EPA-R4-73-030a


July 1973
ENVIRONMENTAL MONITORING SERIES



                                         $i$l$j£^
                                         '^^i^^^^^i^^^^^^^

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                                         EPA-R4-73-030a
URBAN  AIR  SHED PHOTOCHEMICAL
     SIMULATION  MODEL  STUDY
  VOLUME  I  -  DEVELOPMENT  AND  EVALUATION
                        by

               S.D. Reynolds, Mei-Kao Lui,
          T.A. Hecht, P.M. Roth, and J.H. Seinfield

               Systems Applications, Inc.
                9418 Wilshire Boulevard
              Beverly Hills, California 90212
                Contract No. 68-02-0339
               Program Element No. 1A1009
           EPA Project Officer:  Herbert Viebrock

                 Meteorology Laboratory
           National Environmental Research Center
         Research Triangle Park, North Carolina 27711
                    Prepared for

          OFFICE OF RESEARCH AND DEVELOPMENT
         U.S. ENVIRONMENTAL PROTECTION AGENCY
               WASHINGTON, D.C.  20460

                     July 1973

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This report has been review jd by the Environmental Protection Agency and




approved for publication.  Approval does not signify that the contents




necessarily reflect the views and policies of the Agency, nor does




mention of trade names or commercial products constitute endorsement




or recommendation for use.
                                 11

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                                ABSTRACT

     During the period July 1970 to June 1971, Systems Applications,
Inc., under Contract CPA 70-148, undertook "Development of a Simulation
Model For Estimating Ground Level Concentrations of Photochemical
Pollutants".  The results of this work have been presented in Roth et
al.  (1971), a seven volume project report which describes in detail
all aspects of the year's efforts.  The abstract of that report states
the following:

          "In this report we describe the progress that has been
          achieved to date in the development and validation of
          a simulation model for estimating ground level concen-
          trations of photochemical pollutants.  This model is
          based on the finite difference solution of the equations
          of conservation of mass, using the method of fractional
          steps.  The bulk of the effort reported here is develop-
          mental, involving the compilation of a comprehensive
          source emissions inventory, the development and valida-
          tion of a kinetic mechanism for photochemical reactions,
          the adaptation of the method of fractional steps for
          use in the solution of the governing equations, and the
          preparation of maps displaying spatial and temporal vari-
          ations in wind speed and direction and in the height of
          the inversion base.  The details of these various efforts
          are described in a series of appendices to this report.
          Although a validated kinetic mechanism has been developed
          and incorporated in the simulation model, validation
          efforts have thus far been restricted to carbon monoxide.
          Provisional validation results for the Los Angeles Basin
          are presented."

     The work that has been carried out under the present contract is
a continuation of the earlier developmental study.  However, while
the emphasis in the initial project was on model development, we have
been concerned in the present study with

          Limited model development and improvement

          Extensive evaluation of the photochemical kinetics
          mechanism, involving fourteen experimental studies
          and four hydrocarbon systems

          Extensive evaluation of the urban airshed model for the
          Los Angeles Basin for six days on which pollution levels
          were high.  Five pollutants were considered — carbon monoxide,
          nitric oxide, nitrogen dioxide, hydrocarbon, and ozone.

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It is the purpose of this report to fully document the procedures
and results of this effort.

   This report consists of two parts — Volume I, which discusses
all technical aspects of the work (this document) and Volume II, which
presents a description of the computer programs that embody the model
and contains a user's guide.

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                                CONTENTS


                                                             Page

INTRODUCTION  	    1

I.   AN OVERVIEW	    3

II.  THE AIRSHED MODEL	    5

     A.   Theoretical Formulation of the Model  	  .    5

     B.   The Model Developed in this Study	   14

     C.   Modifications and Extensions to Original
          Formulation of Model  	   23

          1.   Emissions	   23
          2.   Photochemistry	   24
          3.   Meteorology	   24
          4.   Numerical Analysis   	   30
          5.   The Model	   34
          6.   Modeling of Subgrid  Scale Phenomena  ....   37
          7.   Computer Programs 	   38
          8.   Air Quality Data	   39

III. EVALUATION OF THE MODEL	   42

     A.   The Evaluation Procedure	   43

     B.   The Results	   53

     C.   Discussion of Results	   69

IV.  RECOMMENDATIONS FOR FUTURE WORK	   95

V.   REFERENCES	   98

THE EVALUATION RESULTS,	

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CONTENTS (Continued)


This final report includes the following Appendices:

Appendix A     Extensions and Modifications of a Contaminant
               Emissions Model and Inventory for Los Angeles

Appendix B     Further Validation of a Generalized Mechanism
               Suitable for Describing Atmospheric Photochemical
               Reactions

Appendix C     A Microscale Model for Describing the Contribution
               of Local Vehicular Sources to Pollutant Concentrations
               Measured at Monitoring Stations

Appendix D     Numerical Integration of the Continuity Equations

and

Volume II      User's Guide and Description of the Computer
               Programs

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INTRODUCTION

     During the period July 1970 to June 1971, Systems Applications,
Inc., under Contract CPA 70-148, undertook development of a computer-
based mathematical model capable of estimating ground level concentra-
tions of photochemical pollutants.  The results of this work have been
presented in Roth et al.(1971), a seven volume project report which
describes in detail all aspects of the year's efforts.  The work that
has been carried out under the present contract is a continuation of
the earlier developmental study.  However, while the emphasis in the
initial project was on model development, we have been concerned in
the present study with

     •    Limited model development and improvement

          Evaluation of the photochemical kinetics
          mechanism, involving fourteen experimental studies and
          four hydrocarbon systems

          Evaluation of the urban airshed model* for
          carbon monoxide, nitric oxide, nitrogen dioxide, hydro-
          carbon, and ozone for six validation days.

It is the purpose of this report to fully document the procedures and
results of this effort, which we will refer to hereafter as the
Phase II study.

     The report describing Phase II consists of six parts.  It is
broadly divided into two portions—Volume I, which discusses all
technical aspects of the work (this document) and Volume II, which
presents a description of the computer programs that embody the
model and contains a user's guide.  Volume I, however, has four tech-
nical appendices, each of which is an independent report describing a
particular aspect of the work.  The four appendices are:

Appendix A.  Extensions and Modifications of a Contaminant Emissions
     Model and Inventory for Los Angeles
*We will use the term "urban airshed model" both to refer to the model
 developed in Phase I and validated in Phase II and to describe any
 model capable of simulating transport, diffusion, and reaction in the
 atmosphere on a regional scale.

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Appendix B.  Further Validation of a Generalized Mechanism Suitable
     for Describing Atmospheric Photochemical Reactions

Appendix C.  A Microscale Model for Describing the Contribution of
     Local Vehicular Sources to Pollutant Concentrations Measured at
     Monitoring Stations

Appendix D.  Numerical Integration of the Continuity Equations.

     The main volume (I)  itself  is divided into two main parts.
The first  (Section II)  is concerned with the urban airshed model, its
theoretical foundation and its formulation, as well as with the modi-
fications and improvements made during Phase II.  The second (Section
III) focuses on the validation of the model—procedures, results, and
discussion and evaluation of results.  Discussion of the validation
of the photochemical kinetics mechanism is confined in its entirety to
Appendix B; it is not considered in the main text.  Moreover, with the
exception of the commentary in this volume dealing with the theoretical
foundations and formulation of the urban airshed model, there has been
no attempt made to repeat any portion of the seven volume Phase I
report by Roth et al. (1971).  The interested reader is referred to
this report if he wishes to obtain a full understanding of the model
and its initial development.

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I.   AN OVERVIEW

     Urban airshed models are mathematical representations of atmos-
pheric transport and chemical reaction processes which, when combined
with a source emissions inventory and pertinent meteorological data,
may be used to predict pollutant concentrations as a function of time
and location in the airshed. Models capable of accurate prediction over
a range of meteorological and source emission conditions will serve as
an important aid in urban and regional planning, including use in:

     1.   Simulating the effects of alternative emission control
          strategies on pollutant concentrations in the airshed

     2.   Real-time prediction in an alert warning system

     3.   Examining the air pollution impact of new sources, such as
          freeways and power plants.

     A dynamic airshed simulation model that is to be generally useful
in urban planning studies must meet several requirements.  First, it
should be capable of predicting accurately the ground level concentra-
tions of inert pollutants, as well as those formed in the atmosphere
by chemical reactions.  Second, the model should have a spatial and
temporal resolution appropriate for the analysis of concentration vari-
ations which occur in a city throughout the course of a day.  For a
typical large urban area, the horizontal spatial resolution may be of
the order of a mile, and the temporal resolution, of the order of an
hour.  The resolution of the model will, of course, be influenced by
the availability of data of similar resolution.  Third, the complexity
of the model, and thus the computing time and computer storage require-
ments, should be such that the model can be operated at a reasonable
cost using computers of general availability.  The objective of the
combined Phase I and Phase II programs is to develop and validate an
airshed simulation model for photochemical air pollution that satisfies
the stated requirements.

     As we have noted earlier, Phase I was primarily developmental.
We first selected a suitable modeling approach, one based on the numeri-
cal integration of the nonlinear, coupled equations of conservation of
mass.  We then compiled a comprehensive source emissions inventory for
the region to be modeled.  At the same time, we undertook the development
and validation of a kinetic mechanism for photochemical reactions and
selected and adapted a method for numerical integration of the continu-
ity equations.  We concluded initial development with (1) preparation of

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hourly maps displaying spatial and temporal variations in wind speed
and direction and in the height of the inversion base for two "vali-
dation days" and  (2) preparation and testing of the computer codes em-
bodying the model.  In addition, validation runs were carried out for
carbon monoxide for the two days selected.  We refer the reader to
Roth et al. (1971) for a full discussion of the development program.

