United States
Environmental Protection
Agency
Health Effects Research
Laboratory
Research Triangle Park NC 27711
EPA-600/3-79-001b
January 1979
Research and Development
Modeling of
Simulated
Photochemical
Smog with Kinetic
Mechanisms

Volume 2.
Interim Report
Apnendix

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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 nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination  of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.   Environmental  Health Effects Research
      2.   Environmental  Protection Technology
      3.   Ecological Research
      4.   Environmental  Monitoring
      5.   Socioeconomic Environmental Studies
      6.   Scientific and Technical  Assessment Reports (STAR)
      7    Interagency  Energy-Environment Research and Development
      8.   "Special" Reports
      9.   Miscellaneous Reports

This report has been assigned to the  ECOLOGICAL RESEARCH series. This series
describes research on  the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed  for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic, terrestrial, and atmospheric environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia  22161.

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                                            EPA-600/3-79-0015
                                            January  1979
MODELING  OF SIMULATED  PHOTOCHEMICAL
    SMOG WITH KINETIC MECHANISMS
   Volume 2.   Interim  Report Appendix
                    by

               G. Z. Whitten
                  H. Hogo
               M. J. Meldgin
               J. P. Kill us
               P. J. Bekowies

      Systems Applications, Incorporated
            950  Northgate Drive
        San  Rafael,  California  94903
            Contract No. 68-02-2428
               Project Officer

               Mareia C. Dodge
 Atmospheric Chemistry and Physics  Division
 Environmental Sciences Research Laboratory
 Research Triangle Park, North Carolina   27711


 ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
 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.

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                                ABSTRACT


     Computer modeling of smog chamber data is discussed in three parts.
First, a series of detailed chemical  mechanisms were  developed  to describe
the photochemical formation of ozone from nitrogen oxides and the follow-
ing compounds (alone and in various combinations):  formaldehyde, acetal-
dehyde, ethylene, propylene, butane, 1-butene, trans-2-butene,  and
2,3-dimethylbutane.  The aldehyde mechanisms were verified independently
using data from experiments containing only nitrogen  oxides and the
appropriate aldehyde.  The hydrocarbon mechanisms were then developed by
adding the chemical reactions detailing the photooxidation steps of the
particular hydrocarbon to the aldehyde mechanisms.  Second, a generalized
kinetic scheme intended for use in models simulating  the formation of ozone
in urban atmospheres was refined.  The generalized mechanism includes a
condensed version of the explicit mechanisms developed in the first part
plus a semi-emipirical scheme to describe the oxidation of aromatic hydro-
carbons.  Third, the effects of smog chambers on ozone formation were
examined.  For this part of the study, similar experiments using propylene
and nitrogen oxides in eight different smog chambers  were simulated.  The
main chamber effects identified thus far are apparently due to nitrogen
oxides degassing from the walls during experiments and differences between
chambers in the spectral distribution of ultraviolet irradiation.

     Volume 1 contains all textual material; this volume contains graphs
of measured and simulated pollutant concentrations for many smog chamber
experiments.  The  two-volume report was submitted to the U.S. Environ-
mental Protection Agency in fulfillment of Contract No. 68-02-2428 by
Systems Applications, Incorporated.  This report covers the period
23 August 1976 to 23 August 1978, and work was completed as of
18 August 1978.
                                 m

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                                CONTENTS


