase of the program,  it was decided to obtain
 documentation photos of the piston head, cylinder head,  and  valve deposits
 of both engines.  These documentation photos were obtained  prior to engine
 cleanup and the deposits represent  approximately 2000  miles of repetitive
 LA-4 cycles.  Photos of typically cleaned piston heads  and cylinder heads
 are illustrated in Figure 15.  The piston deposits for all four test fuels
 are shown in Figure 16 for  the 1972 350 CID Chevrolet engine.  The major
 difference in the appearance of the  piston deposits of the four test fuels
 was the white deposits  observed with EM-231-F.  This was the only fuel/
 additive package which contained lead.  The remainder of the piston deposits
 were black in color and were generally of a crisp, flaky nature.

        Cylinder head deposits for the four fuel/additive packages for  the
 1972 350 CID Chevrolet engine are  presented in Figure  17.  The base fuel
 EM-214-F cylinder head deposits are slightly lighter in color than either
 of the two fuel/additive packages (EM-215-F and EM-216-F).  The  final
 fuel/additive package containing lead had  a substantial increase in the
 quantity of white deposits on the cylinder  head.   It is assumed that these
                                    52

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                 Cleaned  Piston Heads
                  Cleaned Cylinder Heads
FIGURE 15.  TYPICALLY  CLEANED PISTON HEADS AND
   CYLINDER HEADS, 1972 CHEVROLET 350 ENGINE

-------
it*
                                EM-214-F, Baa,- Fui-1 al 0.1 Percent Sulfur

                     tM-<;i(j-K,  Basi fuel al 0.1 Percent Sulfur with 0.48b g/gil Paradyne 506
                                                                                                      Base Fuel a.t 0.1 Percent Suliur with 0.378 g/gal Lubrizol 8101
                                                                                                          EM-
-------
                                          EM-Z14-F, Base Fuel at 0.1 Percent Sulfur
                                EM-Z15-F, Base Fuel at 0.1 Percent Sulfur with 0.378 g/gal Lubrizcl
                              EM-216-F, Base Fuel at 0.1 Percent Sulfur with 0.486 g/gal Paradyne 506
                                         EM-213-F, Base Fuel at 0.1 Percent Sulfur
                                        ith 0.378 g/gal Lubrizol 8101 and 0.05 g/gal TL
FIGURE  17.   CYLINDER HEAD  DEPOSITS OF  1972 350  CID CHEVROLET  ENGINE
      OPERATING THE FOUR  TEST  FUELS  AT  2000  MILES OF LA-4  CYCLES
                                                        55

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are lead salt deposits, since no further work regarding their composition
was performed.

        Valve deposit documentation was obtained for the three  final fuel/
additive packages.  Figure 18 represents typically cleaned valves and the
valve deposits that were  observed after ZOOO miles of repetitive LA-4
cycles.  As  observed,  a  significant amount of intake valve deposits were
found with all three fuel/additive packages.  However, it should be pointed
out that although documentation photos were not obtained using  the base
fuel,  visual  inspection of the valves indicated little difference between
base fuel and the fuel/additive packages.

        The base fuel was supplied without any additives , and between the
initial analysis by the supplier and completion of the final test fuel,  the
ASTM D-381 existent gum values had doubled. Documentation photos
of the  1975 350 CID Chevrolet engine piston and cylinder head were ob-
tained, but the similarity of deposit characteristics for the four fuels did
not warrant  inclusion in this  report.

        Although the scope of work for this program did not include deposit
 documentation, it was felt that this could be considered an important factor
 in the characterization as a  function of fuel and  additive composition.   Future
 work  may want to consider looking  for differences in engine deposits as a
 function of fuel/additive packages.

D.      Statistical Analysis

        The amount  of emissions  rate data generated during the course of
of the  program provided  a basis for statistical analysis.  This  data was
obtained during the  program and  examination of this  data from  a  statistical
standpoint is "after-the-fact".  The design of the experiment was not such
that statistical analysis of the data was of primary concern.  It is,  how-
ever,  an important  aspect that should not be overlooked.

        The use of the two engine configurations provided an opportunity
to make comparisons of emission testing standard deviation (S^  and stand-
ard deviation in percent of mean  value (% Sx).  Preliminary experiments
were  conducted during the emission qualification testing phase  using hot
starts and during the full scale emission testing.  Generally, two four-
emission tests were conducted during the full scale testing; and consequently,
the data presented must be viewed accordingly.  Table 16 illustrates the  Sx
and %  Sx values determined on the 1972 350 CID  Chevrolet engine for all
four fuels.   The Sx  and % Sx  values  found for  the 1975 engine are presented
in Table 17.

        A summary  of the Sx  and  % Sx values from the full-scale  testing,
initial "hot start" qualification testing,  and standard certification values
                                    56

-------
             Typically Cleaned Valves
EM-216-F,  Base Fuel at 0. 1 Percent Sulfur
      with 0.486 g/gal Paradyne 506
         EM-215-F, Base Fuel at 0. 1 Percent
         Sulfur with 0.378 g/gal Lubrizol 8101
  EM-231-F,  Base Fuel at 0.1  Percent
  Sulfur with 0.378 g/gal Lubrizol 8101
          and 0.05 g/gal TEL
FIGURE 18.   TYPICALLY CLEANED VALVES AND VALVE DEPOSITS FROM
  1972  350  CID CHEVROLET ENGINE OPERATING ON THREE  TEST  FUELS
                         WITH 2000 MILES  OF LA-4 CYCLES
                                              57

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00
                     TABLE 16.
STANDARD DEVIATION (Sx) AND STANDARD DEVIATION
IN PERCENT OF MEAN VALUE (% Sx) FOR
    1972 350 CID CHEVROLET ENGINE
       WITH ALL FOUR TEST FUELS
                                   EM-214-F
                     EM-215-F
EM-216-F
EM-231-F
Emission
HC
HC
HC
CO
CO
CO
NOX
NOX
NOV
Miles
0
1000
2000
0
1000
2000
0
1000
2000
Sx
0.21
0.09
0.03
1.00
1.27
0.21
0;03
0.02
0.04
%SX
13.2
6.0
2. 1
5.5
6.6
1.0
1.5
1.2
2.5
Sx
0. 11
0.03
0.02
1.79
0.43
1.38
0. 11
0. 16
0.02
% Sx
11. 1
4.0
2.6
13.8
3.7
10.5
7.9
10.2
1.3
sx
0.03
0.01
0.02
1.00
1.35
0.61
0.25
0.04
" 0.08
%sx
2.2
1.0
2.4
4.2
11.4
4.6
13.8
2.7
5.0
Sx
0.01
0.02
0.06
0.69
0.66
0.47
0.04
0. 15
0.08
%SX
1.0
2.2
6.8
2.8
4.0
2.9
3.0
9.7
5.8
                                           1972 350 CID Chevrolet
                                         Average % Sxfor HC = 4. 6
                                         Average %Sxfor CO = 6.0
                                         Average % Sxfor NOX =5.4

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UI
                   TABLE 17.  STANDARD DEVIATION (Sx) AND STANDARD DEVIATION
                              IN PERCENT OF MEAN VALUE (% Sx) FOR
                                  1975 350 CID CHEVROLET ENGINE
                                     WITH ALL FOUR TEST FUELS
                                 EM-214-F
EM-215-F
EM-216-F
EM-218-F
Emission
HC
HC
HC
CO
CO
CO
NOX
NOX
NO,,
Miles
0
1000
2000
0
1000
2000
0
1000
2000
Sx
0.01
0.01
0.01
0. 11
0.16
0.01
0. 12
0.05
0.08
% Sx
10.0
12.5
3.8
6.3
7.4
0.3
10.3
3.7
6.3
Sx
0.02
0.01
0.02
0.28
0.29
0.25
0.03
0. 12
0. 15
%Sx
16.7
7.7
22.2
14.2
17.3
18.7
3. 1
10.2
10.7
Sx
0.03
0.01
0.01
1.41
0.40
0.26
0. 15
0.08
0.01
% Sx
17.6
5.6
6.7
30.4
16.6
10.9
14.6
5.9
0.6
Sx
0.01
0.01
0.01
0. 11
0. 11
0. 03
0.06
0. 01
0.03
%SX
9. 1
11. 1
9. 1
7.5
7.8
3.0
6.9
0. 9
2.4
                                        1975 350 CID Chevrolet
                                      Average % Sx for HC  = 11.0
                                      Average % Sx for CO  = 11. 7
                                      Average % Sx for NOX = 6. 3

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supplied by the Project Officer are presented in Table 18.  The % Sx
observed from the emission tests conducted during the program indi-
cated a noticeable improvement in the % Sx.  The 1972 engine hot start
dynamometer test was a much more statistically reliable test procedure
based on the standard cold start % Sx.  These values were  1/2 to 1/3 of
the standard cold start certification tests.  The % Sx for the 1975 was
slightly  better than the standard cold start certification tests.  When
determining the effects due to the fuel additive on regulated emissions,
a number of factors should be considered.  The first is the variability
of the emissions test itself, and a second consideration should be the
deterioration of emissions due to a number of factors.  Calculated de-
terioration factors based on the base fuel run indicate that  there  were
no significant increase in regulated or- non-regulated emission rates
that could be solely attributed to the fuel additive package.

       Using the  same rationale employed in the Federal Register,  de-
termination of deterioration factors  was attempted.  It became apparent
that there was no deterioration for HC or NO,, and the increase in CO
                                            J*V.
emission rates for the 1972 engine.  A similar comparison was made
with the  1975 engine but decreases in  CO and HC indicate no deterioration
during the short mileage accumulation used in this program.   After  at-
tempting to determine  deterioration factors for both engines operating
on the base fuel,  it became apparent that no deterioration could be ob-
served that could not be explained by the inherent variability  of the emis-
sions test procedure.

       Hydrocarbon was *he only emission which was found to be affected
by the fuel additive packp.ge.   Lower HC emissions were observed with
the three fuel additive packages on the 1972 engine than with the base
fuel.  Other changes in the regulated emission rates  can be explained
by the emission test variability and variable engine emission deterio-
ration.   Statistical analysis of the limited data available on the "worst
case" 1975 engine was  applied to determine the number of tests required
to detect a deterioration of 10 or 25  percent change in emissions  due to
a fuel additive package, if  such an effect were present.  The t-test is
generally used for testing the  difference of two population means  when the
number of samples are small.  This test assumes that the variances (rf)
of the two populations  are equal.  In order to determine the number of
tests required,  an estimate ofju,  - J*2 *s nee^ed (wherejuj andju are
the population means).  For the emissions data on the 1975 350 CID
Chevrolet engine, the  largest  average % Sx was 11.7 for CO for all tests.
Using this for estimation purposes yields
        A- ~  9               n,  = 9c/
       o'  ~                ^
                                 60

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        TABLE 18.  COMPARISON OF STANDARD DEVIATION
               IN PERCENT OF MEAN VALUE (% Sx) OF
   STANDARD COLD START FTP, HOT START QUALIFICATION
    TESTING AND FUEL SCALE HOT START EMISSION TESTING

                  Standard Deviation in Percent of Mean Value
Standard Qualification Tests *
Emission FTP 1972 1975
HC 13.0 4.7 3.6
CO 18.2 6.8 25.0
NOX 9.1 3.7 2.9
Avg. Emission Tests**
1972 1975
4.6 11.0
6.0 11.7
5.4 , 6.3
Busing "hot start" 1975 FTP testing
##Average of emission inspection test for all  four fuels
                               61

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Assume that U2 differs from u^ by 10 percent or more;  i.e.,

       * -ul ~ ,W2 !   -  - i ul  = 0.9 cf

Assume that the probability of rejecting the hypothesis of no difference
when the hypothesis is true is 0.05,  commonly referred to as a( .  Fur-
ther assume that the probability of accepting the hypothesis of no differ-
ence is 0. 1, commonly referred to as ft .  A  final assumption is that
the baseline (i.e. , the emissions from the fuel with no additive) does not
change.