     Some comments are in order at this point as to the selection of
an urban area for the purpose of validation.  The Los Angeles area was
chosen as the region for initial application of the model for three
reasons.  First, the meteorological and pollutant data base in Los
Angeles is one of the richest available for any major urban center.  A
network of nearly three dozen wind speed and direction sensors and
twelve air quality monitoring stations dot the Basin.  In addition,
during the summer of 1969, the Scott Research Laboratories carried
out an extensive data gathering program in Los Angeles (1970).  Particu-
larly valuable were the vertical temperature profile data they gathered
over three sites in the Basin, thereby permitting much more accurate
specification of the depth of the mixing layer than is normally possible.
Second, Los Angeles smog represents the most serious and persistent in-
cidence of photochemical air pollution in the United States.  Third,
because of its lack of proximity to other large urban areas, Los Angeles
has an air pollution problem which is entirely locally generated.  Thus,
we avoid the need to account for the influx of significant amounts of
pollutants from upwind areas.

     In contrast to Phase I, the present, or Phase II, study has focused
primarily on model evaluation   To be sure, a number of modifications
and improvements to the model have been made during this effort.  For
example, the source emissions inventory was revised and extended (par-
ticularly for automotive emissions), the numerical integration procedure
was modified, a microscale model was developed for describing the con-
tribution of local vehicular sources to pollutant concentrations measured
at monitoring stations, treatment of both the chemistry and meteorology
were modified, and an additional computer program was written for the
purpose of data plotting and presentation.  But, taken together, these
efforts constitute only a relatively minor portion of the overall study.
Primary attention was given to (1) evaluation of the photochemical kinetic
mechanism using smog chamber data and (2) evaluation of the airshed model,
first for an inert (carbon monoxide) to test the computer program and
to examine  the treatment of meteorological variables, then for nitric
oxide (NO), nitrogen dioxide (NO ), hydrocarbon (HC), and ozone (0 ) for
six pre-selected "validation days".  As we have indicated, evaluation
of the kinetic mechanism is discussed fully in Appendix B.  In this
report,  we devote our attention to evaluation of the airshed model.  But
first we discuss and describe the model itself.

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II.  THE AIRSHED MODEL

     In this section we present a complete description of the model
we have developed.  In the first part of the section we discuss the
theoretical foundation for the model, derive the governing equations,
and enumerate the assumptions upon which the model is based.  In the
second part, we present the model as it has been developed for appli-
cation purposes.  In particular, we transform the governing Equation (5)
into a form suitable  for  computation, describe the region that has been
modeled, and specify the spacing and extent of the grid of nodes that
has been overlaid on the region.  We conclude the section by discus-
sing the various modifications and extensions of the original formula-
tion,  as presented in Roth et al.  (1971), that have been made during
the current effort.

A.  Theoretical Formulation of the Model
     The simulation of photochemical air pollution entails giving
description to the behavior of a number of chemically reactive species
in the turbulent atmospheric boundary layer.  Consider  N  chemically
reactive species in a fluid.  The concentration Ci(x,y,z,t) of each
constituent must satisfy the continuity equation,
     3t   9x
                                             \dx     dy     dZ /
                                                                       (1)
          + R. (c.,-••,c ,T) + S. (x,y,z,t)       i = 1,2,...,N
where  u,v  and  w  are the components of the wind velocity, D^  is the
molecular diffusivity of species  i  in air, R^  is the rate of forma-
tion of species  i  by chemical reaction,  T  is the temperature, and
S^ is the rate of emission of species  i  from sources.  In most fluid
dynamics problems involving chemical reaction, it is necessary to carry
out the simultaneous solution of the coupled equations of mass, momen-
tum and energy to account properly for the changes in c^, u, v, w and T
and the effects of the changes in each of these variables on each other.
In considering air pollution, however, it is often quite reasonable to
assume that the presence of pollutants in the atmosphere does not
affect the meteorology to any detectable extent.  An important excep-
tion is the attenuation of incoming radiation by photochemically-
generated haze, a common occurrence, for example, in the Los Angeles

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 area during the summer and autumn months.  While the variation in
 pollutant concentrations may, in this way, alter the energy input to
 the system, and thus affect both the energy and momentum equations, it
 is possible to incorporate this effect in the equations of continuity
 alone  (by treating measured intensities as data) if it is not of in-
 terest to predict temperature and velocity.  Thus, the equations of
 continuity  (1) may be solved independently of the coupled Navier-Stokes
 and energy equations.

      Since atmospheric flows are turbulent, it is customary to represent
 the wind velocity components as the sum  of a deterministic and stochas-
 tic component; e.g.,  u = u + u'.  Substituting u = u + u', etc., into
 Equation (1), taking the expected value of the equation and assuming
 that molecular diffusion is negligible when compared with turbulent
 dispersion yields the following equation governing the mean concentra-
 tion ,*
                                           a  -
                                  <>  +
                  + 4-  + v-                          (2)
                     i    3y     i    3z     i
                                                  Si(x,y,z,t)
 where c. =  + c!,  = 0, and turbulent fluctuations in temperature
 have been neglected.

      Equation  (2) is the basic equation for the mean concentration of a
 reactive pollutant species in the atmosphere.  Its direct solution is
 precluded by the appearance of the new dependent variables, ,
 , and , as well as any variables of the form  which arise
 from .  Considerable attention has been given to means for approximating
* We employ different notation for the mean wind components, u, v, and w,
  and the mean concentrations   .   The bars are used for time-averaged
  quantities, whereas the brackets are used for ensemble-averaged quantities.

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the variables , , and   (see for example, Kraichnan  (1962),
Saffman (1969), and Monin and Yaglom  (1971)).  The simplest and most pop-
ular  means is through the so-called K-theory (Calder, 1949; Pasquill, 1962;
Monin and Yaglom, 1971) in which one sets
It is well known that in the proper general form of the K-theory, the
set of quantities Kvv, K..,,, etc. constitute the components of a second
                   A J\.   ^*j
order tensor 1C.  In most reported applications of the K-theory, off-
diagonal terms" of the form K  , etc. are set equal to zero.  For the
diagonal form of K to be valid at all points of the region it is neces-
sary for the tensCr to have the coordinate axes as principal axes at all
points of space.  Such a situation can occur in the surface layers of
the atmosphere, where the mean wind vector can be regarded as everywhere
parallel to a given vertical plane  (Calder, 1965).  In a large airshed
this is clearly not the case.  If it is possible to assume merely that
the mean velocity is parallel to the ground, with components u ^ 0,
v ^ 0, w = 0, then the only valid form of the K-theory, as given by
Equation (3), can be that in which K   = K  .  Henceforth, we denote
K   and K   as K , and K   as K .         ^
 xx      yy     H       zz     V

     While there has been considerable study of means for relating the
variables , , and  to the mean concentrations, there
has been comparatively little examination of approximations for terms
of the form  which arise when chemical reactions are taking place
in turbulence.  ^This lack of study is primarily a result of both the
enormous theoretical difficulties associated with the description of
turbulent chemical reactions and the lack of experimental data against
which to compare the predictions of the turbulence theories which have
been developed.*   As a consequence of this situation, we make one final
*We refer the reader to Corrsin  (1958), Lee  (1966), and O'Brien  (1966,
1968ab, 1969, 1971) for further information  concerning initial studies
of means for approximating joint moments of  the .  In spite of
these studies, it is still not possible to assess the importance of
the contribution of fluctuating terms of the form  to the mean
rate of reaction  in atmospheric chemical reactions, although an
initial effort along these lines has been made by Donaldson and Hilst
(1972).
                                                                           (3)

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simplifying assumption relative to Equation (2), namely that the mean
rate of reaction can be approximated by the rate based on the mean
concentrations; i.e.,
                 ^,...,  + c^, T)> = Ri(,..., ,T)         (4)
Substituting Equations  (3) and  (4) into  (2) yields
                                        3
                                 .) + —
                          3y     i     9z
                         / + ¥ \KH ""ay/ + ** \v ~^/
(5)
               R (,..., , T) + S (x,y,z,t)
                11         N         1
     Contrary to the impression conveyed in a number of earlier air
pollution modeling studies, Equation (5) is not the fundamental
equation governing the dynamic behavior of air pollutants in the atmos-
phere; rather, by virtue of Equations (3) and (4), it is an approximate
equation, valid only under certain circumstances.  We shall employ
Equation (5) as the basic model in this study.  However, before doing
so, it is necessary to consider the limitations inherent in Equation
(5) that restrict its applicability in describing the transport and
reactions of air pollutants in the atmosphere.

     Assessing the validity of Equation  (5) for modeling air pollutant
dynamics has been the subject of two recent studies (Lamb, 1973; Lamb
and Seinfeld, 1973).  It has been shown in these studies that Equation
(5) is a valid representation of atmospheric transport and chemical
reaction provided that the:

     1.    Time resolution  of  the model,  At  , is large compared with the
           Lagrangian time  scale of the  turbulence.

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     2.   Characteristic temporal and spatial scales for gradients
          in the mean velocity field are large compared with the
          time resolution At and the average distance that a fluid
          particle travels in At.

     3.   Characteristic temporal and spatial scales for gradients
          in the turbulent velocity correlations are large compared
          with the time resolution At and the average distance that
          a fluid particle travels in At.

     4.   Characteristic temporal and spatial scales for gradients
          in the source emission functions S^ are large compared with
          At and the distance a particle travels in At.

     5.   Characteristic temporal scale for changes in the rate of
          generation or depletion of species by chemical reaction,
          R. ,  is large compared with At.