ABSTRACT	        iii
ABBREVIATIONS  	        vii
APPENDIX:  SIMULATION RESULTS  	          !
     Part A:  Simulation Results with Explicit Mechanisms  	          2
          1.  Formaldehyde Experiments by Bufalini,  Gay,
              and Brubaker (1972).  Simulated with explicit
              formaldehyde mechanism  	         3
          2.  Experiments by Bufalini, Gay, and Brubaker  (1972).
              Simulated with explicit formaldehyde mechanism
              with added reactions for peroxynitric acid  (HOONO?)  •  •         8
          3.  UCR Formaldehyde Experiments  	        11
          4.  UNC Formaldehyde Experiment   	        21
          5.  UCR Acetaldehyde Experiments  	        23
          6.  UCR Ethylene Experiments	        31
          7.  UCR Propylene Experiments   	        49
          8.  UCR Butane Experiments	       114
          9.  UCR 1-Butane Experiments	       153
         10.  UCR Trans-2-Butene Experiments  	       160
         11.  UCR 2,3-Dimethylbutane Experiments	       168
         12.  UCR Ethylene/Propylene Experiments  	       179
         13.  UCR Propylene/Butane Experiments  	       190
         14.  UCR Propylene/Trans-2-Butene Experiment 	       225
         15.  UCR Multiolefin Experiments 	       230
     Part B:  Simulation Results with the Carbon-Bond Mechanism .  .  .       250
          1.  UCR Formaldehyde Experiments  	       251
          2.  UCR Acetaldehyde Experiments  	       260
          3.  UCR Ethylene Experiments	       265
          4.  UCR Propylene Experiments   	       269
          5.  UCR Butane Experiments	       280
          6.  UCR 1-Butene Experiments	       285
          7-  UCR Trans-2-Butene Experiments (with trans-2-butene
              treated as an olefin)	       288

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     8.   UCR Trans-2-Butene Experiments  (with  trans-2-butene
         treated as  a  carbonyl)	     291
     9.   UCR 2,3-Dimethylbutane  Experiments   	     293
    10.   UCR Toluene Experiments	     296
    11.   UCR Propylene/Butane  Experiments   	     316
    12.   UCR Multiolefin  Experiments  	     321
    13.   UCR Seven-Hydrocarbon  Experiments  	     326
Part C.   Simulation  Results of Propylene Experiments  Performed
         at Various  Chambers   	     371
     1.   UNC Chamber Experiments	     372
     2.   RTI Chamber Experiments	     378
     3.   Battelle Chamber Experiments   	     382
     4.   NAPCA Chamber Experiments  	     386
     5.   UCR-AGC Chamber  Experiments  	     394
     6.   CALSPAN Chamber  Experiments  	     397
     7.   Lockheed Chamber Experiments   	     401
                                 VI

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                                ABBREVIATIONS
ALD2       Acetaldehyde                       03
ALD3       Propionaldehyde                    OLE
ALD4       Butyraldehyde                      PAN
AONE       Acetone                            PAR
ARO        Arornatics                          PPN
BLA        Blacklamp irradiation              PROP
BUT        n-Butane                           SCN3
BUT1       1-Butene                           SPN3
BUT2       Trans-2-butene                     SUN
CO         Carbon monoxide                    SUNLAMP
C2N3       Ethyl nitrate                      UCR
C4N3       n-Butyl nitrate
C6N3       2,3-Dimethylbutyl nitrate          UNCB
DBUT       2,3-Dimethylbutane
EC         Evacuable chamber (at UCR)         UNCR
ETH        Ethylene
FORM       Formaldehyde
HCHO       Formaldehyde
H202       Hydrogen peroxide
MEK        Methyl ethylketone
MEN3       Methyl nitrate
NO         Nitrogen oxide
NOX        Oxides of nitrogen (NO + N02)
N02        Nitrogen dioxide
Ozone
Olefins
Peroxyacetyl nitrate
Paraffins
Peroxypropionyl nitrate
Propylene
Sec-butyl nitrate
Isopropyl nitrate
Sunlamp irradiation
Sunlamp irradiation
University of California
at Riverside
University of North Carolina
("blue" side of
chamber)
University of North Carolina
("red" side of chamber)
                                        vii

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                                APPENDIX
                           SIMULATION RESULTS
     Volume I of this two-volume report discusses the results  of this
study.   This volume (II) is the data volume:   It presents  graphs of
simulated and measured pollutant concentrations in smog chamber exper-
iments.  In all figures, the symbols represent measured concentrations
and the solid lines represent simulation concentrations.   The  pollutants
are identified in the graphs by two- to four-space codes,  which are given
in the list of abbreviations.  Simulations with explicit mechanisms (Part
A)  are presented first, followed by simulations with the  Carbon-Bond
Mechanism (Part B), and simulations with the explicit propylene mechanism
in the study of chamber effects (Part C).