       In summary,
                        A =
                        c* =  0.05
                        (3 =  o.i

Based on this information and published literature*   ', it can be deter-
mined that the sample size is 27.  This means that 27 tests would be
required from both the baseline and fuel additive package.

       Using the same reasoning for a deterioration of 25 percent in
emissions and assume
then    A = 2. 25   and results in a corresponding sample size of 6.
This indicates that six tests would be necessary from both the baseline
and the fuel additive package.
                                 62

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                    IV.   SUMMARY AND CONCLUSIONS

       The objectives of this project, which were to characterize gaseous
emissions  as a function  of fuel/additive composition and evaluate tho useful-
ness of the 1975 LD FTP as a satisfactory screening procedure, were
achieved.  Sufficient data has been presented to satisfactorily characterize
the two 350 CID Chevrolet engines on  four test fuels.  Chemical analytical
procedures were obtained from EPA-RTP while others were  developed by
SwRI during the procedural development phase of the research effort.
These  procedures are described in sufficient detail to allow others to imple-
ment them.  The two special engine dynamometer tests facilities were
designed to simulate vehicle operation  and  to allow mileage accumulation
using an  automatic tape  controlled servo-driver.  These test facilities were
successfully employed and proved reliable and durable.

       Although a substantial amount  of baseline characterization data has
been generated with the  two  engines operating on both fuels, a number of
findings  seem apparent as a result of  this research project, and the most
important  ones are described as follows:

       1.   Of the various sulfur  compounds evaluated, the only ones  present
in the exhaust of both engines were SO2 and SO^-.  Hydrofi^T fm1ifHi*T  cap-.
      sulfide. methyl yrf "*= pta^. a^d ethvl  mercapf^r
of dete^frahjlity. {<>* ^he method of analysis employed in this pro_g?^tP-  The
SO2 emission rates for the 1972 engine were greater;  since the oxidation
catalyst on the 1975 engine converted SO2 to SO." and also stored some
S-iilfate  levelsjpf the 1975 engine were 20 to  100 times those of thf> nnnj-ajta-
                   engine.  JJulfalu bluraUB aTid the relatively light driving
cycle of the l^rli LD' I1' I1? indicate that this  is not a satisfactory test procedure
for measuring sulfate.  Sulfate accounted for 30-45 percent of the total partic-
ulate weight in the 1975 engine as compared to 1-11 percent for the 1972
engine.   Of the fuel sulfur, less than 0. 1 percent appeared as SO^" in the ex-
haust of the 1972 engine;  whereas, 18-45 percent was observed as SO^" in the
1975 engine.   Additional work is warranted  for the measurement  of SO?, SO4=,
and particulate using a more appropriate test cycle.  More work  for the  analy-
sis of other sulfur compounds should also be conducted if another test cycle
is employed and other catalysts and  fuel/additive combinations are included.

        2.  Of the nitrogen compounds evaluated, nitromethane was the only
nitrogen compound detected in the  exhaust of both engines  with all four fuel/
additive combinations.  No ammonia or dimethylnitrosamine was  detected
throughout the testing on  either engine on any of the four test fuels.  There
was no  significant differences in the concentrations of nitromethane due to
the engine configuration or test fuel  using the 1975 LD FTP.  Additional work
may be  warranted if an alternative test procedure is proposed or  if other
fuel/additives, catalysts, or engines are employed.
                                   63

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       3.   The ability of the IjJ1! LTl FTP to .deter mine the
additive  composition on regulated emissionraj__w^s_^aund_to bemarginal).
This is not surprising since no specific effort was made to make thol975
LD FTP discriminate between fuels and  fuel additives when it was developed.
A  substantial procedural development effort,  not within the  scope of this
project,  is needed to demonstrate a suitable, discriminatory fuel additive
test protocol.  The nature of the  program required minor engine overhaul
at the conclusion of each test fuel and the baseline emission rates were
slightly different after each rebuilding.  This was  particularly true for CO
and HC making it difficult to distinguish  between engine and fuel additive
effects on  emissions except on a  percent change basis.

            Non-reactive  hydrocarbons accounted for 15-20 percent of total
hydrocarbons in the 1972  engine with no  apparent trend  as a function of mile-
age accumulation.  Although the fraction of NRHC  in the total hydrocarbon
varied considerably at the 0- and 1000-mile  emission inspection, the results
of the 2000-mile inspection with the base fuel was within the range observed
with the  test fuels; namely,  30-50 percent.   No changes in the NRHC/HC
were noted for a given fuel/additive package that could be attributed strictly
to the test fuel on either engine.

       4.   Particulate  and  sulfate were non-regulated emissions where
changes  in emission rates could be attributed to the fuel/additive package.
The high aromatic fuel was  observed to produce nominally twice  the sulfate
and particulate emission rate as  the base fuel with the same fuel additive
in the 1975 engine.  Although EM-231-F was treated with TEL, motor mix,
the treatment level of 0. 05  */gal should  be considered only a trace level;
and, consequently, the paniculate emission rates from the 1972  engine
were not substantially higher than the unleaded fuel additive packages.
Since particulate and sulfate emissions appear  to be more sensitive to
fuel composition than to additive  formulation, additional work involging
fuel composition effects on  sulfate and particulate emissions may be warranted.

       5.   The engine dynamometer configuration designed to simulate
vehicle operation using  the  1975 LD FTP was successfully used with both
engines for all four test fuels.  The automatic driver arrangement was
found to  be an invaluable aid in the  simultaneous mileage accumulation on
the two engines.   The system was designed to allow substitution of other
driving cycles for mileage accumulation. Actual driving for record was
accomplished using a manual driver just as is normally done when testing
cars on the chassis dynamometer.

       6.   For the majority of chemical species  measured during this pro-
cram,  the  1975 LD FTP was insufficiently sensitive to detect effects  due to
rhe fuel additive treatments  evaluated.  The  1975  LD FTP is basically a light
driving schedule,  and the problem of sulfate storage could be eliminated by
using a more appropriate driving cycle.
                                   64

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       7.   The relative light driving cycle (1975 LD FTP) for mileage
accumulation made the engines prone to intake manifold and valve deposits.
These deposits were observed with both additive packages and to a lesser
extent with the base fuels.

       8.   The gaseous emissions variability was improved using the
hot start engine dynamometer.  Comparison of accepted standard devia-
tion in percent of mean values indicate an improvement in the reliability
of the gaseous emissions test procedure.

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                       LIST OF REFERENCES

 1.  "Regulation of Fuels, " Section 211, Clean Air Act Amendments of
     1970 (P. L. 91-604) to Clean Air Act of 1969 (P. L.  88-206).

 2.  Federal Register,  Vol.  37, No.  221, Part II, November 15,  1972.

 3.  "Effects of Fuel Additives on Particulate Emissions, " Dow Chem-
     ical Final Report to the Environmental Protection Agency under
     Contract No.  22-69-145, EPA Report No. APTD-0618, April 1972.

 4.  Beltzer, Morton,  "Particulate Emissions From Prototype Catalyst
     Cars. "  Exxon Research and Engineering Final Report to the Environ-
     mental Protection Agency under  Contract No. 68-02-1279, EPA Report
     No.  EPA-650/2-75-054, May 1975.

 5.  Hare, Charles T. , "Methodology for Determining Fuel Effects on
     Diesel Particulate  Emissions. "  Final Report to the Environmental
     Protection Agency  under Contract No. 68-02-1230,  EPA Report
     No.  EPA-650/2-75-056, March 1975.

 6.  Habibi, K., et al. ,  "Characterization and Control of Gaseous and
     Particulate Exhaust Emission From Vehicles. "  Paper presented
     at the SAE Air Pollution Control Association West Coast Section,
     Fifth Technical Meeting, October 1970.

 7.  Wagman, Jack, "Recent Developments  in Techniques  for Monitoring
     Airborne Particulate Emissions  From Sources. " AIChE Symposium
     Series, No. 137, Vol.  70, pp. 277-284.

 8.  Black,  F. M.,  High, L. E.,  and Sigsby, J. E.,  "Methodology for
     Assignment of a Hydrocarbon Photochemical Reactivity Index for
     Emissions from Mobile Sources. "   Final Report to  the Environ-
     mental Protection Agency, EPA  Report No. EPA-650/2-75-025,
     March 1975.

 9.  Tejada,  Silvestre,  "Determination of Soluble Sulfates. "  Unpublished
     Procedure developed by the Environmental Protection Agency, 1974.

10.  "CRC Handbook of Tables for Probability and Statistics. " Chemical
     Rubber Company Publishing Company,  W. H. Beyer (editor), 1966,
     p. 232.
                                 67

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           APPENDIX A

METHODS OF CHEMICAL ANALYSIS

1.  Non-Reactive Hydrocarbons (NRHC)
2.  Sulfur Dioxide (803)
3.  Sulfate (SO4=)
4.  Nitrogen Compounds
5.  Sulfur Compounds

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1.     Non-Reactive Hydrocarbons (NRHC)

       The measurement of NRHC was performed using a gas chroma-
tograph procedure developed by EPA (RTF)'   '.  This procedure uses a
single flame ionization detector with a multiple column arrangement and
dual gas sampling valves.   The timed sequence selection valves allow
for the baseline separation of air,  CH4,  C2H4, C>2^-2> C3H8>  CsHfc,  C6H6'
and CyHg.  Although only CH4,  C2H&,  CzH2  C3H8 and C6H6 are con~
sidered non-reactive, C2H4, 03^, and  C^Hg were determined during
the course of the analysis.   Only the non-reactive hydrocarbons are used
in the  calculation of NRHC  emission rates, but all individual hydrocarbon
data is useful in the characterization of emissions from the two Chevrolet
engines.

       Samples were obtained .directly from the bag samples  of 1975 LD
FTP and analyzed in the NRHC  system.  Individual NRHC values were
determined and a NRHC value for the bag was calculated.  This value was
then used to determine the  NRHC emission rates for these tests.  By
knowing the NRHC and HC emission rates, it  was possible to  determine
the fraction of NRHC in the total HC.  A detailed description of the indi-
vidual columns, temperatures,  flow rates, etc. may be found in Reference 8
Figure A-l illustrates the NRHC  analytical instrumentation that was used
for this analysis.
                                A-2

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FIGURE A-l.  NON-REACTIVE HYDROCARBON
 GAS CHROMATOGRAPH INSTRUMENTATION
   FIGURE A-2.  TECO MODEL 40 PULSED
       FLUORESCENT SO2 ANALYZER
                   A-3

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 2.      Sulfur Dioxide (SO2)

        A pulsed fluorescent analyzer was used for the measurement of
 sulfur dioxide.  This unit was manufactured by the Thermo Electron Corp-
 oration and is designated as their TECO Model 40 and is shown in Figure
 A- 2.  This instrument was used to monitor dilute exhaust both on a conti-
 nuous basis and from CVS bag samples.  The sampling interface used
 with the TECO Model 40 is presented in Figure A-3.  A supplementary
 pump was incorporated into the system to keep the response time less
 than three seconds.  All sample lines were Teflon, and the use of stain-
 less steel was minimized when possible.

        The use of the TECO Model 40 SO2 instrument required the ac-
 quisition of zero and span gases for daily calibration. Since the intended
 application for this instrument was dilute (air rich) exhaust, the use of
 air balance SO2 span gases and air zero was selected for calibration pur-
 poses.  Although the instrument was advertised not to have interferences,
 a series of experiments were conducted to verify this.  These experiments
 included various concentrations of CO, NOX, and HC in N2, as well as
 several individual hydrocarbons in N and  air. Based on the  results of
 these experiments,  it was apparent that a number of  potential problems
 could be avoided provided certain precautions were observed. Best re-
 sults from the TECO Model 40 were observed when sampling  from dilute
 auto exhaust (without an ice trap) using a fluoropore filter and to use air
 balance span gases and air zero gas.   Even using all of the precautions
 previously mentioned, the fuel sulfur recoveries  consistently exceeded
 100 percent throughout the program.