     These conditions may be expressed more precisely in quantitative
forms.   In particular, conditions 2 and 3 imply that each of the fluid
velocity components should satisfy the requirements*:
                    «  -3-            i » 1,2,3
           =i3t
                3ui
                                        lj =  1>2>3
*For convenience in stating these conditions we employ the notation
 u.,, u ,  u  and KI , x_, x  in place of u,v,w and x,y,z, respectively.

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where R.    (3£,t) is the Lagrangian time correlation function,
                      oo

                   = C

                    J n
 di        k = 1,2,3
and v  (sc,t) is the Lagrangian velocity at position x_ and time t.
Conditions 4 and 5 can be written as:

                                       ,
                                  At]               k=1'2'3
              3R.
          R.   at    At
These conditions, of course, impose restrictions on  t  and on the
temporal and spatial resolution of the velocity field and the source
emission functions that are to be used in Equation  (5).  Therefore, we
must determine the extent to which these restrictions apply for condi-
tions typically observed in the Los Angeles Basin.  Only then can we
specify the appropriate spatial and temporal scales for the model.

     In the Los Angeles airshed there are roughly three dozen wind
monitoring stations, with an average separation between them of roughly
seven miles.  At most stations the wind speed and direction data are
averaged over a one-hour period.  From these hourly-average values the
mean surface wind field, u(x,y,t) and v(x,y,t), can be constructed.  Sub-
tracting the mean values from the instantaneous readings at each
                                10

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station and averaging over time yields the Eulerian correlations
, i,j = 1,2,3.   An Eulerian time scale for the turbulence,
can be estimated from these correlations.  Although the precise re-
lationship between the Eulerian and Lagrangian time scales, T  and T ,
where                                                        E      L
is unknown, a convenient estimate is that  T  =4r    (Hay and Pasquill,
1959).  Having estimated T  from the wind station data, for the condi-
tion that At » T , we can place a lower limit on At, such as ST .
Using a At » T   insures that the four conditions pertaining to the
fluid velocity components will be satisfied.

     Once At has been selected, we must specify the spatial and temporal
resolutions for S^ and the temporal resolution for R^ that satisfy the
final three conditions.  These conditions will determine the degree of
detail required for the source emissions inventory and the chemical
reaction mechanism, one which is commensurate with that of the meteoro-
logical data.

     Unfortunately, data of the type needed to estimate the Eulerian
time scale of the turbulence in the Los Angeles Basin are not generally
available.  In an effort to gather data of this type, Lamb and Neiburger
(1970) measured the turbulent structure of the atmosphere at a height of
20 meters in West Los Angeles.  The wind velocities were averaged over
a period of T = 0.3 hours.  From these data, TE was estimated to be 50
seconds.  Assuming that TJ^  = 4TE, TL equals 200 seconds.  We therefore
estimate that At >_ 103 seconds  on the basis that At >_ STL-  The
Lagrangian correlation functions were estimated to be:  R^ - 100 m2sec~ ,
                                11

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           2-1               2-1               3
R22 ~ 10° m sec ' and R33 ~ 10 m sec  .  With At = 10  seconds and
these values of the Rj^, the conditions limiting the validity of
Equation (5) assume the quantitative values shown in Table 1.  Since
the conditions in Table 1 are based on data for which the averaging
time was 0.3 hours, they are less stringent than those based on data
for which the averaging time is 1 hour.

     We have found that the minimum temporal and horizontal spatial
resolution in the source emission function must be 10  seconds and
2000 meters, respectively.  Thus, the averaging time and distance
for source emissions should be, say, at least twice these values.
We note that, in spite of the fact that many major pollutant sources
are point and line sources, emissions must be averaged over relatively .
large distances to conform with the resolution of Equation (5).  In the
source emissions inventory described in Appendices A of Roth et al. (1971)
and this report, we have spatially and temporally averaged source emis-
sions over 2 miles (approximately 3000 meters) and 1 hour, respectively
Thus, the spatial averaging we have employed is of somewhat finer reso-
lution than that suggested by the conditions in Table 1.  The condition
on R£ states that the characteristic time scale for changes in the con-
centrations as a result of chemical reaction should be greater than 103
seconds—perhaps of the order of one hour.  Finally, Lamb and Neiburger
(1970) estimated that the minimum vertical resolution of concentration
changes is of the order of 20 meters or greater.  The minimum vertical
mesh spacing employed is roughly 20 meters.

     In summary, we find that Equation (5) is applicable in resolving
those perturbations in the concentration field which have horizontal
scales greater than 2 kilometers, vertical scales greater than 20 meters,
and temporal scales greater than 10  seconds.  These conditions serve
as a guide to the choice of grid size and averaging time to be used in
the solution of Equation  (5).
*In the early morning, in order to account for the nonuniform distribu-
tion of trip starts, motor vehicle emissions are temporally averaged
over 15-minute periods for the first hour (6-7 a.m.).
                                12

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Table 1.  Conditions Limiting Equation (5)  Based on the  Measurements

          of Wind Turbulence of Lamb and Neiburger (1970).
1.  Source emission function
                                         as.
                                                   1   meter"1, k =  1,2
                                                  2ooo
2.  Chemical reaction rate

        «
3.  Mean velocity components
i!^i
-   3t
u.
                                                         -1

                                      u.
                                                             ',  k  =  1,2
                                                   -rrr  meter  ,  k  =  3
4.  Turbulent velocity

    components
       8    ..-3   -1
          i ^     10  sec
          9t
                                                        2000
                                                             meter  ,  k  =  1,2
                                                        -rr  meter  ,  k  =  3
                                13

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B.   The Model Developed in this Study

     The model developed is based on the solution of the N coupled
partial differential equations  (5) defined on the region, x^ _<_ x _<_ x
VS — y - VN'
            h(x,y) ^ z ^ H(x,y,t) for t ^ t0, where
                                                             XE,
                                                                    are
the west, east, south and north boundaries of the airshed, h(x,y) is
ground elevation above sea level at (x,y), and H(x,y,t) is the elevation
above sea level of the base of a temperature inversion or an assumed
upper limit for vertical mixing or transport.  The initial condition on
Equations (5)  is that the mean concentration be specified at all loca-
tions ,
                                                                      (6)
(At this point and henceforth, for convenience, we omit brackets on
the concentrations and overbars on the velocities.  However, all concen-
trations and velocities continue to be mean and time-averaged quantities,
respectively.)
     The vertical boundary conditions are:

     1.        z = h(x,y)         - K X^-n^ = Qi(x,y,t)
                                                                 (7)
     where K is the eddy diffusivity tensor,
                          K =
                            0   K   0

                           _°   °  V
     n.  is the unit vector normal to the terrain directed into the
     atmosphere, and QJ is the mass flux of species  i  at the surface.
2.
                            z = H(x,y,t)
                         = 0
                                                  if
                                                  if
                                                                      (8)
                                                     > 0
                                14

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     where V is  the  advective  velocity  of pollutants  relative to the
     moving  inversion base,  given by
                        V =  ui +  vi +
     n^j is the outwardly directed  unit  vector  normal  to  the  surface
     defined by the inversion base,  and g.  is  the mean concentration
     of species  i  aloft  (just above the inversion base).

     The condition V-njj ^  0 in equation (8)  applies when material  is
transported into the modeling region from above the inversion base.
This boundary condition simply states that  the normal component  of the
mass flux is continuous across the upper boundary.  The  condition
V*ri  > 0 applies when pollutants are transported up through  the  inversion
base.  Because of the abrupt stability  change  associated with an in-
version layer, it is reasonable to assume that the turbulent diffusive
flux across the boundary is zero,  thereby attributing any pollutant
transport into the inversion layer to   advection alone.   The second
boundary condition in Equation (8) expresses the negligibility of  the
turbulent diffusive flux at the inversion base.

     The horizontal boundary conditions are:


               (Uc. - KVc.) 'n = £g. (x,y,z,t) •£     if £-n_ <_ 0
                                                                       (9)
                    - KVc. -ri = 0                    if IJ-ri > 0
where £ = ui^ + vj_, n_ is the outwardly directed unit vector normal  to
the horizontal boundary, and g^ is the mean concentration of species
i  just outside the airshed boundary.  The first condition is, as
before, a statement of the continuity of mass flux across the boundary
when the flow is directed into the airshed.  The second condition
specifies that the diffusive component of the total mass flux be set
equal to zero when the wind is directed out of the airshed.  This  con-
dition is equivalent to that conventionally employed at the exit of
tubular chemical reactors (Wehner and Wilhelm, 1956), although  the
                                 15

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conditions prevailing at the boundary of the region are not precisely
the same as those at the exit of such a reactor.  Since the horizontal
advective component of the mass flux generally dominates the horizontal
diffusive component, the error incurred due to this approximation is
generally small.

     In this study, we applied Equations (5) - (9) to the prediction of
pollutant concentrations over much of a fifty-mile square area that
includes virtually all centers of population in the Los Angeles Basin.
The region was divided into a grid of 625  2-mile x 2-mile squares,
198 of which lie over oceans or mountainous terrain having no pollutant
sources.  These "source-free" grid squares were not included in the
region actually modeled, which is shown in Figure 1.  Source emissions
and meteorological variables are distributed in conformance with this
grid; i.e., two miles is the resolution of the model, or the spatial
dimension over which all quantities are averaged.  Furthermore, for
reasons to be discussed, the grid actually used in the solution of
Equations (5) is a three-dimensional array of five layers of cells
occupying the space between the ground and the base of the inversion
and lying directly over the area shown in Figure 1.  Thus, each cell
has a base two miles square and a height of (H - h)/5.  The center of
each cell, or node, is the point to which values of all variables are
assigned or referenced.  Unfortunately, due to variations in both H and
h with x and y and, in the case of H, with t, the three-dimensional
modeling region has an irregular "roof" and "floor".  To eliminate these
irregularities, which hamper the solution of the equations, we performed
the following change of variables:
                                            z - h(x,y)
                 = x      n = y      r	*
                                     ^   H(x,y,t) - h(x,y)

     With these changes, Equations (5) becomes
          •J- (AHc.) + -^r (uAHc.) + -j- (vAHc.)  + -~- (We.)
          