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                  Part A
Simulation Results with Explicit Mechanisms

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FORMALDEHYDE EXPERIMENTS BY BUFALINI, GAY,  AND BRUBAKER (1972),
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EXPERIMENTS BY BUFALINI,  GAY,  AND BRUBAKER  (1972).
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           EC-168
           C2N3   «
  0.002
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         EC-17B
  o.6or
   0.45
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a.
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                              TIME (MINUTES)
          EC-17B
  o.ioor
  0.075 -
  0.050
N02    +
N0     •
o
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B
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  0.025 -
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              70     140     210     260     350     420

                               TIME  (MINUTES)
                         490     560
                                       148

-------
          EC-178
   2.00r
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210     260     350

  TIME (MINUTES)
420     490     560
          EC-178
      PfiN    +
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  0.050 -
UJ
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                                     149

-------
          EC-17B
F0RM
  0.028r
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                              TIME  (MINUTES)
          EC-178
HEK    •
   o.i2r
   0.09 -
   0.06 -
   0.03 -
   0.00
                     140     210    260     350     420    490     560

                              TIME  (MINUTES)
                                   150

-------
           EC-17B
C2N3   +
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CL-
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-------
          EC-178
                       SCN3
  o.020r
                                                      *  *  *
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  70      140      210     280     350     420     490     560

                    TIME  (MINUTES)
                                   152

-------
UCR 1-BUTENE EXPERIMENTS
                         153

-------
          EC-122
NB2    x
Nfl     *
83     •
   0.40p
   0.30
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                               TIME (MINUTES)
          EC-122
  0.220
  0.165
i- 0.110
  0.055
BL03   x
FBRM   +
BUT1   •
  0.000.
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                               TIHE (MINUTES)
                                480
                                     154

-------
           EC-122
PPN   x
PflN   *
RLD2  •
   0.044r
   0.033 -
   0.022 -
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              60     120     180     240     300    360    420     480
          EC-122
C2N3
RL04
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S
  0.0000
                                155

-------
         EC-123
N02   x
N0    *
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fc
  0.20 -
kl
U
  0.10 -
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             60      120     180     240    300     360     420    480
                                156

-------
           EC-123
RLOZ   x
PPN    *
PHN    •
   O.lOOr
   0.075
 t- 0.050
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   0.006
        0      60     120     180    240     300

                                TIME (MINUTES)
                 360    420     480
           EC-123
C2N3   *
BLD4   •
  0.0028r
  0.0021
                                      «           X   *      XX
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                                TIME (MINUTES)
                                       157

-------
        EC-124
N82   x
N0    *
83    •
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  0.60  -
a.
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  O.QO
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            80     160    2*0    320    400    480    560     640
                            TIME (MINUTES)
         EC-124
  0.44 -
  0.33
  0.22
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  0.11
  0.00
RL03  x
F0RH  *
BUT1  •
      0     80     160    240    320     400     480     560     640
                            TIME (MINUTE3I
                                   158

-------
           EC-124
BLD2   x
PPN    +
PRN    •
   O.lOOr
   0.075 -
   0.050 -
   0.025 -
   0.000
               80     160    240     320     400    480     560     640
           EC-124
C2N3  x
MEN3  *
HLD4  •
  0.0044r
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I

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  0.0022 -
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  0.0011  -
  0.0000
        0      80      160     240    320     400     480     560     640
                                  159

-------
UCR TRANS-2-BUTENE EXPERIMENTS
                          160

-------
         EC-146
N02    x
N0     +
03     •
  0.40r
  0.30
CL.
a.
t- 0.20
oc
z
IB
o
  0.10
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             50      100     150    200     Z50     300     350