        Span gases were named using the procedure supplied by Matheson
 Gas  Products as the method they used to name the cylinders initially.
 Sulfur dioxide span gases are particularly  susceptible to absorption and
 initially it was difficult to obtain a span gas that would maintain the SO
 level that it had when received in the lab.  By the beginning of the mileage
 accumulation, SO span gases were in hand that had been sufficiently pre-
 conditioned to allow a stable 803 concentration.
       Although the SO instrument was not totally free of interferences,
it was felt that it was the most satisfactory instrument available at that
time.  During the course of the program,  it was found that the bag SO
values were consistently lower than the continuous  readings.  When cal-
culating sulfur balances,  the recoveries based on 803 continuous values
were generally high ranging from 110 to 125 percent in most cases.  Based
on the experience obtained during this program, it  is questionable that
this  instrument is satisfactory for measuring  SO2 in automotive exhaust.
                                A-4

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A-5

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3.     Sulfate (SO4 )

       The measurement of sulfate in dilute automobile exhaust was ac-
complished by obtaining an iso-kinetic  sample from a 10 foot length of
an 8 inch dilution tunnel.  These samples were obtained using a 3/8" iso-
kinetic probe at a flow rate of 0.45 CFM.  The sulfate was collected on
a 47mm  0. 5u fluoropore  filter.  Each filter was weighed before and after
the test to allow the determination of particulate data.  The extraction
and analysis was performed according  to the procedure developed by
(RTP) for the analysis of water soluble sulfates.  A copy of this analysis'
is included in this  section for reference.

       A flow schematic of the  sulfate  sampling system is illustrated in
Figure A-4 while the analytical instrumentation employed in the analysis
of SO^= is presented in Figure A-5.  The specific instrument utilized in
the measurement of SO^= was a Beckman Model 25 UV-VIS Recording
Spectrophotometer.  An  18jiil flow-through cell was incorporated into
the system, along with necessary columns and pumps as specified in the
analysis of soluble sulfates.  Figure A-6 illustrates the barium chloranilate
system used to measure  the sulfate emissions during this program.  Sul-
furic acid standards were prepared to  determine the sulfate concentrations
in the filter extracts.  Sulfate emission rates  were calculated based on a
single filter per test; and consequently, the sulfate and particulate emission
rates are not weighted.
                                 A-6

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8" tunnel
Flowmeter
1
uti
be
c 	
Drier lJ
i ^ S
m
7UJ
r
Fluor opore
filter

Pump



t
Dry gas
meter
         FIGURE A-4.  SULFATE SAMPLING SCHEMATIC
                                      '
 FIGURE A-5.  SULFATE
   SAMPLING SYSTEM
FIGURE A-6.  BCA SO^ SYSTEM
                              A-7

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                      FOP. DISCUSSION AND EEVIEV/ OIIiY
                             KOT FOR RELEASE

    Determination of Soluble Sulfates:  Automated Method

1.  Principle and Applicability
    1.1  This method is for the determination of water-
         soluble sulfates from diluted automobile exhausts
         collected on Fluoropore filters.   The method is
         quite general and may be  used for trace sulfate
        analysis of any sample from.which .sulfstes can be
         leached out with water or aqueous alcoholic solutions.
         There are interferences from  some anions and methods
         for minimizing or eliminating these are still being
                                                          
         worked out.  The method as written  is applicable to
         sulfate analysis of exhaust emissions from cars run on
         non-leaded gasoline.
    1.2  Auto exhaust is mixed with air  in a dilution tunnel and
         sampled through isokinetic probes.   SO, reacts with
         available moisture in the exhaust to form I^SO,  aerosols
         and is trapped  on Fluoropore*-filters with 0.45 n pore
         size.   The filter is  extracted with 60/40 isopropyl
        alcohol/water solution (i.e.  60 ml  isopropyl alcohol
         (IPA)  +40 ml water).   The extract  is fed by a high
        pressure liquid (chromatographic) pump through a
        column of cation exchange resin to  remove cationic
        interferences and then through a  column of solid
        barium chloranilate where BaSO, precipitates out.
        An  ecuivalent amount  of reddish colored acid chlor-
                                1  2
        anilate  ion is  released   and is measured colori-
                            3  4
        metrically  at 310 m|i  ' .  .To use  this method for
        aqueous  sulfate  solutions, four parts by volume  of
        the solution  are  mixed with six parts of  IPA  before
        feeding  through  the columns.  Manual  method  or  a
        dynamic  sampling  system can be used.

        ^Registered trade mark.  Obtainable from Millipore Corp.
                              A-8

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                                                       2
Rany.e and Sensitivity
Working concentration range and sensitivity depend on sample
size.  A sensitivity better than 0.5 p.g S07   per ml in
60% IPA and working range of 0 - 25 |ig/ml were obtained
using a 0.5 ml external sampling loop injection system in
conjunction with a du Pont liquid chromatograph UV detector.
Sensitivity may be further increased by increasing the
alcohol content of the solvent, as this would further
decrease the solubility of BaSO,  and barium chloranilate.
This, however, requires a much tighter control of the
water/IPA ratio in the sample and in the mobile phase.  To
minimize spurious results arising from water imbalance, it
is recommended that both the extracting solvent and the
mobile phase for analytical runs  be taken from the same
stock solution.  Sample size as large as 1.5 ml has been
successfully used.

Interferences
Cations interfere negatively by reacting with the acid
chloranilate -to form insoluble salts.  These, however, are
conveniently removed by passin'g the sample through a cation
exchange resin in the acid form.   Some anions such as
Cl", Br~, F~, P0|   interfere positively by precipitating
out as barium salts with subsequent release of acid
                                        2  r
chloranilate ions.  Some buffer systems   J    are reported
to minimize anion interference.  These systems are being
investigated for possible incorporation in the present
procedure.  Alternative clean-up  methods are also under
consideration.  Fortunately, for  non-leaded exhaust samples
collected on filters, ionic interference is minimal.
Interference,from aromatic compounds is minimized by using
a 300 rnu. cut-off filter in the optical path of the detector
system.
                          A-9

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                                                           3
4.  Precision. Accuracy, and Stability
    4.1  Precision
         With an external sampling loop of about 1.5 ml,
         photometer attenuation set to read .04 absorbance
         units full scale, standard deviation of 0.05 M-g
         S0//ml was obtained for a sample containing 4.0 ug
         SO^/ml.
    4.2  Stability
         4.2.1  Sulfuric acid standards containing 10 and
                100 jig SO?/ml in 60% IPA are stable for at
                least one month when stored in tightly capped
                volumetric flask which has been cleaned with
                1:1 nitric acid and copiously rinsed with
                deionized water.  Alternative storage containers
                are capped polyethylene reagent bottles.
         4.2.2  The cation exchange resin and the barium
                chloranilate columns as described in apparatus
                section last for over two months.  For samples
                known to contain cations, it is advisable to
                remove these cations by external treatment
                with cation exchange resin prior to injection
                into the sampling loop.
         4.2.3  As the barium chloranilate column is depleted
                each time sulfate samples are fed through, it
                is good practice to run sulfuric acid standards
                before and after the sample.
         4.2.4  Exposure of alcoholic samples, standards, and
                solvents to the atmosphere should be minimized,
                since IPA solution picks up atmospheric water
                on standing.
                             A-10

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                                                       4
Apparatus
A schematic of the principal components of the automated
set-up is shown in Figure 1.
5.1  Hardware
     a.  Reservoir (LR) for the solvent (60% IPA),
     b.  High pressure liquid pump (LP) capable of
         delivering liquids at flow rates of up to
         3 ml/min at pressures as high as 1000 psi.
         Most liquid pumps used in high pressure liquid
         chromatography would be satisfactory.
     c.  Flow or pressure controller (FC).
     d.  Six-port high pressure switching valve (SV) 
         equipped with interchangeable external loop (L).
     e.  Ultraviolet detector (D) equipped with appropriate
         filters to isolate a narrow band of radiation
         centered at 310. imi.  A microscope cover glass was
         found to be satisfactory.
     f.  Recorder to monitor detector response.
     g.  Automatic sampler (AS), such as the one used for
         a Technicon AutoAnalyzer.
     h.  Peristaltic pump (PP). to draw sample into sampling
         loop.
     i.  Cation exchange resin column (CX) - standard
         1/4" 0. D. x 10" stainless steel column packed
         with analytical grade Dowex 50W-X2   cation exchange
         resin in hydrogen form.
     j.  Barium chloranilate column (BC) - standard  1/4"
         0. D. x 5" stainless steel column packed with
         barium chloranilate.
                        A-11

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                                                       5
5.2  Principle of Operation
     Solvent (60% I?A) in reservoir (LR) is continuously
     fed through cation exchange (CX)  and barium chloranilate
     columns at flow rates of about 3  ml/min. by a high
     pressure liquid pump (LP).   Background absorbance is
     continuously measured by a  UV detector (D) at 310 rop.
     and visually monitored in a strip chart recorder.
     A solenoid actuated air operated  switching valve (SV)
     is used for filling the external  sampling loop (L)
     with samples in conjunction with  an automatic sampler
     (AS) and peristaltic pump (PP) and injecting the sample
     into the columns.  At CX cations  are removed and at
     BC, color reaction takes place.  The BaSO, precipitate
     is retained in the column while the acid chloranilate
     is carried by the solvent through the detector system
     for colorimetric measurement.

     For an automated sampling system such as shown in
     Figure 1, both SV and PP are electrically coupled to
     AS by electric relays such  that both are activated
     vhenever AS is sampling (I.e.  L  is being filled and
     mobile phase bypasses L).  At the end of the sampling
     cycle, PP and AS stop and SV switches to the injection
     mode (i.e. mobile phase passes through L and carries
     sample through CX and BC columns).

     For manual operation SV may be retained or replaced
     by a similar switching valve equipped with an extended
     handle for manual switching.  Samples may be introduced
     into the sampling loop by syringe injection or by
     peristaltic pump system similar, to the one used in
     the automated system.
                          A-1Z

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6.  Reagents
    6.1  Isopropyl alcohol (IPA)  spectroquality grade or
         equivalent.   Volatile  solvent,  safety class IB.
    6.2  60% IPA.   Add four parts water  to six parts IPA
         by volume.  Store in tightly  capped bottle.  About
         three liters are  needed  for a 12  hour operation.
    6.3  Barium chloranilate, suitable for sulfate analysis.
    6.4  Dowex 50U-X2  cation exchange resin, hydrogen form,
         100-200 mesh.
    6.5  Hydrochloric acid (4N).  Add  30 ml .concentrated
         hydrochloric acid to 60. ml deionized water.  (Danger,
         strong acid.)
    6.6  Standard sulfuric acid  (IN)-.  Dilute to the mark
         2.8 ml of concentrated  sulfuric acid with deionized
         distilled water in a liter volumetric flask which
         has been washed in 1:1  nitric acid and copiously
         rinsed with  deionized  distilled water.  Standardized
         against accurately weighed sodium carbonate to get
         exact normality.   O.IK lUSO,  is-equivalent to 4800
         p.g/SO, = /ml.  (Danger, strong acid.)
    6.7  Standard sulfate  solution  (1000 p.g S0,=/ml).  Dissolve
         1.4787 gm sodium sulfate which  has been heated up to
         105C for four hours and cooled in a dessicator and
         dilute to 1000 ml.