-------
113   45-
•113
             5   fc  7
»0  II   II  O  lf  "  '7  '6 .«!»  2.0 ti  21 13  H-  ZS
                     Figure  1.   The Modeling  Region
                                   17

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                                             i   v   3h    3AH    i
                                           ~ " KH \    + p~
                                       +        +

                                  35      AH  3n   P3n/    AH  3p
                    + R.AH + S.AH                                     (10)
where



                        AH = H(x,y,t) - h(x,y)




and



                W •"• Vr — U I r\ >. *
                                           3h    3AH\    3AH

                                              + P—J - P—
     The initial boundary conditions now become:
                          (£,11,P,  TQ)  = f± (5fT),P)                     (ID
1.    p = 0




          Q4(5,n,i

                                18

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2.   p = 1
                               (**\ !i + K  (**\ !!t
                               \3C/ 35    H V^n/  3n
                               \  r          \  /
AH
                                    Ik fe
                                    AH  8n
                             AH/  3p
                                           if W < 0
    35
                                          3n
3.
                        AH \3n/    AH
                                           if w > o
                                                                  (13)
Ugi = UCi ' KH
            AH
                                                    3p
                                           if U-n <  0
                                  AH
                                           if U-n >  0
                                                                  (14)
                            19

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4.   n = ns or nN
                                           if U-n  < 0
                         H V 3n ~ AH \3n   p~3n 7  3p
                                                                       (15)

                                           if U-n  > 0
     Equations (10) -  (15) are the transformed form of Equations  (5) -
(9).  Fortunately, several of the terms appearing in the  above  equations
are small when compared with other terms  and can thus be neglected.
For example, in the Los Angeles Basin the changes in ground elevation
and inversion height with location are generally sufficiently gradual
that the derivatives,  3h/3£, 3h/3n,  3AH/3£, and 3AH/3n are considerably
smaller than one.  With the assumption that terms in Equation  (10)  con-
taining these derivatives can be neglected, this equation becomes
             (AHc.) +     (uAHc.) +     (vAHc.) +     (Wc.)
                              3C /  3n
                                                                       (16)
                    + R.AH + S.AH
                                20

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We might note that, whereas  the  assumption  that the derivatives 3h/3£,
etc. are small is generally  satisfied in the flat portions of the
Los Angeles airshed, it  is violated in the  mountainous areas, such as
the Palos Verdes Hills and the Santa Monica Mountains.  However, since
the terms omitted in Equation  (10)  involve  horizontal diffusion, which
is generally less important  than horizontal advection, we do not expect
to incur significant errors  in using Equation (16)  even in these regions.

     Under the assumptions invoked  in obtaining Equation (16),  the
boundary conditions in Equations (12)  - (15)  become:
1-   P = °          Ql(e,n,T)--^^                              'I?'


                       K^  3c.
2.   p = l       Wci ' AH  "V" = Wgi(?'n'lfT)       if W - °

                                                                       (18)

                     - -^  -r-1- =0                  if W > 0
                       AH  3p
3.
                           3c.
                 uc. - K,T -T7T- =  ug.                if U-n < 0
                   X    n  at,      1                   ~™ "~ ™"

                                                                       (19)
                           3c
                     - K  -r^- =0                  if U-n > 0
                        H  oE,                         — —
4.   n = ns or nN
                           3c.
                 vc. - K  -r-i- =  vg.                if U-n < 0
                   i    H  3n     ^i                   	
                     - KH — = 0                  if D-n > 0
                                  21
                                                                       (20)

-------
The entire airshed is thus transformed into a three-dimensional array
of cells in the (5,n,p) space having all sides parallel to a Cartesian
coordinate system.  The actual model, then, is based on the solution of
Equations (16) -  (20) and  (11) over a region comprised of 427 x 5 cells.

     Having specified the governing equations and having described the
modeling region, we now consider those components of the model that must
be developed prior to its evaluation and/or application.  In particular,
the following tasks must be carried out:

     1.   The development of a contaminant emissions inventory for
          the Los Angeles Basin, that is, specification of the functions
          S.(5,n,P,T)(elevated sources)  and Q.(C,n,T)(ground-level
          sources).  Refer to Appendix A of this report and Appendix
          A of Roth et al. (1971) for complete details.

     2.   The development of a kinetic mechanism capable of describing
          the rates of chemical reactions occurring in the atmosphere,
          and the adaptation of this mechanism for inclusion in the
          airshed model* that is, specification of the functional form of
          the R. (c ,..., c ).  Refer to Appendix B of this report and
          Appendix B of Roth et al. (1971)  for complete details.

     3.   The development of a means for including in the model the
          meteorological parameters, u(C,n,P,t), v(?,n,p,T), w(£,n,p ,T) ,
         . H(?,n,T), KjjUjiifpfT) and Ky(C,n,p,T).  Refer to Part C
          of this section and Appendix C of Roth et al (1971) for
          complete details.

     4.   The selection and adaptation of a numerical method suitable
          for the solution of Equations  (16) - (20).  Refer to
          Appendix D of this report and Appendix D of Roth et al. (1971)
          for complete details.

Thus, the Appendices to both this and the Phase I report, taken together,
provide a full description of all individual components of the model.
In the last part of this section, we briefly enumerate, for the benefit
of those who are familiar with the work completed in Phase I, the modi-
fications and extensions to the model that have been carried out during
the present effort.
                                 22

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C.   Modifications and Extensions to Original Formulation of Model

     We have divided into eight categories the discussion of modifi-
cations and extensions to the original formulation of the model that
have been carried out during this study—emissions, photochemistry,
meteorology, numerical analysis, the model itself, treatment of sub-
grid scale phenomena, the computer programs, and the interpretation
of air quality data for the purposes of validation.  Where a particu-
lar model change is discussed in an Appendix, we merely cite the
change and make proper reference.  However, a more complete discus-
sion is given for those changes not described elsewhere in the text.

     1.   Emissions

          a.   General,  Assignment of fractional splits of NO and
               NO_ emissions from various source categories (as
               percent NO ).  Clarification of ambiguity in Appendix
               A of Roth et al  (1971) concerning treatment of NO  emis-
               sions from all sources.  All NO  emissions rates are re-
               ported as being  100% NO , whereas they are more nearly
               100% NO.  Thus,  all NO  emissions rates in the earlier
                                     x
               report should be reduced by a factor of 30/46.

          b.   Automobiles. Adoption of average pollutant emissions
               rates (grams/mile) based on the Federal Driving Cycle,
               inclusion of a correlation between emissions rate and
               average speed to account for temporal and spatial vari-
               ations in emissions from freeways, and incorporation of
               a factor to account for variations in emissions result-
               ing from a nonuniform temporal distribution of vehicle
               starts.   Treatment of emissions in the downtown Los
               Angeles area also modified.


          c.   Aircraft.  Emissions from airborne operations now neglected
               due to their small influence on  the  calculated pollutant
               concentrations.   New information included, pertaining to  emissions
               from reciprocating aircraft engines  and  to average number of  jet
               aircraft flights per day  made at Los Angeles  International Airport.

          d.   Refineries and Distributed Fixed Sources.  Revised
               treatment of hydrocarbon emissions with regard to
               reactive/unreactive split.  Incorporated assumptions as
               to molecular weights of emitted hydrocarbons.

     All extensions and modifications cited are described in detail in
     Appendix A of this report.
                                23

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2.    Photochemistry

     a.   Addition of second hydrocarbon and NO^-particle reaction
          to mechanism for validation using smog chamber data.
          However, changes not included in airshed model.

     b.   Additional validation of mechanism using fourteen sets
          of experimental data and four hydrocarbon systems.

     c.    Estimation of reaction rate constants for which literature
          values are not available.   Estimation of stoichiometric
          coefficients.  Elimination of variable stoichiometric
          coefficient.

     d.   Method for estimating hydrocarbon rate constants in the
          atmosphere for the different validation days.   This pro-
          cedure, which is discussed in more detail in Section III,
          involves the use of gas chromatographic data to compute
          average percentage (over a day)  of reactive paraffins,
          aromatics, ethylene, and other olefins present in the at-
          mosphere.  Hydrocarbon rate constants (with 0, OH, and
          03) were calculated as weighted averages of average rate
          constants for each group, weighted in proportion to the
          mole fraction of the group present in the atmosphere at
          the time in question.  Average constants were then calcu-
          lated for the  entire day, as the averages at any time
          vary only slightly with time.

     A full discussion of the photochemical mechanism and its eval-
     uation  (but not topic d above)  is given in Appendix B.