                              TIME (MINUTES)
                               400
         EC-146
  0.36r
  0.27
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GC
ALD2   +
BUT2   »
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-------
           EC-H6
      PAN
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   0.025
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                                       I	I	I	I
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150    ZOO     250

  TIME (MINUTES)
300     350     400
           EC-146
      HEN3
  0.0032r
  0.0024
4- 0.0016
  o.oooe
  o.oooo
                                            *    *   *
                                       i       i
               50     100     150    200     250    300     350     400

                                TIME (MINUTES)
                                       162

-------
         EC-147
                            83     a
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  0.15
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cc
ae
  0.05
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                            150     ZOO    250

                              TIME (MINUTES)
                                            300     350     400
         EC-H7
                            N02
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x
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Ul
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             50      100
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                        TIME (MINUTES)
300     350     400
                              163

-------
         EC-147
      ALD2   +
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  0.56r
  0.42 -
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  TIME (MINUTES)
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         EC-147
      F0RH   +
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  TIME (MINUTES)
                       300     350     400
                                  164

-------
           EC-H7
HEN3   •
  o.oioor
  0.0075 -
CL.
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  0.0025
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                                 TIME (MINUTES)
                                 400
                                     165

-------
         EC-157
      N02    x
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  0.44 r
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150    200     250

  TIME IHINUTES)
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         EC-157
  0.28
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  0.07
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             50     100    150     200     250    300     350    400

                             TIME (MINUTES)
                                    166

-------
          E0157
              FiRH   «•
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100     150     ZOO     250     300     350

          TIME  (MINUTES)
                                                                    400
          EC-157
                                    HEN3
 0.0028r
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                      100     150     ZOO     Z50     300     350     400

                               TIME  (MINUTES)
                                     167

-------
UCR 2,3-DIMETHYLBUTANE EXPERIMENTS
                         168

-------
          EC-165
                            83
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240     320    400

  TIME (MINUTES)
                                                             I	1
480     5SO     640
          EC-165
  o.ioor
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a.
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cc
  0.025
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                                                «*»«**»*«*«**
       0      80      160     240     320     400     480     560     640

                               TIME  (MINUTES)
                                  169

-------
          EC-165
OBUT   •
   2.oor
   1.75
   1.50
 OB
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   1.25
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              80      160     240    320     400     480    560
                              TIME  (MINUTES)
                               640
          EC-165
  0.032p
SPN3   *
PRN    •
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              80      160     240    320     400     480     560     640
                              TIHE (MINUTES)
                                  170

-------
          EC-165
C6N3   a
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                                                        X  *  *
z
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                               TIME (MINUTES)
         EC-165
R8NE
  0.52r
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A.
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cr
St.
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KB

-------
         EC-169
83     •
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                              TIME  (MINUTES)
                                 720
         EC-169
N02

NB
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                              TIME  (MINUTES)
                         630     720
                                  172

-------
          EC-169
      DBUT
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270     360    450

  TIME (MINUTES)
540     630     720
          EC-169
      fiLD2
      PHN
  0.028r
  0.021
»- O.OH
G:
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               90      180     270     360     450     540     630     720

                                TIKE (MINUTES)
                                   173

-------
           EC-169
                                    SPN3   •
  0.0100
  0.0075
  0.0050
u
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  0.0025
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               90     180     270     360     450     540    630     720
                                TIME (MINUTES)
           EC-169
C6N3
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               90     180     270     360     450     540     630     720
                                TIME (MINUTES)
                                   174

-------
         EC-171
03
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                              TINE (MINUTES)
                        560     640
         EC-171
 0.100
N02
N8
             80      160     240     320    400     480     560    640
 0.000
                                175

-------
         EC-171
DBUT   •
  0.50
O_
0.
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u
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ts
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      0      80     160     240     320     400     480

                              TIME CHINUTES)
                         560     640
         EC-171
C6N3   +
PRN    •
  0.04r
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IB
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                              TIHE (MINUTES)
                                 176