7.  Procedure
    7.1  Column preparation
         7.1.1  Barium chloranilate column (BC).  In order to
                prepare a  full  column  with minimum dead volume
                connect two lengths of standard 1/4" 0. D.
                stainless  steel  tubings  as shown in Figure 2.
                b = 2", a  - 5".   Connect a small funnel to
                open  end of B with  a Tygon tubing sleeve.
                            A-13

-------
       Till the -funnel "half way with barium
       chloranilate and use a vibrator (i.e. electric
       pencil engraver) to pack the solid in column.
       Continue operation until B is about half filled.
         move funnel, plug empty space with glass wool,
       arid cap the end with a 1/4" to 1/16" reducer.
       Plumb column B directly to SV in Figure 1.
       Connect a Tygon tubing at A and direct tubing
       to waste reservoir.  Activate liquid pump, set
       flow controller at pressure drop of about 600
       psi.  Let solvent flow for 20 minutes.  Deactivate
       pump, disconnect column from SV.  Disconnect
       column A from column B.  Connect a glass wool
       plugged 1/4" to 1/16" reducer to uncapped eno
       of column A.
7.1.2  Cation exchange resin column (CX).  Add cation
    -   exchange resin, 100-200 mesh, Dowex 50W-X2
       to 80 ml of 4N HC1 in a 150 ml beaker until a
       wet volume equivalent to 20 ml has settled at
       the bottom.  Let soak for at least three hours
       with occasional stirring using a glass rod.
       Decant the acid, add 100 ml deionized distilled
       water, stir and slowly, decant the liquid as
       soon as most of the solid has settled down at
       the bottom.  Repeat rinsing procedure several
       times until rinse liquid gives a neutral reaction
       to pH paper.

       Connect two standard 1/4" 0. D. stainless
       steel tubings as in 7.1.1 with b = 5" and
       a = 10".  Connect a small funnel to open end
       of B with Teflon or Tygon tubing sleeve.
       Clamp composite tube vertically and connect
                          A-14

-------
                                                       8

            open end of A to vacuum line equipped with
1            liquid trap.  Fill funnel with deionized
            distilled water and turn on vacuum slowly until
            composite tube is completely filled with water.
            Add water until funnel is half -filled, stop
            vacuum and add slurry of freshly washed resin.
            Let resin settle by gravity until resin top
            is seen above B.  Turn on vacuum slowly,, keep
            adding resin slurry until composite tube is
            completely filled.  Proceed as in 7.1.1
            beginning with sentence:   "Remove funnel, plug
            empty space. . . "
7.2  Priming System for Analytical Run
     Connect the cation exchange and barium chloranilate
     columns with 1/4" union packed with glass wool as
     shown in Figure 1.  Fill solvent reservoir (LR) with
     60% IPA, activate liquid pump, detector, recorder,
     switching valve, sampler, and peristaltic pump.
     Allow to cycle normally to clean out  all components.
     For this initial operation, dip the sampling probe
     in at least 100 ml of 60% IPA.  Set liquid flow rate
     at about 3 ml/min.  Let run for at least 30 minutes.
     Deactivate switching valve, sampler,  and peristaltic
     pump.  Leave other components in operating mode.
     When background is stable at attenuation of .01
     absorbance units full scale, system is ready for
     analysis.
7.3  Preparation of Calibration Standards       /
     Either sulfuric acid or sodium sulfate standards may
     be used.
     Add 200 ml of 0.1 N J^SO,  aqueous  stock  solution to
     300 ml 100% IPA in 500 ml  volumetric  flask.   (Note:
     There is a volume decrease of about 2.7% when these
                         A-15

-------
                                                    9
     proportions of water and IPA are mixed.)  Dilute
     to the mark with 60% IPA.  This is equivalent to
     l,920M-g S04=/ml in 60% IPA.  Prepare from this
     alcoholic stock solution calibration standards in
     the range 0.5 - 25 |J.g S0^=/ml by dilution of appropriate
     aliqiiots with 60% IPA.
7.4  Extraction of Soluble Sulfates from Fluoropore Filters
     Place filter in one oz. polyethylene bottle, add 10 ml
     60% IPA and cap tightly.  Shake until filter collapses
     and is completely immersed in liquid.  Let stand
     overnight.
7.5  Analysis
     Set instrument in operating mode, remove sampling probe
     from holder, an'd dip in 100 ml 60% IPA.  Let it run
     at flow rate of 3 ml/min until stable background is
     obtained, then remount sampling probe to holder.
     In the meantime, fill sample cuvettes with sample
     extract and  blank  solutions (60% IPA) and place
     on turntable.  Sampling pattern is blank, blank,
     sample, blank, blank at .the rate of about six minutes
                              *
     per sample or blank.  Blanks are used to wash out
     system between samples and minimize sample overlap.
     One blank between samples is adequate for dilute samples,
     (See also 5.2.)
     A series of standards (see 7.3) is run, preferably
     before sample runs and calibration curve, peak height
     vs. concentration, is plotted.  A control standard
     may also be placed after every ten samples as a
     quality check on the stability of the system.
     The plot of peak height (detector response) vs.
     concentration (u.g S0,=/ml) is non-linear in the low
     concentration end as would be expected from solubilities
     and kinetics consideration.  Non-linearity is also
     observed at the upper end of the curve.
                          A-16

-------
                                                          10

6.  Calculations
    Calculate the concentration o sulfate as pig S0,=/ml
    using the calibration curve.  Total soluble sulfates
    [SO,=]F in filter Is then given by:
         [S04=]F = (ktg S04=/m) x Vo x. d
         where:  Vo = total volume of original sample extract
                 d  = dilution factor
    Example:  Suppose 10 ml 60% IPA was used to extract the
    soluble sulfates in the filter and that 2 ml of this was
    diluted further to 6 ml with 60% IPA to bring detector
    response within calibration r,ange.  Suppose that the.
    concentration of the diluted sample was found to be
    5 tig/ml.  Then,                    6
         [S04=3F - (5 ug/ml) x 10 ml x 1 - 150 ug.
                             A-17

-------
                       References

1.  R. J. Bertolacini and J.  E.  Barney II,  "Colorimetric
    Determination of Soilfate  with Barium Chloranilate,"
    Anal. Chem. 29., 281 (1957).

2.  Ibid, "Ultraviolet Spectrophotometric Determination
    of Sulfate, Chloride and  Fluoride with  Chloranilic
    Acid," Anal. Chem. 30, 202 (1958).

3.  H. N. S. Schafer, "An Improved Spectrophotometric
                                          ^        
    Method for the Determination of Sulfate with .Barium
    Chloranilate as Applied to Coal Ash and Related
    Materials," Anal. Chem. 19,  1719 (1967).

4.  S. C. Barton and H.' G. McAdie, "An Automated Instrument
    for Monitoring Ambient l^SO,  Aerosol11 in Proceedings
    of the Third International Clean Air Congress,
    Dusseldorf, Federal Republic of Germany, 1973,
    VDl-Verlag GmbH, 1973, p. C25.
                             

5.  M. E. Gales, Jr., W. H. Kaylor and J. E. Longbottom,
    "Determination of Sulphate by Automatic Colorimetric
    Analysis," Analyst 93, 97 (1968).
                         A-18

-------
                   FIGURE 1
FLOW SCHEMATIC FOR AUTOMATED SULFATE INSTRUMENT?
LR
                                           RECORDER
                                          sr-TO WASTE
             
         c
                                         O AS
TO WASTE

-------
            FIGURE 2
CONFIGURATION FOR LOADING COLUMN
                             1/4" TO 1/lff' REDUCER
  1/4" UN ION
GLASS WOOL PLUG
        t    I

-------
        Barium Chloranilate Interference Experiments - During the course
of the project, several fuel and fuel additive combinations will be used,
all of which will require sulfate analysis using the barium chloranilate
procedure.  Although a cation exchange column is included as part of the
sampling system,  concern has been expressed for the analysis of sulfate
on engines operating on leaded fuel.  The Dowex SOW X-2 cation exchange
column has  been included to eliminate or at least reduce any lead that
might be collected on the filters for sulfate analysis.  Since the efficiency
of the cation exchange column may not remove all of the lead ions,  it was
decided to conduct a series of experiments to  determine how much inter-
ference from lead might be expected.  These experiments were conducted
with an ion exchange column, which had been used for about one month on
lead free samples.

       A working  sulfate standard of 23. 93^ug SO4~/ml was used to  make
comparisons with the various lead blends.  Lead nitrate blends were pre-
pared in 60  percent  IPA in concentrations of 25. 0, 12. 5, and 5. Ojug Pb"'"'"/ml.
These solutions were analyzed in the same manner as an extracted sample.
and the corresponding peak was calculated as  response as^pg SC>4~/ml.
These data is presented in Table A-l arid shown graphically in Figure
A-7.  The response as^ug SO^~/ml varied from 2.7  to 0. 7jig SO4~/ml
with Pb   concentrations ranging from 25 to 5jug Pb  /nil.  It was appa-
rent that not all of the lead is being removed by the ion exchange column.

       Since lead  is generally added to the fuel in the form of a motor
mix containing ethylene dichloride and ethylene dibromide as scavengers,
it was decided to determine if these could produce erroneous results.
The first experiment involved the preparation of three concentrations of
chloride in 60 percent IPA.  Sodium chloride was used in the preparation
of the 24.3, 12.1, and 4. 8jag Cl~/ml.  Again, these blends were analyzed
just as a normal sulfate sample'and the corresponding peak calculated as
response asjug/SO  ~/ml.  These results are found in Table A-l, arid ug
Cl~/ml as a function of response as^ug SO4 = /ml is shown in Figure A-7.
The response as jig  SO^~/ml varied from 7. 1  to 2.1  with a range injug
Cl~/ml of 24. 3 to  5. 0.  In comparison with the experiment in lead inter-
ference, it was found that the chloride ions produced some three to four
times greater interference than the lead ions alone.

       A similar experiment involving the interference of bromide ions
was conducted.  Sodium bromide was added to 60 percent IPA in concen-
trations 31.1, 15.5, and6.2jag Br"/ml.  These blends were also analyzed
according to the standard barium chloranilate procedure. The range of
response as^ug SC>4 = /ml was from 5. 1 to' 1. 9 for the concentrations of
Br" tested.

       Of the three  interference species  evaluated, it appears that with
the normal barium chloranilate procedure lead has the least interference
                                A-21

-------
TABLE A-l.   EFFECT OF LEAD CHLORIDE AND BROMIDE IONS


    ON SULFATE RESULTS USING THE BARIUM CHLORANILATE


              LIQUID CHROMATOGRAPH PROCEDURE
                         Response as


 Sample Description     yiig SO4~/ml        jug Pb^/mlipg SO4=/ml





23.93 jug SO4=/ml          23.93





25.0 jug Pb^/ml             1.71                      14.6





12. 5 jag Pb"* /ml             0.66                      18.9





 5.0 jag Pb-* /ml             0.33                      15.1





                                             jag Cr/ml; /ug SO4=/ml
                                            ^^ "^" "^*^^^^M"*^^^^^ ^">>^-^'^^-"




24.3 jug Cl~/ml             7.06                       3.4





12. 1 jag Cl-/ml             4.23                       2.9





 4.8 /ig Cl-/ml             2. 12                       2.3





                                                Br"/ml;
31. 1 jag Br-/ml              5.07                      6.1




15.5 yig Br"/ml              4.04                      3.8




  6.2 jag Br'/ml              1.92                      3.2
                                 A-22

-------
I.' V'V
                      a CSSUH en.

-------
and chloride the greatest.  A nominal 1 }ig Pb  /ml concentration pro-
duced a response as 1 ug SO4=/ml.  A bromide concentration of 3jig
Br~/ml provide an equivalent response to 1/ig SO4=/ml.  The chloride
ion concentration required to give a response as jag SO4~/ml ranged
from 2 to 3 ug Cl~/ml.
                                A-24

-------
4.     Nitrogen Compounds

       The nitrogen compounds included in this analysis were nitromethane
(CH3NO2), dimethylnitrosamine (DMNA),  and ammonia (NH3).   This anal-
ysis was conducted using two different analytical systems.  A gas chroma -
tograph equipped with a Hall Electrolytic Conductivity detector was used
for each analysis.  The major  difference was column arrangement in that
the DMNA and CH3NO2 used a  3' x 1/4"  glass column packed with Chromo-
sorb 101.  The furnace was maintained at 600 C with the detector in the
reductive mode.  A helium carrier gas flow rate of 80  ml/min was used,
and the column was programmed from 100 C to 165 C  at 7.5C/min.
Dilute liquid calibration standards were  prepared and comparisons were
made to the samples.  Individual bag samples were analyzed for DMNA
and CH3NC>2 using a 5 ml gas tight syringe.   A summary of the  gas chro-
matograph operating  conditions for the analysis of Cf^NC^  and  DMNA are
presented in Table A-2.