3.    Meteorology

     There is no appendix associated with this report dealing with
     the treatment of meteorological variables, as there was in
     the Phase I report.  As a result we discuss extensions and
     modifications in the treatment of these variables more fully
     than we do in the case of most other parameters.

     a.   Treatment of wind field aloft.   In Appendix C of Roth et
          al. (1971), pages C-39 to C-42, we outlined two procedures
          for estimating the speed and direction of winds aloft in
          the absence of a data base.  Comparative tests of the two
                            24

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methods, carried out during Phase II, showed little
difference in predicted concentrations.  Due to this
observation and the fact that the first method requires
far less computation, we adopted the first method as
the standard procedure for estimating wind speed and
direction in all layers of cells above the ground.  The
method is based on the assumption that


 9_u   3jy   3 u> _          3u   3 v _
 3 x   3 y   3~z ~ °  an    3~z~3~y~

Treatment of surface wind fields.  In Appendix C, Section
II, of Roth et al. (1971) we describe the procedures used
in the construction of hourly surface wind maps.  These
maps, which are illustrated in Figures C-17 to C-19 of
that report, are detailed representations of the flow
fields, representations that several of us believed
could not be justified, given the level of consistency
and accuracy of the available meteorological data.  We
felt that the wind maps should be no more complex than
the data could support and thus elected to prepare less
detailed maps.  The newly drawn maps, illustrated in
Figures 2,3, and 4 for the same three times on 29 September
1969 as the maps in Figures C-17 to C-19, are much smoother
and simpler; yet they appear to provide "good representation"
of the data.

Using the revised maps, we carried out validation experi-
ments for carbon monoxide to compare predictions with
those calculated using the original wind maps.  Estimated
concentrations based on use of the revised maps showed
significant improvements when compared with air quality
data reported by those monitoring stations for which
discrepancies between original predictions and measured
values were large.  In only a few cases did discrepancies
between prediction and measurement increase when the re-
vised maps were used.  Based on these observations we
concluded that the initially prepared maps are more ela-
borate and detailed than is either necessary or justifiable.
                   25

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                             ic  li	12  13  _/6  IS
  I   2.  3
 7   8  q   »o  ||  J2.  '3

-fc—  Streamlines
(8  19  10 2.1  22  23  2fr  25
                	—  Isotachs  (wind speeds  in mph)
Figure 2.  Modified Surface Wind Map for  Los  Angeles Basin
            (29  September 1969, 6:30-7:30  PST)
                                    26

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I   I  3
              5  6  7
  >0  |l  12.  13  l
-------
                  €>  1  8  <)  io  |l  12.  '3

                             Streamlines
1C  (7  <8 II  io 2.1  2.2  23 24-
               —•———     Isotachs  (wind speeds in mph)
Figure 4.  Modified Surface Wind Map  for Los Angeles Basin
            (29  September 1969, 12:30-13:30  PST)
                                    28

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Preparation of inversion maps.  On pages C-17 to C-21
of Roth et al.  (1971), we have outlined an algorithm
for the preparation of hourly maps of mixing depth.  The
basic variable in the algorithm is height of the inver-
sion base, H(x,y,t) .  However, the variable of interest
is the mixing depth, that is, H(x,y,t)  less the terrain
elevation, h(x,y) .  If maps are prepared and smoothed
using  H(x,y,t)  , (H-h)  as a function of  x  and  y  is
an irregular, or "bumpy", surface.  We have thus elected
to prepare maps with   (H-h)  as the basic variable, so
that surfaces of mixing depth are reasonably smooth.

Movement of the inversion with time,  in calculations
carried out during Phase I, the height of the inversion
base was held constant during the full hour over which
it applied.  When the inversion base was moved, new material
(i.e., pollutants) was introduced at a concentration
equal to that just below the inversion prior to its
displacement upward.  During the Phase II effort, we
made the two changes in this procedure.  First, we now
move the inversion base at each time step/ using linear
interpolation between hourly maps to determine its
vertical position at the location   (x,y) .  We believe
that this procedure is more consistent with reality.
Second, we introduce material through the rising inver-
sion at a concentration determined according to the
algorithm discussed in part 5d of this section (pages
35-36).  This procedure was adopted as we believe that
introduction of high concentration material beneath a
rising inversion is probably inconsistent with actual
behavior.  Measurements indicate that contaminant con-
centrations aloft (with the exception of ozone) are
generally lower than those specified using the
original algorithm.  Thus, the new procedure introduces
pollutants beneath the inversion at concentrations
that correspond more closely with those observed.
                    29

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     e.   Use of actual radiation intensity data.   In Appendix
          B of Roth et al. (1971) we presented curves represent-
          ing the effect of the diurnal variations in solar in-
          tensity on the rate constants for the photolytic disso-
          ciation of N02 and HN02-  These curves,  however, are
          representative only for clear skies and in the absence
          of photqchemically-generated haze.  In the evaluation
          studies carried out in the current project, we used
          actual intensity data, as measured by Scott Research
          Laboratories at Commerce and El Monte for the six vali-
          dation days.  We present the curves used in the next
          section under evaluation Procedures.

4.   Numerical Analysis

     a.   Finite difference procedure.  We discovered early in
          the evaluation studies that, in employing the second and
          fourth-order differencing procedures given by Crowley  (1968)
          and Fromm  (1969)  respectively  (see  Appendix D of Roth et al.
          (1971)), negative concentrations were generated on occasion
          in the vicinity of large concentration gradients.  To
          eliminate the possibility of introducing this type of
          error, we have adopted a finite difference procedure
          described by Price, Varga, and Warren (1966).  While
          this procedure is somewhat less accurate than the second
          order technique of Crowley, it is, of course, more
          accurate than a first order method.  And the main pur-
          pose, elimination of negative concentrations, has been
          realized.

     b.   Solution of the nonlinear difference equations in the
          p direction.  In Appendix D of Roth et al. (1971) we de-
          scribe the method we have used for solving the nonlinear
          difference equations in the integration step in the  p
          direction.  In essence, the method is a simple iterative
          procedure that has displayed no convergence problems and
          has given consistently good results.  During the current study we
          have experimented with  the  use of  Newton's method  (Isaacson and Keller,
          1966)  for solving  the nonlinear equations.  Test results indi-
          cated that this procedure is  somewhat more accurate than
                               30

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     the method we have used previously.  TVs a result£ we
     have incorporated Newton's method into the operating
     program.

c.   Tests of accuracy.   We carried out four sets of compu-
     tations to examine questions pertaining to the accuracy
     of the numerical procedure.  Using the differencing
     algorithm of Price et al.  (1966), we

     (1)  executed a simulation with no wind, no emissions
          fluxes, constant inversion height, and a uniform
          concentration field in order to evaluate the
          accuracy of the treatment of photochemistry in the
          airshed model.  Predicted concentrations were
          compared with those generated using Gear's routine (1971)
          in integrating the coupled, first-order, ordinary
          differential equations that represent the photo-
          chemistry alone.  (See Appendices B of Roth et
          al. (1971) and of this report for a discussion
          of Gear's method.)  Predictions differed by no
          more than 2% between the two methods, confirming
          the validity of the treatment of photochemistry
          in the urban airshed model.

     (2)  compared predictions -of the  full  airshed model under typical
          simulation conditions  using  time  steps of various magnitudes.
          We found that  predictions  based on a  one-minute time step
          differed only  slightly from  those based on a four-minute time
          step.   This test confirmed that it is not necessary to restrict
          time steps to  short  intervals  (1  minute or less).

     Comments made thus far regarding numerical procedures
     are summaries of more complete discussions to be found
     in Appendix D of this report.  Omitted from the Appendix D,
     however, are the results of two tests of the numerical
     procedure that were carried out prior to the adoption
     of the Price  et al. differencing scheme.   We present
     them here because we believe that the results are both
     of value and of general interest.

     Early in the current study, using the Crowley and Fromm
     differencing procedures,  we
                      31

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(3)  carried out a series of test runs for carbon monoxide
     to establish the merits of using numerical approxi-
     mations of various orders.  Using an initial concen-
     tration distribution based on 29 September data and sim-
     plified wind profiles,  we found that truncation errors
     realized using first, second, and fourth order approxi-
     mations are roughly in  the ratio of about 2:1.5:1.  These
     results clearly indicated that accuracy improved sub-
     stantially with .increasing order of approximation.
     At the same time,  as  we discussed earlier,  we  observed
     the occasional occurrences  of negative concentrations
     in areas of steep  concentration gradients when second
     and fourth-order approximations were adopted.   Search-
     ing for a means for eliminating these  errors, we
     found the procedure suggested by Price et al., which
     is a second-order  approximation.   Unfortunately, we
     were unable to find a suitable fourth-order procedure.
     Confronted, then,  with the  choice of a second-order
     procedure and elimination of negative concentrations
     or a fourth-order  procedure and the  occurrence of
     negative concentrations,  we selected the former.   It
     is, of course, very much worthwhile  to develop or
     locate a fourth-order procedure having the  described
     properties.

(4)   carried out two test  runs to explore the relationship
     between the spatial resolution of the model and both
     the accuracy of the model and of the numerical inte-
     gration procedure.  The two test runs were  made for
     the following conditions:

     (a)   Reduce grid size from  2x2 mile to 1  x 1 mile
          and integrate the equation of continuity  for
          CO using the  same emissions and meteorological
          data as in the simulation described in Roth et
          al.  (1971).   Assign  one-fourth  the traffic volume
          of each 2x2 mile grid square  to the  new 1x1
          miles squares.   It was the purpose of  this run
          to explore the accuracy of the  numerical  technique.
          (The effect of a finite grid approximation on the
          numerical accuracy of  a computation can be inves-
          tigated in two ways.   The first is to  change  the
          order of the  finite  difference  approximation;
          this source of error was discussed earlier.   The
          second way is  to vary  the grid  size.)
                 32

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 (b)  Assign the fraction of freeway emissions calcu-
     lated for each 2x2 mile square to the appro-
     priate new 1 x 1 mile squares, thereby increas-
     ing the spatial resolution of the automotive
     emissions inventory.  The purpose of this run
     is to test the accuracy of the model with respect
     to major line sources of emissions by comparing
     results of the integration with those obtained
     in the first test.

Because of the relatively complex nature of the model
and the associated emissions patterns/ the tests were
not expected to be definitive.  However, we thought
it preferable to carry out the runs under the actual
modeling conditions, as fabricated conditions might
be less revealing.