-------
           EC-171
      RLD2
      F0RM
    o.04p
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    0.02 -
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240    320     400

  TIKE (MINUTES)
                                                   480     560     640
           EC-171
  o.oioor
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                               TIKE (MINUTES)
                                177

-------
         EC-171
      H0NE
  0.40r
  0.30
a.
a.
  0.20
  0.10
  0.00
                     I	I	i	   i
80     160
240     320     400

  TIME IH1NUTES)
                                                  480     560     640
                                178

-------
UCR ETHYLENE/PROPYLENE EXPERIMENTS
                         179

-------
         EC-144
83     •
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t~ 0.60
«
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UJ

-------
         EC-144
ETH    a
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  1.65
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                              TIHE (MINUTES)
         EC-114
  0.24r
PRBP
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0      50      100
                            150     200     250

                              TIHE (MINUTES)
                 300    350     400
                                 181

-------
          EC-144
PRN    •
  o.ioop
  0.075
                                       *   *
i- 0.050
ui
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                               TIME (MINUTES)
          EC-144
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FBRN   •
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                               TIME (MINUTES)
                                     182

-------
                                 RL02
0.12
0.09
0.06
0.03
0.00.
            I	I	1	I	i	I
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                             TIME (MINUTES)
                              183

-------
         EC-U5
      N02    x
      N0     +
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  TIME (MINUTES)
                                                   300     350     400
         EC-145
  1.20
      ETH
  0.90
i- 0.60
oc
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             50      100     150     200     250    300     350     400
                              TIME  (MINUTES!
                                      184

-------
     EC-145
O.Mr
     EC-MS
                      TIRE
                       185

-------
          EC-145
      RLD2
      PRN
   0.16
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   0.06
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150    200     250

  TIME (NINUTES)
300     350     400
          EC-145
  0.008
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              50      100     150     200     250     300    350     400
                               TIME (MINUTES)
                                      186

-------
          EC-160
      NB2    x
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  0.75
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-------
         EC-ISO
      FORM

      PRBP
  0.60
K- 0.40
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  0.20
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      0      50     100
150    200     250

  TIME (MINUTES)
300    350     400
         EC-160
      RLD2
      PRH
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cc
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ISO    200     250

  TIME (MINUTES)
300     350    400
                             188

-------
         EC-160
MEN3   *
RL03   «
O.OlOOr
0.0075
0.0050
                                          *   m
                                 IK   *
0.0025
0.0000
             50     100     150     ZOO    250     300     350     400

                             TIME  (MINUTES)
                                    189

-------
UCR PROPYLENE/BUTANE EXPERIMENTS
                           190

-------
         EC-97
             N02    x
             N0     i-
             03     •
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  0.60 -
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100    150     200     250     300     350
         TIME (MINUTES)
                                                                 400
         EC-97
             PR0P
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      0      50     100
       150     200     250
         TIME (MINUTES)
300     350     400
                              191

-------
        EC-97
BUT   •
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                             TIME  (MINUTES)
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MEK   +
PRN   *
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  0.00
                                  192

-------
           EC-97
fll04   *
RL03   •
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  0.0075
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UJ
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               50      100     150    200     250     300    350     400

                               TIME (MINUTES)
           EC-97
FfRM
RLOZ
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                               TIME  (MINUTES)
                                 193

-------
           EC-97
SCN3
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                               TIME (MINUTES)
           EC-97
C2N3
MEN3
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ct
oc
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                                            K   *   *   *   *
        0      50     100    150     200    250     300     350     400
                               TIME (MINUTES)
                                    194

-------
         EC-99
N02   x
N0    +
83    H
             50     100     ISO     200     250    300     350     400
  0.00
         EC-99
PR0P
RLD2
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flc
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             50     100     150     200     250
                             TIME (HIWUTES)
                300     350     400
                             195