       The analysis for ammonia in the  dilute exhaust  bag samples was
conducted using a Hall Electrolytic Conductivity detector without the fur-
nace, connected directly to the detector.  A 3' x 1/4" Teflon column
packed with 20 to 30 mesh Ascarite was  used to remove any acid gases.
A helium carrier gas was used at a flow rate of 150 ml/min and was op-
erated isothermally at room temperature.  Calibration standards  were
prepared and used for direct comparison to the dilute exhaust samples.
Sample injections of both standards and  samples  were made using a 1 ml
gas tight syringe. A  summary of the gas chromatograph operating con-
ditions is presented in Table A-2.  Figure A-8 illustrates the gas chroma-
tograph system used in the analysis of the nitrogen compounds.
                                A-25

-------
        TABLE A-2.  SUMMARY OF GAS CHROMATOGRAPH
       OPERATING CONDITIONS USED IN THE ANALYSIS OF
               SULFUR AND NITROGEN COMPOUNDS
Parameter
Instrument
Column
H2S, COS,
Mercaptans
Tracer MT 220
12" x 1/8" teflon
Column Packing    Chromosorb 102
Carrier gas

Carrier flow

Column temp

Detector


Sample size
Minimum
detection
limits
60 ml/min
room
Flame photometric
(S-mode)

10 ml  sample loop
 50 ppb H2S
 25 ppb COS
 100 ppb CH3SH
 300 ppb C2H5SH
CH3NO2, DMNA
Tracer MT 200
3' x 1/4" glass
                      Chromosorb 101
                      He
80 ml/min
Ammonia
Tracer MT 200
3' x 1/4" teflon
                     20-30 mesh Ascarite
                     He
 150 ml/min
                       100-165 @7. 5C/min  room
Hall ECD @ 600 C
(Reductive mode)
0. 04 ppm CH3NO2
0. 06 ppm DMNA
Hall ECD
(no furnace)
5 ml glass syringe   1 ml syringe
 0. 5 ppm
                                        A-26

-------
FIGURE A-8.  GAS CHROMATOGRAPH SYSTEM USED FOR ANALYSIS
   OF NITROMETHANE, DIMETHYLNITROSAMINE AND AMMONIA
     FIGURE A-9.  GAS CHROMATOGRAPH SYSTEM USED FOR
     ANALYSIS OF HYDROGEN SULFIDE, CARBONYL SULFIDE,
                METHYL AND ETHYL MERCAPTAN
                              A-27

-------
5.     Sulfur Compounds

       The measurement of sulfur compounds was conducted using a Tracer
MT 220 gas chromatograph equipped with a flame photometric detector op-
erating in the S mode.  A 12" x 1/8" Teflon column'packed with Chromosorb
102 operating isothermally at room temperature was used.  A nitrogen car-
rier gas  flow rate of 60 ml/min was found to give a satisfactory separation
of H2S, COS, CH3SH,  and C2H3SH in dilute automotive exhaust.  A 10 ml
gas sampling loop was used for sample and calibration standard injections.
Standards were prepared for the individual sulfur compounds on a daily
basis as  needed.   The minimum detection  limits as well as a summary of
the gas chromatograph operating conditions are found in Table A-2.  Figure
A-9 illustrates the gas chromatograph system used in the analysis of the
various sulfur compounds.
                                 A-28

-------
               APPENDIX B




INDIVIDUAL HYDROCARBON DISTRIBUTION

-------
TABLE B-l.  HYDROCARBON DISTRIBUTION OF NON-REACTIVE AND
      SEVERAL REACTIVE HYDROCARBONS MEASURED DURING
         1975 LD FTP ON 1972 350 CID CHEVROLET ENGINE
               (EM-214-F,  Base Fuel at 0. 1% Sulfur)
                        NRHC Concentration, ppmC
  Reactive HC's
Measured,  ppmC
Date Run
12-16-74 1
(0 Miles)


12-16-74 2
(0 Miles)


12-23-74 1
(1000
Miles)

12-23-74 2
(1000
Miles)

12-31-74 1
(2000
Miles)

12-31-74 2
(2000
Miles)

Bag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
CH4
13.7
9.5
10.8
2. 2
10.5
10.0
9.6
2. 1
13.9
10.2
12. 2
2.2
11.6
8.8
9.8
4.9
11.2
10.5
12.4
2.2
11.6
11.4
13.1
2.2
C2H6
2.1
1.2
1.8
0.0
1.8
1.0
1.6
0.0
1.6
1.0
1.7
0.0
1.7
0.9
1.5
0.0
1.5
1.0
1.3
0.0
1.5
0.9
1.4
0.0
C2H2
14.4
10. 2
13. 1
0.0
12.7
8.2
11.6
0.0
13. 1
11. 1
14.4
0.0
13.4
9.3
11.7
0.0
13.2
10.3
11.8
0.0
13.3
10.0
12.9
0.0
C3H8
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
C6H6
3.3
2.5
3. 1
0.0
3.2
2. 1
2.3
0.0
2.7
1.6
3.2
0.0
3.0
2.6
2.4
0.0
8.2
9.2
8.3
' 0.0
9.0
6.6
7.9
0.0
C2H4
20.7
14.8
21.4
0.0
20.9
11.5
19.1
0.0
19.9
13.1
20.6
0.0
20.2
11.9
17.9
0.0
17.8
12.2
16.5
0.0
17.6
11.5
11. 1
0.0
C3H6
9.5
6.0
8.9
0.0
12.7
4.9
7.9
0.0
8.3
4.9
8.2
0.0
8.4
4.5
7.4
0.0
7.2
4.6
6.7
0.0
7.0
4.2
6.8
0.0
C7H8
32.8
15.8
28.4
0.0
31.9
11.6
23.9
0.0
21.8
12.2
23.8
0.0
22.7
10.2
23.0
0.0
15.5
9.3
17.8
0.0
19.2
8.7
17.5
0.0
                                 B-2

-------
TABLE B-2.  HYDROCARBON DISTRIBUTION OF NON-REACTIVE AND
    SEVERAL REACTIVE HYDROCARBONS MEASURED DURING
        1975 LD FTP ON 1972 350 CID CHEVROLET ENGINE
       (EM-215-F at 0. 1% Sulfur + 0.378 g/gal Lubrizol 8101)
                                                      Reactive HC's
                                                    Measured, ppm C
Date Run
2-10-75 1
(0 Miles)

2-10-75 2
(0 Miles)


2-13-75 1
(1000
Miles)

2-13-75 2
("1000
Miles)

2-18-75 1
(2000
Miles)

Z-18-75 2
(2000
Miles)

Bag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1N\ n
CH4
7.9
6.6
7.8
2.3
6.4
5.6
7.0
2.4
6.9
6.7
6.8
3. 1
6.2
5.4
6.0
2.2
7.2
6. 1
6.3
2. 1
6.8
5.2
6.2
2.1
^, V^UJIV.
C2H6
1.2
0.7
1. 1
0.0
0.9
0.6
1.0
0.0
0.8
0.5
0.8
0.0
0.8
0.5
0.8
0.0
0.8
0.5
0.8
0. 0
0.8
0.5
0.7
0.0
C^J.1 \f . UJ.*w
C2H2
9.0
6.6
9.0
0.0
7.4
5.7
8.1
0.0
6.7
5.0
6.6
0.0
6.9
5.2
6.5
0.0
8.3
6.2
7. 1
0.0
7.4
4.9
6.9
0.0
'" fr
C3H8
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0. 0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0. 0
0.0
0.0
0.0
0. 1
0.0
0.0
l'6"6
2.7
2. 1
2.7
0.0
2.2
1.7
2.6
0.0
2.0
1.5
2.0
0.0
2. 1
1.6
2.2
0.0
2.5
1.9
2.4
0. 0
2.3
1.4
1.9
0.0
C2H4
12.4
8.5
13.0
0.0
11.6
7.6
12.2
0.0
11. 1
6.9
10.6
0.0
10.7
6.8
10.0
0.0
11.6
7.3
10.8
0.0
11. 1
6.5
10.3
0.0
C3H6
5. 1
3.4
5.6
0.0
4.8
2.9
5.2
0.0
4.7
2.7
4.4
0. 0
4.5
2.6
4.1
0.0
4.7
2.8
4.6
0. 0
4.5
2.5
4.2
0.0
C7H8
15. 1
7. 3
16.9
0.0
12.0
5.2
14. 1
0.0
11.2
4.8
10.7
0. 0
11.2
4.4
10.7
0. 0
10.7
5.2
11.5
0.0
10. 5
4.4
10.0
0.0
                                B-3

-------
TABLE B-3.  HYDROCARBON DISTRIBUTION OF NON-REACTIVE AND
     SEVERAL REACTIVE HYDROCARBONS MEASURED DURING
          1975 LD FTP ON 1972 350 CID CHEVROLET ENGINE
         (EM-216-F at 0. 1% Sulfur + 0.486 g/gal Paradyne 506)
                   NRHC Concentration, ppmC
 Reactive HC's
Measured,  ppmC
Date Run Bag
1-10-75
(0 Miles)


1-10-75
(0 Miles)


1-13-75
(1000
Miles)

1-13-75
(1000
Miles)

1-20-75
(2000
Miles)

1-20-75
(2000
Miles)

1 1
2
3
BG
2 1
2
3
BG
1 1
2
3
BG
2 1
2
3
BG
1 1
2
3
BG
2 1
2
3
BG
CH4
12.7
10. 1
12.9
3.6
11.4
8.9
10.3
2.3
6.8
5.2
7.1
2.2
7.2
4.8
5.5
2.1
8.0
9. 1
7.6
2.2
7.3
5.6
6.2
2.2
C2H6
1.6
i.o'
1.5
0.0
1.6
0.9
1.3
0.0
0.9
0.4
0.8
0.0
0.8
0.4
0.7
0.0
0.8
0.5
0.8
0.0
0.8
0.4
0.7
0.0
C2H2
16.0
11.8
15.0
0.0
14.3
10.3
12.5
0.0
7.8
5.1
7.1
0.0
8.3
4.5
6.1
0.0
8.1
5.4
8.5
0.0
8.6
5.3
6.7
0.0
C3H8
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.6
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
C6H6
3.9
2.3
3.8
0.0
4.3
3.0
2.9
0.0
1.5
1.4
1.4
0.0
1.5
1.2
1.5
0.0
1.8
1.5
1.9
0.0
1.7
1.2
1.3
0.0
C2H4
19.3
13. 1
19.2
0.0
18.5
12.2
16.8
0.0
11.9
6.7
10.5
0.0
12.3
6.9
10. 1
0.0
12.3
7.0
11.6
0.0
11.7
7.0
10.6
0.0
C3H6.
7.9
4.7
7.8
0.0
7.5
4.4
6.8
0.0
4,9
2.4
4.2
0.0
5.0
2.5
4.0
0.0
5.0
2.7
4.7
0.0
4.6
2.6
4.2
0.0
C?H8
22. 1
10.5
25.9
0.0
22.7
8.9
19.7
0.0
14.5
4.3
12.2
0.0
14.8
4.9
11.4
0.0
10.6
4.4
10.3
0.0
11.9
4.1
10.1
0.0
                              B-4

-------
TABLE B-4.  HYDROCARBON DISTRIBUTION OF NON-REACTIVE AND
    SEVERAL REACTIVE HYDROCARBONS MEASURED DURING
         1975 LD FTP ON 1972 350 CID CHEVROLET ENGINE
 (EM-231-F at 0. 1% Sulfur + 0.378 g/gal Lubrizol 8101 +  0. 05g Pb/gal)
                                                       Reactive HC's
                   NRHC Concentration, opmC         Measured, ppmC
Date Run
3-11-75 1
(0 Miles)


3-11-75 2
(0 Miles)


3-14-75 1
(1000
Miles)

3-14-75 2
(1000
Miles)

3-21-75 1
(2000
Miles)

3-21-75 2
(2000
Miles)