The two test runs were carried out for a 24 x 24 mile
 (or 12 x 12- grid square) test region, that included
between rows 7 and 18 and columns 5 and 16 of the
actual 50 x 50 mile modeling region.  Comparisons of
predictions with actual data were made for the West
Los Angeles (WEST), Lennox (LENX), Commerce (COM),
Long Beach (LONB), and downtown Los Angeles (CAP) lo-
cations.  For the test run (a), predictions for each
set of four 1x1 miles squares were averaged for
hourly comparisons with predicted values computed on
a 2 x 2 mile grid (and for comparison with the data).
While no pattern of differences emerged, we observed
that the average of the 4 - 1 x 1 mile values typi-
cally differed by no more than 1 or 2 ppm from the
2x2 mile grid predictions (only rounded integers
are printed out).  These results indicate how dif-
ferent the predictions might be if a smaller grid
were used; they do not represent a true measure of
accuracy.  What we can conclude is, that in light of
the minor changes in predicted values that were ob-
served, the added cost associated with adopting a
1x1 mile grid system is a cost that is not worth
incurring.

The results of test run (b) clearly demonstrate that
the model is sensitive to the degree of resolution
            33

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               employed in the treatment of freeways.   Comparisons,
               in this case, were made between measured values and
               predicted values computed on the basis  of the loca-
               tion of the monitoring station.  If the station is
               located within a 1 x 1 mile square, the prediction
               for that square was used; if the station is located
               on a border between two 1x1 miles squares, the
               average of the predicted values is used.  (We also
               noted the fraction of freeway emissions that was
               assignable to each of the 4-lxl mile squares
               that comprise a 2 x 2 mile square.)  In general, ac-
               curacy improves with increasing fineness of resolu-
               tion, and increases or decreases in the magnitude
               of predicted concentrations correlate directly with
               the fraction of freeway traffic assigned to the
               1x1 mile grid square that includes the monitoring
               station.  However, as before, the degree of improve-
               ment in accuracy is not sufficient to justify the
               increased costs associated with the adoption of a
               finer grid.  In fact, it is clear that  an area-wide
               model cannot incorporate the needed resolution and
               remain practical; rather, a model having resolution
               of the order of a freeway width is the  appropriate
               "tool" for dealing with the type of inaccuracies in
               prediction that are observed in the vicinity of a
               monitoring station adjacent to a freeway (see
               Appendix C).
5.    The Model
          The size of the grid.   In the original formulation we
          adopted a grid of nodes for integration of the governing
          equations that was comprised of 625 (or 25 x 25)  2 mile
          x 2 mile squares.  Furthermore, the space between the
          ground and the base of the inversion in the transformed
          coordinate system was divided into ten strata.  In the
          current version of the model we have eliminated 198
          of the 625 squares covering the 2500-square mile area,
          as these squares lie over the ocean and mountainous
          areas having no pollutant sources of consequence.
          Moreover, we found in carrying out CO evaluation runs that
                            34

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     predicted concentrations vary only slightly with large
     variations in the number of strata incorporated in the
     vertical.  In particular, simulations involving five
     strata display concentration profiles that are only
     slightly flatter than those calculated using ten, and
     the differences in predicted concentrations at the ground
     are not significant.  We thus reduced the number of
     vertical strata in the model to five.  (Further reduction
     in number of strata may also be appropriate, subject to
     the results of additional sensitivity studies.)

     Form of the continuity equations.  We have adopted the
     conservative form of the continuity equations.  Previously
     we have used a non-conservative form of the governing
     equations (D-l) of Roth et al. (1971), Appendix D, one given
     by Equations (D-4) of that report.  The conservative form
     ensures that a material balance is maintained across all
     cell boundaries; the non-conservative (or advective) form
     does not (except for the case of uniform flow).  The present
     equations are:
                                a(Wc±)
   9t        3?         8n        9P
                                               i=l,2,...,N
     The horizontal boundary conditions have been altered some-
     what since horizontal diffusion is allowed in this formula-
     tion of the governing equations.

c.   Form of the transformed equations.  The transformed equa-
     tions now include horizontal turbulent diffusion.  While
     horizontal diffusion is generally unimportant in a model
     of a two-mile spatial resolution, the model can now be applied
     when the spatial grid is much finer, and thus when the
     effects of horizontal diffusion may be significant.

d.   Treatment of the boundary conditions at the inversion base.
     In order to specify the concentration of pollutants that
     enter the modeling region as the inversion rises, we must,
                         35

-------
  in the absence of concentration data aloft, make some
  assumption as to the nature of the vertical concentration
  distribution.  Thus, at the beginning of a simulation
  (t=t ), we establish the following concentration distri-
  bution aloft over each grid square:
                       H-h
                   750'..
              H(x,y,tQ)

               - h(x,y)
                                            A-
                              concentration

  where

       c  = initial concentration in the column of grid
            cells above a particular grid square.

       c.  = assumed background concentration aloft above
            the grid square.

H(x,y,t )  = height of the inversion base at  tQ  and location
   h(x,y) = terrain elevation at (x,y).
  In the profile shown, AB  denotes the initial condition,
  and BCD  denotes the assumed concentration profile aloft
  (above the inversion base).   As the base of the inversion
  rises, the concentration of pollutant  in the air engulfed
  is given by the location of the height of the inversion
  base and the corresponding concentration on the segment
  BCD.  A profile is constructed for all species except
  ozone.  In the case of this  pollutant we calculate the
  concentration at the boundary through use of the steady-
  state approximation involving HC, NO, and N02.
                   36

-------
     e.   Development of a tuo-dimensional version of the model.
          We prepared a two-dimensional version of the airshed
          model for use in the initial phases of model implemen-
          tation and testing.  As vertical gradients in concen-
          trations were found to be small and the cost of opera-
          ting a three-dimensional model is considerable, use of
          the two-dimensional formulation  served as an inexpen-
          sive means for carrying out tests involving numerical
          procedures, treatment of the chemistry, etc.  We were
          also able to compare predicted concentrations using
          both the two- and three-dimensional models to determine
          if, in fact, a three-dimensional formulation, with its
          additional complexity, was needed.  While the dif-
          ferences in prediction were generally (though not always)
          rather small, we elected to carry through with the
          three-dimensional version.  We recommend, however, that
          the question of dimensionality be further explored in
          future studies of model sensitivity.

6.   Modeling of Subgrid Scale Phenomena

     a.   Development of a miaroscale model for predicting concen-
          trations of carbon monoxide in the vicinity of roactoays.
          Evaluation of a model having two-mile resolution is at
          best a questionable undertaking if available data are
          based on samples collected at a point.  As an example,
          consider carbon monoxide emissions from automobiles in
          the vicinity of a monitoring station.  Clearly, these
          emissions can influence measured concentrations at the
          station.  In other words, the measurements are not neces-
          sarily (and are in fact unlikely to be) representative
          of the two-mile square in which the station lies if the
          station is adjacent to a major roadway (which is gener-
          ally the case in Los Angeles).  In an initial and limited
          study to examine the utility of combining regional and
          subgrid scale models to resolve problems in validation
          attributable to mismatches in scale, we developed a micro-
          scale model for describing the contribution of local
          vehicular sources to pollutant concentrations measured at
          monitoring stations.  This work is fully described in
          Appendix C of this report.
                           37

-------
     b.   Revision of the power plant emissions model.   During
          the current effort we made a number of revisions to
          the power plant emissions model described in Appendix
          A of Roth et al. (1971) , particularly with regard to

                  the apportionment of emissions from a power
                  plant among cells downwind of the source

                  the inclusion of temporal variations in emis-
                  sions rates

                  the treatment of "inversion penetration"

                  the calculation  of the average molecular weight
                  of emitted hydrocarbons.

          These modifications are  discussed in Appendix A of this
          report.

7.   Computer Programs

     a.   'Emissions calculations,   in Appendix F of Roth et al.
          (1971) we referred to an Aircraft Emissions Program.
          We have  taken that part  of the Aircraft Emissions Program
          used to  calculate emissions from ground operations and
          included it in the newly-created Emissions Data Prepara-
          tion Program.  In addition, all ground level emissions
          are now  calculated in this program and written on tape
          (or disc) for input to the Atmospheric Pollution Simula-
          tion Program (APSP).   Thus, emissions from all sources,
          with the exception of power plants, are input to the
          APSP from tape (or disc).  The APSP has been altered to
          the extent necessary to  incorporate the changes.

     b.   Plotting of concentration profiles.   As a part of the
          current  effort,  we have  developed a program for plotting
          predicted concentration-time profiles (concentrations
          being hourly averages) for all pollutants for which time
          histories are computed [CO, hydrocarbon (inert, reactive,
          and total), NO,  N02,  and 03].  Experimental results,  urban
          scale model predictions,  and micro-model corrections  can
          all be displayed.  These  plots serve as the main mode of
          presentation of data and predictions in Section III of
          this report.
                           38

-------
     In addition to these changes, we have made a number of
     improvements in input and output procedures, attempting
     to maintain both simplicity and generality.  One result
     is that total printed output of a simulation has been
     reduced by more than 50%.  We have also "streamlined"
     the program to eliminate unnecessary calculations,  par-
     ticularly those introduced for evaluative or comparative
     purposes at an earlier stage of model development.   Finally,
     we have made it considerably easier to make alterations
     in the photochemical kinetics mechanism, should such
     changes prove necessary in the future.  The complete set
     of programs comprising the urban airshed model is des-
     cribed in Volume II of this report.