-------
         EC-99
F8RM
PRN
  0.32p
             50      100     150     200    250    300     350    400
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BUT
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s
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             50      100     150     200    250     300     350     400

                             TIME  (HINUTES)
                                  196

-------
           EC-99
                                    HEX
    0.00
                      100     ISO     ZOO     250     300     350

                                TIHE  (MINUTES)
                                                    400
           EC-99
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                 TIHE  (MINUTES)
                                                                   400
                                  197

-------
          EC-99
  o.024p
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f- 0.012
£
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                               TIME  (MINUTES)
          EC-99
  0.004
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s
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  0.001
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150    200     250
  TIHE (MINUTES)
300     350    400
                                    198

-------
         EC-106
NB2    x
N0     +
83     •
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  0.60

-------
         EC-106
BUT
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t- 1.80

-------
           EC-106
                                    MEK
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                                TIME  (MINUTES)
                                ISO
           EC-106
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a.
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  0.0025
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fiLD3
RLD1
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               60     120     180     240     300     360     420
                                TIME  (MINUTES)
                                480
                                       201

-------
           EC-106
      C2N3   *
      MEN3   «
  O.OOZOp
  0.0015
o.
0.
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                    Part B
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350
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          E0251
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                              TIME  (MINUTES)
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           EC-252
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                                TIME  (MINUTES)
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         EC-255
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                            TIME (MINUTES)
                                                  300     350     400
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                               TIME  (MINUTES)
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UCR ACETALDEHYDE EXPERIMENTS
                            260

-------
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                              TIME (MINUTES)
                                    262

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-------
UCR ETHYLENE EXPERIMENTS
                           265

-------
         EC-H2
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                              TIME  (MINUTES)
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  TIME (MINUTES)
300     350     400
                                    267

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         EC-H3
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                               TIME (MINUTES)
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-------
UCR PROPYLENE EXPERIMENTS
                            269

-------
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                               TIME  (MINUTES)
                       300     350
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-------
           EC-256
      OLE
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300     350     400
                                      271

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         EC-276
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         EC-277
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                              TIME (MINUTES)
                                   275

-------
         EC-278
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                             TIME (MINUTES)
                                  276

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         EC-278
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  TIME (MINUTES)
                                                  300
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         EC-279
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                             TIME (MINUTES)
                                   278

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         EC-279
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-------
UCR BUTANE EXPERIMENTS
                          280

-------
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                 TIME  (MINUTES)
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                                282

-------
          EC-178
   0.60r
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                               TIME (MINUTES)
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                                 284

-------
UCR 1-BUTENE EXPERIMENTS
                          285

-------
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          EC-123
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-------
UCR TRANS-2-BUTENE EXPERIMENTS
(With trans-2-butene treated as an  olefin)
                          288

-------
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                                                   300     350     400
                                   289

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                                 290

-------
UCR TRANS-2-BUTENE EXPERIMENTS
(with trans-2-butene treated as a carbonyl)
                        291

-------
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  TIME (MINUTES)
                                                    300    350     400
                                292

-------
UCR 2,3-DIMETHYLBUTANE EXPERIMENTS
                          293

-------
         EC-169
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                                 294

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                                 295

-------
UCR TOLUENE EXPERIMENTS
                        296

-------
          EC-77
  o.020r
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                               TIME  (MINUTES)
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                               TIME (MINUTES)
                                      299

-------
        EC-78
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                               TIME  (MINUTES)
                                     301

-------
         EC-79
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                             TIME (MINUTES)
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                                    302

-------
          EC-BO
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                                      303

-------
         EC-BO
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150    200     250     300
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                                   304

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                 TIME  (MINUTES)
300     350     400
                                     305

-------
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                              TIME  (MINUTES)
                        350     400
                                   306

-------
          EC-82
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300     350     400
                                    307

-------
         EC-B2
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                              TIME  (MINUTES)
                                   308

-------
         EC-83
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  TIME (MINUTES)
                                                                 400
                                     309

-------
         EC-83
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  TIME (MINUTES)
300     350    400
                                   310