Bag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
CH4
8.6
7.2
8.4
1.6
8.3
7.4
8.3
1.6
8.2
6.5
8.2
2.4
7.4
6.7
8.0
2.4
7.7
7.3
7.8
2.2
9.2
7. 1
8.3
2.2
C2H6
1. 1
0.7
1. 1
0.0
1. 1
0.7
1.1
o.o
0.9
0.5
0.9
0.0
0.9
0.5
0.9
0.0
0.7
0.6
0.9
0.0
1.0
0.7
1.0
0.0
C2H2
9.6
7.1
9.2
0.0
9.2
7.6
9.4
0.0
9.3
6.3
8.8
0.0
8.2
6.5
8.5
0.0
8.8
7.2
8.8
0.0
10.6
7.5
9.3
0.0
C3H8
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
C6H6
3.4
2.5
3.2
0.0
3.4
2.8
3.4
0.0
2.9
2. 1
2.8
0.0
2.7
2.2
2.7
0.0
3. 1
2.6
3.0
0.0
3.3
2.6
3. 1
0.0
C2H4
13.8
8.6
12.6
0.0
12.7
9.0
12.6
0.0
12. 1
7. 1
11. 5
0.0
11.3
7.5
11.6
0.0
12.2
8.4
11.6
0.0
13.2
8.3
11.8
0.0
C3H6
5.5
3.3
5.2
0.0
5.3
3.5
5.2
0.0
4.9
2.6
4.6
0.0
4.5
2.9
4.6
0.0
4.9
3. 1
4.7
0.0
5.6
2.9
4.8
0.0
C7Hg
16.6
7.7
15.0
0.0
16. 2
7. 1
14.7
0.0
13.6
5.8
13.4
0.0
12. 3
5.4
12.7
0.0
14.6
6.6
13.5
0.0
15.6
6.5
13.3
0.0
                              B-5

-------
   TABLE B-5.  HYDROCARBON DISTRIBUTION OF NON-REACTIVE AND
        SEVERAL REACTIVE HYDROCARBONS MEASURED DURING
             1975 LD FTP ON 1975 350 CID CHEVROLET ENGINE
                   (EM-214-F, Base Fuel at 0. 1% Sulfur)
                      NRHC Concentration,  ppmC
 Reactive HC's
Measured,  ppmC
Date Run
12-17-74 1
(0 Miles)


12-17-74 2
(0 Miles)


12-20-74 1
(1000
Miles)

12-20-74 2
(1000
Miles)

12-30-74 1
(2000
Miles)

12-30-74 2
(2000
Miles)

Bag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
CH4
10.8
8.1
9.8
2.0
8.2
6.4
7.8
2.0
10.4
11.2
11.2
5.9
14.0
12. 5
14.8
6.0
14.8
10.6
13.7
2.9
11. 6
10. 1
11.7
2. 1
C2H6
0.8
0.0
0.7
0.0
0.7
0. 1
0.5
0.0
0.6
0.2
0.6
0.0
0.7
0.2
0.7
0.0
1. 1
0.5
1.0
0.0
1.0
0.4
0.9
0.0
C2H2
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1. 1
0.0
1.0
0.0
0.6
0.0
0.9
0.0
C3H8
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
CeHA
0.2
0.0
0.1
0.0
0. 1
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
tr
0.0
tr
0.0
tr
tr
tr
0.0
C2H4
2.5
0.0
1.9
0.0
1.5
0.0
1.2
0.0
1.9
0.2
2.1
0.0
2.3
0.3
1.8
0.0
5.1
1.1
3.9
0.0
5. 1
1.0
4.2
0.0
C3H6
6.9
3.2
1.7
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
tr
0.0
tr
0.0
tr
0.0
tr
0.0
C?HS
0.1
0.0
0.1
0.0
0. 1
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.1
0.0
tr
0.0
tr
0.0
tr
0.0
tr = trace,  less than 0. 05 ppmC but greater than 0. 01 ppmC
                                 B-6

-------
TABLE B-6.  HYDROCARBON DISTRIBUTION OF NON-REACTIVE AND
       SEVERAL REACTIVE HYDROCARBONS MEASURED DURING
           1975 LD FTP ON 1975 350 CID CHEVROLET ENGINE
          (EM-215-F at 0. 1% Sulfur + 0.378 g/gal Lubrizol 8101)
                     NRHC Concentration, ppmC
 Reactive HC's
Measured, ppmC
Date Run
2-7-75 1
(0 Miles)


2-7-75 2
(0 Miles)


2-14-75 1
(1000
Miles)

2-14-75 2
(1000
Miles)

21-7-75 1
(2000 Miles)
Miles)
'
2-17-75 2
(2000
Miles)

Bag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
CH4
8.6
6.5
7.9
2.7
8.4
6.8
8.3
2.7
8.3
6.7
8.1
2.3
7.2
6.5
7.6
2.3
8.0
6.6
8.3
2.5
7.8
6.1
7. 1
2.5
C2H6
0.5
0.2
0.5
0.0
0.5
0.2
0.4
0.0
0.5
0. 1
0.5
0.0
0.4
0.2
0.4
0.0
0.5
0.2
0.5
0.0
0.5
0.3
0.4
0.0
C2H2
0.0
0.0
0. 1
0.0
0.0
0.0
0.0
0.0
0.5
0.2
0.4
0.0
0.2
0.0
0.4
0.0
0.3
0.0
0.1
0.0
0. 1
0.0
0. 1
0.0
C3H8
0.0
0. 0
0.0
0. 0
0.0
0.0
0.0
0. 0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.4
0.0
0.0
C6H6
0.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.4
0.0
0.0
0.0
0.0
0. 0
0.0
0.0
0.0
0.0
C2H4
2.0
0. 1
1.7
0. 0
1.8
0.2
1.9
0.0
1.5
0.0
1.2
0.0
1.3
0.2
1.6
0.0
1.2
0. 1
1.7
0.0
1.7
0. 1
1. 1
0.0
C3H6
0.2
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0. 1
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
C7H8
0.0
0.0
0.4
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
                                B-7

-------
   TABLE B-7. HYDROCARBON DISTRIBUTION OF NON-REACTIVE AND
        SEVERAL REACTIVE HYDROCARBONS MEASURED DURING
            1975 LD FTP ON 1975 350 CID CHEVROLET ENGINE
            (EM-216-F at 0. 1% Sulfur + 0.486 g/gal Paradyne 506)
                       NRHC Concentration, ppmC
 Reactive HC's
Measured,  ppmC
Date Run
1-9-75 1
(0 Miles)


1-9-75 2
(0 Miles)


1-14-75 1
(1000
Miles)

1-14-75 2
(1000
Miles)

1-17-75 1
(2000
Miles)

1-17-75 2
(2000
Miles)

Bag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
CH4
15.4
8.9
14.2
3.1
12.4
8.5
15.1
2.6
10.6
6.3
11.9
2.7
9.4
9.4
8.3
2.5
9.9
6.3
7.9
2.2
10. 1
7.2
9.0
2.2
C2H6
0.9
0.2
0.7
0.0
0.7
0.2
0.5
0.0
0.5
0. 1
0.6
0.0
0.6
0.2
0.4
0.0
0.5
0.2
0.4
0.0
0.6
0.2
0.5
0.0
C2H2
0.4
0.0
0.3
0.0
0.3
0.0
0.0
0.0
0.2
0.0
0.0
0.0
0.0
0.0
0.3
0.0
tr
0.0
0.0
0.0
0.2
0.0
0.0
0.0
C3H8
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
C6H6
3.2
0.0
tr
0.0
1.6
tr
0.9
0.0
3.0
0.0
2.6
0.0
2.6
1.6
1.8
0.0
1.6
0.5
-0.9
0.0
1.6
0.5
1.5
0.0
C2H4
5.0
0.7
3.7
0.0
4.0
0.6
1.8
0.0
2.5
0.3
2.9
0.0
2.8
0.4
1.7
0.0
1.7
0.2
1.4
0.0
3.0
0.2
1.9
0.0
C3H6
tr
0.0
tr
0.0
tr
0.0
0.0
0.0
tr
tr
tr
0.0
tr
0.0
0.0
0.0
tr
0.0
0.0
0.0
0.0
0.0
0.0
0.0
C7Hs
3.6
0.0
tr
0.0
2.3
0.0
1. 1
0.0
1.5
0.0
1.0
0.0
1.0
0.0
0.8
0.0
0.8
0.0
0.6
0.0
0.9
0.0
0.7
0.0
tr = trace, less than 0.05 pprnC but greater than 0.01 ppmC
                                 B-8

-------
TABLE B-8. HYDROCARBON DISTRIBUTION OF NON-REACTIVE AND
     SEVERAL REACTIVE HYDROCARBONS MEASURED DURING
          1975  LD FTP ON 1975 350 CID CHEVROLET ENGINE
         (EM-218-F at 0. 1% Sulfur + 0.378 g/gal Lubrizol 8101)
                   NRHC Concentration, pprnC
 Reactive HC's
Measured, ppmC
Date Run
3-10-75 1
(0 Miles)


3-10-75 2
(0 Miles)


3-17-75 1
(1000
Miles)

3-17-75 2
(1000
Miles)

3-20-75 1
(2000
Miles)

3-20-75 2
(2000
Miles)

Bag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
CH4
8.0
5.9
7.0
2.5
7.4
5.4
6.1
2.5
6.7
5.7
6.6
2.5
7.4
6.1
6.7
2.5
6.5
5.2
6.2
2.2
6.6
5.6
5.4
2. 1
C2H6
0.5
0.3
0.5
0.0
0.5
0.3
0.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
C2H2
0.2
0.0
0.0
0.0
0.2
0. 1
0.0
0.0
0.5
0.3
0.5
0.0
0.5
0.1
0.4
0.0
0.5
0.0
0.5
0.0
0.5
0.2
0.4
0.0
C3Hg
0.0
0.0
0.0
0.0
0.0
0.2
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
C6H6
1.0
0.0
0.0
0.0
0.7
0.0
0.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.5
0.0
0.0
0.0
0.0
0.0
C-H4
1.2
0. 1
1.1
0.0
1.5
0.5
1.2
0.0
1.2
0. 1
1.0
0.0
1.3
0.2
1.3
0.0
0.8
0. 1
1,3
0.0
1.0
0.0
0.8
0.0
C3H6
0.0
0.0
0.0
0.0
0. 2
0.0
0. 1
0.0
0.0
0. 0
0.0
0.0
0.0
0.0
0. 0
0.0
0.0
0.0
0. 0
0.0
0.0
0.0
0.0
0.0
C7H8
1.4
0.0
1.0
0.0
1.4
0.0
0.7
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.9
0.0
0.0
0.0
0.0
0.0
                              B-9

-------
                         APPENDIX C




INDIVIDUAL SULFUR AND NITROGEN COMPOUND DISTRIBUTION

-------
                      TABLE C-l. SULFUR AND NITROGEN COMPOUNDS DETERMINED
                         DURING 1975 LD FTP*WITH 1972 CHEVROLET 350 CID ENGINE
                                        (EM-214-F, Base Fuel at 0.1% S)
O
i
to
        Date

    12-16-74
    (0 miles)
    12-16-74
    (0 miles)
12-23-74
(1000 miles)
    12-23-74
    (1000 miles)
    12-31-74
    (2000 miles)
    12-31 -74
    (2000 miles)
                Run

                 1
Bag

1
2
3
BG

1
2
3
BG

1
2
3
BG

1
2
3
BG

1
2
3
BG

1
2
3
BG
                                         Sulfur Compounds, ppb
H2S
ND
ND
ND
ND
tr
ND
tr
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
COS
40
ND
ND
ND
tr
ND
tr
ND
tr
tr
tr
tr
tr
ND
tr
ND
tr
tr
tr
ND
tr
ND
ND
ND
CH3SH
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C2H^SH