8.   Air Quality Data

     In Appendix E of the Roth et al. (1971) we discussed in some
     detail the air quality data used in model evaluation.  We have since
     reviewed the air quality measurement techniques employed by
     the APCD in terms of accuracy, specificity, and reliability,
     and we make the following observations.  First, accuracies are,
     in general, no better than +_ 10% in the determination of pol-
     lutant concentrations (for any pollutant), and degree of
     specificity and reliability varies greatly, depending upon
     the measurement.  Second, corrections to measurements must be
     made for certain pollutants.  These are as follows:
        CO        No correction needed.

        NO        The oxidation of NO to NO- prior to colorimetric
                  measurement of the product NO^ is 70 to 85% effi-
                  cient.   Thus, reported NO concentrations must be
                  increased by about 20% for use in validation.

        NO-       PAN interferes with measurement of NO-.  Accuracy
                  of measurement is ±10  to 20%.   No correction is
                  recommended, however,  due to lack of information-
                  knowledge of PAN  concentration and other sources
                  of uncertainty.
                              39

-------
oxidant   Presence of NO2 increases oxidant readings by 10
          to 20% of the NO _ concentration; S02 decreases
          readings by an amount approximately equal to the SO2
          concentration.  In Los Angeles, N02 will be the
          most significant interferent, although S02 will
          have a substantial effect in the southwest portion
          of the Basin.  We correct for these interferences
          when they are significant.

total     Flame ionization is specific for carbon, recording
hydro-    oxygenated hydrocarbons as well as hydrocarbons.
carbons   Readings are difficult to interpret  because

               (a)  Calibration is carried out using a speci-
                    fic  hydrocarbon  (APCD uses methane),
                    whereas  the hydrocarbons measured are
                    a complex mixture.  While it is assumed
                    that response is proportional to the number
                    of carbon atoms, significant deviations
                    from this assumption have been observed.

               (b)  Methane is by far the dominant consti-
                    tuent, making determination of nonmethane
                    constituents by difference a highly un-
                    certain matter.

               (c)  Variation in reactivity with type of HC
                    affects measurement.

          We have thus concluded that these measurements are
          too uncertain to be of much value.

In summary, CO and NO2 concentrations are used as reported*
whereas  NO and oxidant are "corrected" in the manner indicated.
Total hydrocarbon measurements are considered to be of little
value.

In applying these corrections, we have made the following ex-
ceptions :

          At Commerce and El Monte, the NO  and 03 measurements
          made by Scott were not corrected, as they were made
          using procedures that do not require a correction.
                      40

-------
At Long Beach, oxidant measurements were not
corrected for SO2 or N02 interference due to the
uncertainty inherent in applying the correction
when the interferents are present in high concen-
trations relative to the species being measured.
            41

-------
III.  EVALUATION OF THE MODEL

      Evaluation of the urban airshed model consists of integrating the
governing equations and comparing predicted concentrations with those
measured at local air quality monitoring stations.  Evaluation was under-
taken in the following sequence for each of six days in 1969,
days for which a rich data base was available.

     1.   Evaluation for carbon monoxide.  Exercise of the model for
          an inert species such as CO provides a basis for evaluating
          the treatment of meteorological variables.  Validation for
          CO, of course, also constitutes a test of most aspects of
          the numerical integration technique and of portions of the
          source emissions inventory.

     2.   Evaluation for total hydrocarbon, nitrogen oxides, and ozone.
          Upon successful completion of 1., and upon the incorporating
          modifications suggested by the results of the validation for
          CO, Evaluation of the airshed model for reactive species may
          proceed.

It is the purpose of this section to describe the evaluation procedure,
to present the results of the evaluation effort, and to examine and
discuss  these results.

     Failure in validation suggests inadequacy of the model, inaccuracies
in the meteorological and/or emissions data that are inputs to the model,
and/or inaccuracies in the observed concentrations.  While it is clear
that deficiencies in the emissions, meteorological, and air quality data
can only serve to enhance discrepancies between prediction and measure-
ment, the impact on evaluation of shortcomings in the model requires
some examination.  In particular, we wish to focus on a problem inherent
in the evaluation of any airshed model in which quantities are spatially
averaged — the comparison of "point" measurements with spatially averaged
predictions.

     Consider the evaluation of the urban airshed model, where carbon
monoxide is the pollutant of concern.  The model is based on the assump-
tion that emissions are uniformly distributed in space and time (over an
hourly interval)  over each 2x2 mile cell and that meteorological conditions
are also invariant over this scale.  The direct result of these assumptions
is that the predicted pollutant concentrations are uniform within each grid
square (or cell).  The observed values of CO, however, typically are rep-
resentative only of the CO concentrations in the immediate vicinity of the
monitoring station.  Of the ten monitoring stations operated by the Los
Angeles County APCD, seven are located within 100 feet of a roadway having
a daily traffic count in excess of 15,000 vehicles.  Ott (1971) has shown
that CO concentrations measured at a monitoring station situated along a
busy city street are approximately twice the background level  (400 feet or
more away from the street) and slightly more than half that measured at
                                  42

-------
the sidewalk located between the street and the station.  Thus, while
we may expect that a properly formulated urban scale model will predict
background levels of CO with reasonable accuracy on a 2 x 2 mile scale,
there is no justification for comparing these predictions with local
point observations.  In the discussion that follows we refer to the
inappropriateness of comparing predicted and measured concentrations
as "the problem of disparate scales".

     The magnitude of the problem of disparate scales varies with the
type of pollutant being considered.  As automobiles are the major source
of hydrocarbons and nitrogen oxides, as well as of carbon monoxide
direct comparison of prediction and measurement for these pollutants
is also invalid.  Hydrocarbons and NO , however, participate in photo-
chemical reactions, and, as a result, the impact of local emissions on
measurements is more complex than in the case of CO.  Ozone, for example,
reacts with nitric oxide (rapidly, of course, when concentrations are
high), thus reducing the concentration of both species in the vicinity
of source, and thus, in Los Angeles, often in the vicinity of monitoring
stations.

     In carrying out the evaluation studies reported here, we plainly had
to accept the fact that, while we wished to have area-averaged measurements,
only "point" measurements were available.  However, resolution of the prob-
lem may be effected not only by obtaining area-wide averages, but also by
developing a model capable of predicting local elevations in concentration
that are due to emissions from nearby sources.  With this need in mind we
undertook a limited effort to develop such a model.  The model is applicable
only for carbon monoxide and was used for validation in the vicinity of only
four monitoring stations.  While the results are promising, it must be em-
phasized that the development study was, in effect, mainly a pilot study
carried out to determine if the development and application of the model
represented a flexible means for resolving the problem of disparate scales.
The developmental work and the results are fully described in Appendix C.
The estimated contributions to measured concentrations made by local sources
at the four stations (as predicted by the subgrid scale model) are shown in
results presented later in this section.

     In closing this discussion, we wish to emphasize that the problem of
disparate scales is perhaps the major barrier to satisfactorily assessing
the performance of urban scale models.  Its lack of resolution has had a
detrimental effect on this work and will continue to be an issue until
spatially averaged measurements are made, or subgrid scale models are
developed.


A.   The Evaluation Procedure

     As we have noted, evaluation of the airshed simulation model for a
particular "validation day" consists of a sequential procedure, evaluation
for carbon monoxide followed by evaluation for nitrogen oxides, hydrocarbons,
and ozone.  The steps involved are the following:

     1.  Preparation of meteorological and emissions data.  Hourly wind
     speed,  wind direction, and mixing depth maps are prepared for each


                                  43

-------
validation day, as described in Appendix C of Roth et al (1971)
and in Section lie of this report.  As it is assumed that
the emissions inventory is applicable for all weekdays in 1969 and
as all validation days are weekdays, we use the inventory without
alteration, as reported in Appendix A of Both et al (1971)  and
Appendix A of this report.

2.   Preparation of other inputs to the model specif-La to the
     validation day.   These include:

     a.   Initial conditions.   Initial concentrations are specified
          in each ground level grid cell by interpolation using the
          data collected at monitoring stations during the hour at
          which solution is initiated.  Maps are needed for CO, NO,
          NO2, and reactive and unreactive hydrocarbon (RHC and UHC).
          Initial ozone concentrations are calculated assuming that
          the rate of reaction of ozone is equal to zero.  (Thus, the
          initial Oo concentration is given by an algebraic expression
          involving initial RHC, NO, and N©2 concentrations.)  Initial
          concentrations in cells aloft are set equal to the concentra-
          tion in the ground level cell.

     b.   Boundary conditions.  Boundary concentrations must be
          specified for each hour for all grid cells that lie along
          an inflow boundary from the ground to the inversion base.
          Also, concentrations must be specified along the upper
          boundary (the base of the inversion) when there is an influx
          of material from above the inversion.  The horizontal
          boundary conditions (east, west, north, and south boundaries,
          where the winds enter the modeling region) are established
          by using the concentrations measured at the nearest monitor-
          ing station at the hour in question as a guide.  Variations
          in concentrations with  x  and  y  along the boundary at a
          given  t  in regions remote from monitoring stations are
          estimated solely on a judgmental basis.  It is assumed
          that concentration is invariant with  z  for a given  x ,
          y , and  t .  Boundary conditions aloft (at the inversion
          base) are established for a particular day, as described in
          Section IIC of this report.  As with initial conditions,
          boundary concentrations of ozone are computed assuming that
          the rate of reaction of ozone is zero.

     c.   Radiation intensity data.  Actual measurements of radiation
          intensity at the ground as a function of time were made by
          Scott Research Laboratories at El Monte and Commerce for the
          validation days.  The measured curves (I vs. t) were corrected
          for variations in solar zenith angle (from tables prepared by
          the Dept. of Meteorology, UCLA (1966)) and normalized.  The
          results, plots of  ]l sec  (z)/[l sec (zJlmax}  vs.  t  for each
          of the validation days are given in Figures  5 through 10.
          Averages of the normalized, angle-corrected intensity measure-
          ments made at the two stations are then related to  k, through
                                44

-------
the relationship given in Figure 11, as reported by
Eschenroeder and Martinez (1970).