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                               TIME  (HINUTES)
                                400
                                       311

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         EC-64
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                              TIME  (MINUTES)
                300     350    400
                               312

-------
          EC-B5
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                               TIME  (MINUTES)
                                     400
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  TIME (H1NUTES)
300     350     400
                                 313

-------
         EC-65
TBL
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-------
                    Part C

Simulation Results of Propylene Experiments
        Performed at Various Chambers
                     371

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RTI CHAMBER EXPERIMENTS
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CALSPAN CHAMBER EXPERIMENTS
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-------
                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-600/3-79-001b
                                                           3. RECIPIENT'S ACCESSION-NO.
 4. TITLE AND SUBTITLE
  MODELING OF SIMULATED PHOTOCHEMICAL  SMOG WITH KINETIC
  MECHANISMS   Volume 2.   Interim  Report Appendix
                                                           5. REPORT DATE
               January 1979
             6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
  G.  Z.  Whitten, H. Hogo, M.J.  Meldgin,  J.P. Killus,
  and P.O. Bekowies
             8. PERFORMING ORGANIZATION REPORT NO.


                  EF78-121B
 9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Systems Applications,  Incorporated
  950 Northgate Drive
  San Rafael, California   94903
             10. PROGRAM ELEMENT NO.

               1AA6Q3	AC-19 (FY-78)
              1. CONTRACT/GRANT NO.
             11. CONTRACT/GRANT

               Contract No. 68-02-2428
 12. SPONSORING AGENCY NAME AND ADDRESS
                                                           13. TYPE OF REPORT AND PERIOD COVERED
  Environmental Sciences  Research  Laboratory-RTP, NC
  Office of Research and  Development
  U.S. Environmental Protection  Agency
  Research Triangle Park,  N.C.   27711
               Interim   7/76-7/78
             14. SPONSORING AGENCY CODE
                EPA/600/09
 15. SUPPLEMENTARY NOTES
  Volume 1.   Interim  Report    EPA-600/3-79-001a
 16. ABSTRACT
       Computer modeling  of  smog  chamber data is discussed  in  three  parts.   First,
  a series of detailed  chemical mechanisms were developed to describe  the photo-
  chemical formation of ozone  from nitrogen oxides and the  following organic
  compounds (alone and  in various combinations):  formaldehyde,  acetaldehyde,
  ethylene, propylene,  butane,  1-butene, trans-2-butene, and 2,3-dimethylbutane.
  Second, a generalized kinetic scheme intended for use in  models  simulating
  the formation of ozone  in  urban atmospheres was refined.  The  generalized
  mechanism includes a  condensed  version of the detailed mechanisms  developed
  in the first part plus  a semi-empirical  scheme to describe the oxidation  of
  aromatic hydrocarbons.   Third,  the effects of smog chambers  on ozone formation
  were examined.  For this part of the study, similar experiments  using nitrogen
  oxides and propylene  in eight different smog chambers were simulated using
  the detailed propylene  mechanism.   The main chamber effects  identified thus
  far are apparently due  to  nitrogen oxides degassing from  the walls during
  experiments and differences  between chambers in the spectral distribution
  of ultraviolet irradiation.
       Volume 1 contains  all textual material.  Volume 2 contains  graphs of measured anc
  simulated pollutant concentrations for many smog chamber  experiments.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                          c.  COSATI Field/Group
     Air pollution
     Reaction kinetics
     Photochemical reactions
     Test chambers
     Mathematical models
     Computerized simulation
                            13B
                            07D
                            07E
                            14B
                            12A
                            09B
18. DISTRIBUTION STATEMENT

  RELEASE TO PUBLIC
19. SECURITY CLASS (This Report I
 UNCLASSIFIED
21. NO. OF PAGES

     414
                                              20. SECURITY CLASS (Thispage)
                                               UNCLASSIFIED
                                                                        22. PRICE
EPA Form 2220-1 (9-73)
                                            406

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