--

--
_ _
--

--
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
                                                                            Nitrogen Compounds,
NH3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH^NO?
0. 15
0. 11
0.19
ND
0.21
0. 12
0.20
ND
0. 13
0.05
0.18
ND
0. 16
0.08
0. 14
ND
0. 15
0.06
0. 17
ND
0. 16
0.05
0.16
ND
DMNA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
   *Hot start
   ND - not detected
   tr - trace

-------
                    TABLEC-2.  SULFUR AND NITROGEN COMPOUNDS DETERMINED
                      DURING 1975 LD FTP* WITH 1972 CHEVROLET 350 CID ENGINE
                        (EM-215-F,  base fuel at 0. 1%S + 0. 378 g/gal Lubrizol 8101)
                                      Sulfur Compounds, ppb
Nitrogen Compounds,  ppm
Date Run
2-10-75 1
(0 miles)


2-10-75 2
(0 miles)


O
i
w 2-13-75 1
(1000 miles)


2-13-75 2
(1000 miles)


2-18-75 1
(2000 miles)


2-18-75 1
(2000 miles)


Bag
1
2
3
BG
1
2
3
BG


1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
H2S
^^!&B_
ND
ND
ND
ND
ND
ND
tr
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
COS
ND
tr
ND
ND
ND
ND
ND
ND


ND
tr
ND
ND
ND
ND
ND
ND
tr
ND
ND
ND
tr
ND
ND
ND
CH3SH
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C.2H5SH
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NH3
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH3NO2
0. 24
0. 15
0.30
ND
0. 32
0. 13
0.30
ND


0.31
0.15
0.32
ND
0.31
0. 13
0.31
ND
0. 18
0. 13
0.31
ND
0. 18
0. 12
0.26
ND
DMRA
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
#not start
ND = not detected

-------
                    TABLE C-3. SULFUR AND NITROGEN COMPOUNDS DETERMINED
                      DURING 1975 LD FTF*WITH 1972 CHEVROLET 350 CID ENGINE
                       (EM-216-F, base fuel at 0. 1%S + 0. 486 g/gal Paradyne 506)
                                      Sulfur Compounds, ppb
Nitrogen Compounds,
Date Run
1-10-75 1
(0 miles)


1-10-75 2
(0 miles)


O
* 1-13-75 1
(1000 miles)


1-13-75 2
(1000 miles)


1-20-75 1
(2000 miles)


1-20-75 2
(2000 miles)


Bag
1
2
3
BG
1
2
3
BG

1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
H2S
vaw^Ki
ND
ND
ND
ND
ND
ND
ND
ND

tr
tr
tr
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
COS
ND
ND
tr
ND
tr
ND
ND
ND

tr
tr
tr
ND
tr
ND
tr
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH3SH
ND
ND
ND
ND
ND
ND
ND
ND

ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CzH^SH
ND
ND
ND
ND
ND
ND
ND
ND

ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
.ND
NHi
ND
ND
ND
ND
ND
ND
ND
ND

ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH3NO?,
0.35
0. 14
0.38
ND
0.40
0.21
0.42
ND

0. 18
0.08
0.20
ND
0.25
0. 14
0.26
ND
0.41
0.19
0.55
ND
0.48
0. 17
0.50
ND
DMNA
ND
ND
ND
ND
ND
ND
ND
ND

ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
#hot start
ND = not detected
tr = trace

-------
                    TABLE C-4. SULFUR AND NITROGEN COMPOUNDS DETERMINED
                     DURING 1975 LD FTP* WITH 1972 CHEVROLET 350 CID ENGINE
                (EM-231-F, base fuel at 0. 1%S, 0.05 g/gal Pb +'0.378 g/gal Lubrizol 8101)
                                     Sulfur Compounds, ppb
Nitrogen Compounds,  ppm
Date Run
3-11-75 1
(0 miles)


3-11-75 2
(0 miles)


O
i
w 3-14-75 1
(1000 miles)


3-14-75 2
(1000 miles)


3-21-75 1
(2000 miles)


3-21-75 2
(2000 miles)


Bag
1
2
3
BG
1
2
3
BG


1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
HzS
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
COS
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CHsSH
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C2H5SH
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NH3
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH3NO2
0.26
0. 11
0.26
ND
0.26
0. 13
0.25
ND


0.36
0. 14
0.32
ND
0.40
0. 16
0. 23
ND
0.29
0. 13
0.35
ND
0. 32
0. 13
0.32
ND
DMNA
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
#hot start
ND = not detected

-------
o
                      TABLE C-5. SULFUR AND NITROGEN COMPOUNDS DETERMINED
                        DURING 1975 LD FTF*WITH 1975 CHEVROLET 350 CID ENGINE
                                       (EM-214-F,  Base Fuel at 0.1% S)
                                        Sulfur Compounds, ppb
Nitrogen Compounds
Date Run
12-17-74 1
(0 miles)


12-17-74 2
(0 miles)


12-20-74 1
(1000 miles)


12-20-74 2
(1000 miles)
-

12-30-74 1
(2000 miles)


12-30-74 2
(2000 miles)


Bag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
H7S
ND
ND
ND
ND
ND
tr
tr
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
COS
ND
ND
ND
ND
ND
ND
tr
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH^SH
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C2Hc;SH



--
 .
--
--
--
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NH^
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH^NO?
ND
ND
ND
ND
0.05
tr
0.09
ND
ND
ND
0.08
ND
0.08
ND
0.09
ND
0.11
0.04
0.11
ND
0.12
0.04
0.14
ND
DMNA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
   *hot start
   ND = not detected
   tr .= trace

-------
                    TABLE C-6. SULFUR AND NITROGEN COMPOUNDS DETERMINED
                     DURING 1975 LD FTP*WITH 1975 CHEVROLET 350 CID ENGINE
                        (EM-215-F, base fuel at 0. 1%S + 0/378 g/gal Lubrizol 8101)
                                       Sulfur Compounds, ppb
Nitrogen Compounds*  PPm
Date Run
2-7-75 1
(0 miles)


2-7-75 2
(0 miles)


O
i
-J 2-14-75 1
(1000 miles)


2-14-75 2
(1000 miles)


2-17-75.. 1
(2000 miles)


2-17-75 2
(2000 miles)


Bag
1
2
3
BG
1
2
3
BG


1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
H2S
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
COS
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH3SH
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C2H5SH
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NH3
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH3NO2
0. 11
0.06
0. 13
ND
0.09
0. 13
0. 10
ND


0. 12
0.04
0. 14
ND
0. 15
0. 04
0. 15
ND
0.15
0.04
0.23
ND
0.30
0.06
0.32
ND
DMNA
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*hot start
ND = not detected

-------
                   TABLE C-7. SULFUR AND NITROGEN COMPOUNDS DETERMINED
                     DURING 1975 LD FTP* WITH 1975 CHEVROLET 350 CID ENGINE
                         (EM-216-F,  base fuel at 0. 1%S + 0.486 g/gal Paradyne 506)
                                      Sulfur Compounds,  ppb
Nitrogen Compounds, ppm
Date
1-9-75
(0 miles)
M

1-9-75
(0 miles)

O
t
00
1-14-75
(1000 miles)


1-14-75
(1000 miles)


1-17-75
(2000 miles)


1-17-75
(2000 miles)


Run Bag
1 1
2
3
BG
2 1
2
3
BG


1 1
2
3
BG
2 1
2
3
BG
1 1
2
3
BG
2 1
2
3
BG
H?S
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
COS
199
tr
38
ND
tr
ND
ND
ND


ND
ND
ND
ND
tr
ND
ND
ND
tr
ND
ND
ND
ND
ND
ND
ND
CHgSH
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CjHsSH
_MJ^MM *
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NH3
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH^NO?
0. 17
0.06
0.20
ND
0. 12
tr
0. 14
ND


0.20
0.04
0.25
ND
0.27
0.08
0.27
ND
0. 11
tr
0. 11
ND
0. 17
0.16
0. 17
ND
DMNA
ND
ND
ND
ND
ND
ND
ND
ND


ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*hot start
ND = not detected
tr = trace

-------
n
          Date
     3-10-75
     (0 miles)
     3-10-75
     (0 miles)
     3-17-75
     (1000 miles)
     3-17-75
     (1000 miles)
     3-20-75
     (2000 miles)
    3-20-75
    (2000 miles)
                        TABLE C-8. SULFUR AND NITROGEN COMPOUNDS DETERMINED
                         DURING 1975 LD FTP* WITH 1975 CHEVROLET 350 CID ENGINE
                       (EM-218-F,  high aromatic fuel at 0. 1%S + 0. 378 g/gal Lubrizol 8101)
Run
                                        Sulfur Compounds,  ppb
                                                        Nitrogen Compounds,  ppm
iag
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
1
2
3
BG
H2S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
COS
tr
ND
ND
tr
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH3SH
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C2H5SH
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NH3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CH3NO2
0. 11
tr
0. 13
tr
0. 14
0.04
0. 17
ND
0. 15
0.04
0. 18
ND
0.26
0.05
0.32
ND
0. 16
0.03
0.20
ND
0. 18
0.03
0.21
ND
DMNA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND 
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
    #hot start
    ND = not detected

-------
     APPENDIX D




SULFUR DISTRIBUTION

-------
            TABLE D-l. SULFUR DISTRIBUTION* FOR 1972 350 CID CHEVROLET USING EM-214-F
S from
Date
12-16-74
12-16-74
12-23-74
12-23-74
12-31-74
12-13-74
Miles Run
0 1
0 2
Avg.
1000 1
1000 2
Avg.
2000 1
2000 2
Avg.
Fuel
S, g
2.64
2.59
2.62
2.40
2.25
2.33
2.43
2.35
2.39
SO2, g
bag
4.79
5.30
5.05
2.48
3.01
2.75
3.87
3.77
3.82
cont
7. 17
6.88
7.03
5.74
5.80
5.77
4.92
5.. 61
5.27
S02, g
bag
2.39
2.65
2.52
1.24
1.51
1.38
1.94
1.89
1.92
cont
3.59
3.44
3.52
2.87
2.90
2.89
2.46
2.80
2.63
S04~
g
0.0063
0.0070
0.0067
0.0039
0.0053
0. 0046
0.0066
0.0057
0.0062
S from
S04=, g
0.
0.
0.
0.
0.
0.
0.
0.
0.
0021
0023
0022
0013
0018
0016
0022
0019
0021
% Fuel
S02 (bag)
90
102
96
52
67
60
80
80
80
S Appearing as
SO2 (cont) SO4=
136 <0. 1
133 <0. 1
135 <0. 1
120 <0. 1
129 -rO. 1
125 <0. 1
101 <0. 1
119 <0.1
110 <0. 1
* Based on hot start 1975 LD FTP

-------
         TABLE D-2.  SULFUR DISTRIBUTION* FOR 1972 350 CID CHEVROLET USING EM-215-F
O
i
u>
S from

Date Miles
2-10-75 0



2-13-75 1000


2-18-75 2000




Run
1
2
3
Avg.
1
2
Avg.
1
2
3
Avg.
Fuel
S, g
2.56
2.45
2.47
2.49
2.40
. 2.39
2.40
2.33
2.35
2.42
2.37
SOz,
bag
4.81
5.22
5.23
5.09
5. 15
5.21
5. 18
5.14
4.81
5.76
5.24
R
cont
7.04
6.48
6.55
6.69
6.59
6. 22
6.41
6.55
6. 19
6.45
6.40
SOz,
bag
2.41
2.61
2.62
2.55
2.58
2.61
2.59
2.57
2.41
2.88
2.62
2
cont
3. 52
3.24
3.28
3. 35
3.30
3. 11
3.21
3. 28
3. 10
3.23
3. 20
so4=
g
0.0039
0. 0045
0.0033
0.0039
0.0029
0.0016
0.0023
0.0028
0.0020
0.0026
0.0025
S from
S04=, g
0.0013
0.0015
0.0011
0.0013
0.0010
0.0005
0. 0008
0.0009
0.0007
0.0009
0.0008
% Fuel
S02(bag)
94
107
106
102
108
109
110
110
103
119
111
S appearing
SOz(cont)
138 <
132
133
134 :
138 <
130
134
141
132
133
135
as
SO4~
-0. 1
-0. 1
0. 1
0. 1
0. 1
: 0. 1
0. 1
0. 1
0. 1
0. 1
0. 1
       * Based on hot start 1975 LD FTP

-------
             TABLE D-3. SULFUR DISTRIBUTION* FOR  1972 350 CID CHEVROLET USING EM-216-F
S from

Date Miles Run
1/10/75 0 1
2
Avg.
1/13/75 1000 1
? 2
Avg.
1/20/75 2000 1
2
Avg.
Fuel
S, g
2.80
2.84
2.82
2.53
2.35
2.44
2.62
2.45
2.54
S02,
bag
4.91
5.61
5.26
4.42
4.76
4.59
4.75
4.97
4.86
g
cont
6.48
7.11
6.80
6.08
5.47
5.78
5.1-5
5.70
5.43
S02,
bag
2.46
2.81
2.64
2.21
2.38
2.30
2.38
2.49
2.44
g
cont
3.24
3.56
3.40
3.04
2.74
2.89
2.58
2.85
2.72
SO4
g
0.0034
0.0028
0.0031
0.0064
0.0052
0.0058
0.0071
0.0068
0. 0070
S
S<
0
0
0
0
0
0
0
0
0
from
IA~, K
.0013
.0009
.0011
.0021
.0017
.0019
.0024
.0023
.0024
% Fuel
S02 (bag)
88
99
94
87
101
94
91
102
97
S appearing
SO? (cont)
116
125
121
120
116
118
98
116
107
as
504-
< 0.1
< 0.1
< 0.1
- 0.1
< 0.1
< 0.1
<0.1
< 0. 1
<
* Based on hot start 1975 LD FTP

-------
            TABLE D-4. SULFUR DISTRIBUTION* FOR 1972 350 CID CHEVROLET USING EM-231-F
S from

Date
3/11/75


3/14/75



3/21/75




Miles Run
0 1
2
Avg.
1000 1
2
3
Avg.
2000 1
2
3
Avg.
Fuel
S, g
2.54
2.54
2.54
2.45
2.50
2.43
2.46
2.38
2.42
2.40
2.40
SO?,
bag
4.20
4.25
4.23
4.93
5.87
5.76
5.52
3.56
3.89
3.94
3.80
g
cont
6.71
6.82
6.77
6.99
7.03
6.88
6.97
5.96
6.26
6.55
6.26
so?,
bag
2.10
2.13
2.12
2.47
2.94
2.88
2.76
1.78
1.95
1.97
1.90
g
cont
3.36
3.41
3.39
3.50
3.52
3.44
3.49
2.98
3.13
3.28
3.13
so4-
g
0.0012
0.0010
0.0011
0.0026
0.0018
0.0040
0.0028
0.0021
0.0069
0.0012
0.0034
S from
SO4~, g
0.00004
0.0003
0.00004
0.0010
0.0007
0.0013
0.0009
0.0007
0.0023
0.0004
0.0011
% Fuel
SO? (bag)
83
84
83
101
118
119
112
75
81
82
79
S appearing
SO? (cont)
132
134
133
143
141
142
142
125
129
137
130
as
so4~
<- 0. 1
0.1
0.1
- 0.1
. 0.1
,0.1
-.0.1
- 0.1
< 0.1
- 0.1
- 0.1
* Based on hot start 1975 LD FTP

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          TABLE D-5. SULFUR DISTRIBUTION* FOR 1975 350 CID CHEVROLET USING EM-214-F
Date Miles Run
12-17-74 0 1
12-17-74 0 2
Avg.
12-20-74 1000 1
O
<> 12-30-74 1000 2
Avg.
12-30-74 2000 1
12-30-74 2000 2
Avg.
Fuel
s, g
2.28
2.17
2.23
2.32
2.27
2.30
2.33
2.34
2.34
S02,
bag
2.36
2.56
2.46
2.66
3.26
2.96
2.75
2.83
2.79
g
cont
3.57
3,04
3.31
4.07
4. 18
4.13
4.86
3.76
4.31
S from
S02, g
bag
1.18
1.28
1.23
1.33
1.63
1.48
1.38
1.41
1.40
cont
1.79
1.52
1.66
2.03
2.09
2.06
2.43
1.88
2.16
S04=
g
0.169
0. 178
0. 174
0. 121
0. 106
0. 114
0.265
0.237
0.251
S
sc
0.
0.
0.
0.
0.
0.
0.
0.
0.
from
54~' g
056
059
058
040
035
038
088
079
084
% Fuel S Appearing as
S02 (bag)
52
59
56
57
72
65
59
60
60
SO2 (cont)
79
70
75
88
92
90
104
80
92
804-
2.5
2.7
2.6
1.7
1.5
1.6
3.8
3.4
3.6
* Based on hot start 1975 LD FTP

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            TABLE D-6. SULFUR DISTRIBUTION* FOR 1975 350 CID CHEVROLET USING EM-215-F
d
i
-o
Fuel
Date Miles
2-7-75 0



2-14-75 1000



2-17-75 2000




Run
1
2
3
Avg.
1
2
3
Avg.
1
2
3
4
Avg.
s,
2.
2.
2.
2.
2.
2.
2.
2.
2.
2.
2.
2.
2.
g
36
27
29
31
30
22
33
28
30
28
33
25
29
S02,
bag
4.73
4. 13
4.73
4.53
2.91
3. 19
3.45
3.18
3.43
4.23
4.51
4.02
4.05
K
S from
SOz, g
cont
4.
5.
5.
5.
4.
4.
4.
4.
4.
5.
5.
5.
5.
80
26
98
35
75
80
94
83
93
13
29
35
18
bag
2.37
2.07
2.37
2.27
1.46
1.60
1.73
1.60
1.72
2. 12
2.26
2.01
2.03
cont
2.40
2.63
2.99
2.67
2.38
2.40
2.47
2.42
2.47
2.57
2. 65
2.68 .
2.59
so4-
{
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
I
23
11
19
18
28
29
20
26
375
578
392
207
388
S from
so4-, g
0.076
0.037
0.063
0.058
0.093
0.097
0.067
0.086
0. 125
0. 193
0. 131
0.069
0. 130
                                                                                    % Fuel S appearing as
SOzfbag)
101
91
103
98
63
72
74
70
75
93 -
97
89
89
SO? (cont)
102
116
131
116
103
108
106
106
107
113
114
119
113
S04~
3
2
3
3
4
4
3
4
5
8
6
3
6
      * Based on hot start 1975 LD FTP

-------
             TABLE D-7. SULFUR DISTRIBUTION* FOR 1975 350 CID CHEVROLET USING EM-216-F
S from

Date Miles Run
1/9/75 0 1
2
Avg.
1/14/75 1000 1
? 2
00 Avg.
1/17/75 2000 1
2
Avg.
Fuel
S. g
2.72
2.34
2.53
2.32
2.34
2.33
2.46
2.40
2.43
S02,
bag
3.93
3.05
3.49
3.54
4.06
3. 80
2.96
2.73
2.85
g
cont
5.71
5.28
5.50
5.03
5.15
5.09
4.12
4.47
4.30
S02,
bag
1.97
1.53
1.75
1.77
2.03
1.90
1.48
1.37
1.43
g
cont
2.85
2.64
2.75
2.52
2.58
2.55
2.06
2.24
2.15
S04 =

0.
0.
0.
0.
0.
0.
0.
0.
0.
g
0547
1025
0786
0927
1973
1450
1531
2088
1810
S from
SO4~, g
0.0182
0.0342
0.0262
0.0309
0.0658
0. 0484
0.0510
0.0696
0.0603
% Fuel
S02 (bag)
72
65
69
76
87
82
60
57
59
S appearing
SO2 (cont)
105
113
109
109
110
110
84
93
89
as
so4-
0.7
1.5
1.1
1.3
2.8
2. 1
2.1
2.9
2.5
* Based on hot start 1975 LD FTP

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            TABLE D-8. SULFUR DISTRIBUTION* FOR 1975 350 CID CHEVROLET USING EM-218-F
S from

Date Miles Run
3/10/75 0 1
2
3
Avg.
? 3/17/75 1000 1
^O o

3
Avg.
3/20/75 2000 1
2
3
Avg.
Fuel
S, g
2.44
2.34
2.35
2.38
2.18
2.20
2.21
2.20
2.26
2.19
2.21
2.22
SO?,
bag
4.15
4.25
3.21
3.87
3.04
3.91
3.72
3.56
1.64
2.77
3.12
2.51
g
cont
4.53
4.97
4.30
4.60
4.13
4.42
4.60
4.38
3.11
3.37
3.85
3.44
so2,
bag
2.08
2.13
1.61
1.94
1.52
1.96
1.86
1.78
0.82
1.39
1.93
1.38
g
cont
2.27
2.49
2.15
2.30
2.07
2.21
2.30
2.19
1.56
1.69
1.92
1.72
SO4 =

0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
g
332
466
378
392
317
489
386
397
460
564
584
536
S from
S04~, g
0.110
0. 154
0.125
0.129
0.105
0.161
0. 127
0.131
0.152
0.186
0.193
0.177
% Fuel
SO? (bag)
85
91
69
82
70
89
84
81
36
63
87
62
S appearing
SO? (cont)
93
106
91
97
95
100
96
97
69
77
87
78
as
S04=
5
7
5
6
5
7
6
6
7
8
9
8
* Based on hot start 1975 LD FTP

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                                   TECHNICAL REPORT DATA
                            (/'lease read Instructions on (he reverse before completing)
1. REPORT NO.
  EPA-600/2-75-048
    2.
                                 3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
  PROTOCOL TO CHARACTERIZE  GASEOUS EMISSIONS AS A
  FUNCTION OF FUEL AND ADDITIVE COMPOSITION
                                 5. REPORT DATE
                                   September 1975
                                 6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
                                 8. PERFORMING ORGANIZATION REPORT NO.
  Harry E. Dietzmann
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Southwest Research  Institute
  8500 Culebra Road
  San Antonio, Texas  78284
                                 10. PROGRAM ELEMENT NO.

                                   1AA002
                                 11. CONTRACT/GRANT NO.

                                   68-02-1275
12. SPONSORING AGENCY NAME AND ADDRESS
  Environmental Sciences  Research Laboratory
  Office of Research  and  Development
  U.S. Environmental  Protection Agency
  Research Triangle Park, N.C.  27711	
                                 13. TYPE OF REPORT AND PERIOD COVERED
                                   Final-Feb. 1974-June 1975
                                 14. SPONSORING AGENCY CODE
                                   EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
       This project  sought to validate an engine dynamometer test schedule for
  additive effects previously used in Dow and Bu Mines programs.   Previous problems
  with vehicle-to-engine  dynamometer comparability were  solved by the use of a
  Clayton power absorption unit and a fixed flywheel as  an  inertia simulator.   Thus,
  adequate road simulation was achieved.  Numerous analytical  techniques were
  developed including  analysis for S02> H2S, COS, methyl  and ethyl mercaptan, ammonia,
  N, N-dimethylnitrosamine, hydrocarbon distribution, and sulfate.  No additive-
  derived products were found in the study of two commercial  additive packages  with
  either catalyst or non-catalyst engine configurations.  The mileage accumulation
  schedule used resulted  in overly-high rates of accumulation of intake manifold
  deposits for both  additive and base fuels.  It is suggested that greater mileage
  accumulations over a heavier duty cycle will be necessary to detect the effects
  of additives on catalyst deterioration.
17.
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                   b.lDENTIFIERS/OPEN ENDED TERMS  C.  COSATI Field/Group
  Evaluation
  Proving
 Automotive  fuels
 *Fuel additives
  Automotive  engines
 *Catalytic converters
 *Exhaust emissions
Air pollution
Chemical analysis
Dynamometers
  14G
  12A
  21D
  21K
  07A
  131
  21B
13B
07D
14B
18. DISTRIBUTION STATEMENT


     RELEASE TO PUBLIC
                                              21. NO. OF PAGES
                                                 136
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22. PRICE
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-------