Kate constants and stoichiometric coefficients for _
hydrocarbon reactions.  Referring to the kinetic mechanism
presented in Appendix C, the following parameters must be
established:  k-^ , k]^ , k^3 , ^15 , a , $ , 6 , and  e .
To do this, we lumped reactive hydrocarbons into four
groupings—paraffins  (excluding methane, ethane, and pro-
pane), aromatics (excluding benzene), ethylene, and olefins
(other than ethylene).  .Taking n-butane to be representative
of the paraffins, toluene of the aromatics, and propylene
of the olefins, we computed lumped rate constants for the
HC-0, HC-OH, HC-ozone, and PAN formation reactions based
on weighted averages of the individual rate constants
established during evaluation, of the kinetic mechanism.
The weights are taken as the proportion of each group
(paraffins, aromatics, etc.) present in the atmosphere.

Gas chromatographic data collected by Scott Research Labora-
tories at Commerce and El Monte on the validation days were
used in determining the averaged parameters.  As there was
little variation in composition with time of day, daily
averages were calculated.  Moreover, as the daily averages
varied little from day to day, at least for the three days
for which they were computed  (29 September, 30 September,
and 4 November), we used the individual averages for each
of the three days (see Table 3) and the 29 September values
for the remaining three days.  Stoichiometric coefficients
were calculated in a manner similar to that used for the
estimation of the lumped rate constants.

The formulas used to calculate the various parameters are as
follows:

                     k.
                      ij        i = 1 paraffins
        k. . =  "'v*	            ^ aromatics
         M      >-Ci               3 ethylene
                                    4 olefins

                  c  e          j = 11, 12, 13, 15
                   i  i             (j corresponds to the
                    	             reaction number in
                    i               Table 1 of Appendix B)
                        Ci
                       45

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                                                                          *'&
                                                                           T
                                                                           fE
                                 j- FIGURE  8.  RADIATION INTENSITY VS. TIME FOR 4-
                                               OCTOBER 30,  1969                t
                                   f-f
                                                     ±1
                              n:
                                        -Commerce

                El Monte
                                  (I sec z)max =41.5 w/m
                                           t-rm-rrt-t-rrrr
                                        ±t±

fa±
                                                                                  4q
                                                                                 ii.
                                                                                 -r
                                                           LA-
                                                          3EI
                                                               TIME
                                                               (PST)
     '-00   6:00    7-'00    8'-00
   Q:00   .10:00    1100   12^00  13:00   14:00   (5-00

                 50

-------
         (.1 sec zj/(.l  sec zj
 LO-
                           max
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                                                                          -rrr-
                                  FIGURE 9 .  RADIATION INTENSITY VS. TIME

                                              NOVEMBER 4, 1969
                         Vt
                                       4-
                                       Conmerce
                                       El Monte
                                       -lr
                                  4-44
                ±
%
                                    sec z)mov = 34.9 w/m
                                                       2  U4
                                          max
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                                                                     d
9:00   10 00   H'OO  12^00  13:00  !4'00  15-00  16 00

              51
                                                                                      TIME

                                                                                      (PST)

-------



















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[from Eschenroeder et al.(1970)]
             52

-------
              Parameter values used in the calculation are summarized
              in Table  2 ,  and values  of the various parameters cal-
              culated for  the three days are given in Table 3.   " The
              rate constants for inorganic reactions may be found  in
              Appendix B.

     3.  Evaluation for carbon monoxide.   The airshed model is  exercised
     from  5 AM to 3 PM for each of the validation days.   Predicted ele-
     vations in concentration in the vicinity of four monitoring stations
     due to local emissions (as given  in Appendix C)  are added  to  the air-
     shed  model predictions.  Alterations were made in the 29 September
     and 30 September wind fields after initial simulations were carried
     out for these days.  No other changes in input were made  for  these
     days, nor were any changes made for the four additional days. Hourly
     averages of predicted concentrations were computed (averages  of  con-
     centration at each node computed  for all time steps falling within
     the hours), with predictions rounded to the nearest ppm.

     4.  Evaluation for nitrogen oxides,  hydrocarbons, and ozone,  upon
     satisfactory completion of the carbon monoxide simulation  for a
     particular day, evaluation was carried out for the reactive species.
     All procedures are as described for CO.  Results are rounded  to  the.
     nearest pphm.

     Comparison of predictions with measured values are made at the sites
shown in Figure 12 and listed in Table 4.  Since monitoring stations  are
not, in general, situated near the center of a ground level grid cell, we
employ an  interpolation procedure to  calculate the predicted station con-
centration.  In Figure 13, we illustrate the computations involved.

     The ratio of simulated to computing time for the validation runs
are as follows  (IBM 370/155):

                    CO                          150:1
                    NO, N02, RHC, UHC, and O3     8:1
                       (as well as CO)


B.   The Results

     Evaluation was carried out  for carbon monoxide  (CO), nitric oxide  (NO),
nitrogen dioxide  (NO.), reactive plus unreactive  (or  total) hydrocarbon  (HC)
and ozone  (0_)  for the  ten hour period 5 AM to  3 PM for the following days
in 1969:

                               11 September
                               29 September
                               30 September
                               29 October
                               30 October
                                4 November
                                  53

-------
                      TABLE  2    RATE CONSTANTS AND STOICHIOMETRIC COEFFICIENTS
                                 USED IN COMPUTING LUMPED PARAMETERS
                          k. ,,      k.         k.  .,       k.  ,c      a.       B.       6.       e.
                           1,11       i,12        i,13        1,15       i        i        i        i
Paraffins
(except methane,
e thane, propane)
 1,920     5,720   1.125x10
                           -4
        1.2
               .61
J£     Aromatics
       (except benzene)
                           6,420    15,000   7.5x10
                                                   -5
                                    30
        1.2
               .61
Ethylene
 7,720     2,500   2.87x10
                                                    -3
16
0.2
                                                                                                    .22
Olefins
(except ethylene)
40,000    25,000   1.65x10
                          -2
16
0.2
                                                                                                    .22
All reaction rate constants are in ppm    min 1.

-------
             TABLE  3.  COMPUTED VALUES OF THE RATE CONSTANTS
      AND STOICHIOMETRIC COEFFICIENTS FOR THREE OF THE VALIDATION DAYS
           29 September
                     30 September
             4 November
 11
 12
 13
 15
   7,300


   9,500


1.9 x 10


   13.8


    12
                     -3
                                       6,300
                                       8,400
                                    1.7 x 10
                                       11.9
                                       11.9
-3
   6,500



   8,000


1.8 x 10


   11.1



   12.4
-3
                .95
                          .95
                 .92
                .51
                          .52
                 .50
All computed parameters are rounded to either two or three significant
figures.
                                   55

-------
Figure  12.  Locations of Monitoring Stations Relative
 to Major Contaminant Sources in the Los Angeles Basin
        •v.  -
        •  —
        A  -
        X  -
        O  _
freeways
oil refineries
power plants
airports
contaminant monitoring stations
                          56

-------
            Table  4.    Addresses and Locations of Contaminant
              Monitoring Stations in the Los Angeles Basin
Station
Number

   1

  60


  69

  71


  72


  74

  75

  76


  78


  79


  80


 OC1


 OC2
 Station
Code Name

   CAP

   AZU


   BURK

   WEST


   LONB


   RESD

   POMA

   LENX


   RB


   PASA


   WHTR


   ANA


   SNA
OC3 LAH

Scott
Research
IELM

COM
                  Address

434 S. San Pedro Street, Los Angeles (at 4th Street)

803 N. Loren Avenue, Azusa (two blocks north of
Foothill Boulevard)

228 W. Palm Avenue, Burbank (at Victory Boulevard)

2351 Westwood Boulevard, Los Angeles (1/2 block
north of Pico Boulevard)

3648 N. Long Beach Boulevard,  Long Beach (at
36th Street)

18330 Gault Street, Reseda (at Etiwanda Avenue)

924 N. Garey Avenue, Pomona (at Kingsley Street)

11408 La Cienega Boulevard, Los Angeles (at
Imperial Boulevard)

615 E. Anita Street, Redondo Beach (at Pacific
Coast Highway)

1201 E. California Boulevard,  Pasadena (at Wilson
Avenue)

14427 Leffingwell Road, Whittier (at Telegraph
Road)

1010 S. Harbor Boulevard, Anaheim (at Vermont
Avenue)

Paulorino Avenue, Near Airport Control Tower,
Orange County Airport, Santa Ana

621 Ocean Avenue, La Habra (at Walnut Street)

El Monte Airport.

4545 E. Washington Boulevard,  City of Commerce
(at Long Beach Freeway)
                                     57

-------
       J+l
                  AY,
                                       AX-

                                      i-H
                8  - monitoring station location
             'station
     where
+C
   i+i
                                            fj+i5]
               I'™
                   AX


               n   AY
               n = —
                   AY



            Cj j = predicted ground level concentration above

                   grid  square  (I,J)


        Cstation = Pre<^ctec* concentration at the monitoring station
FIGURE 13.   INTERPOLATION PROCEDURE FOR CALCULATING THE PREDICTED

            CONCENTRATION AT A MONITORING STATION.
                               58

-------
The results are presented as computer plots of concentration vs. time for
each pollutant at those stations and on those days when data were avail-
able.  As there are five pollutants, fifteen monitoring stations, and six
validation days, a large number of plots is required.  (However, since NO
and NO_ are plotted together, since hydrocarbon is measured at a maximum
of six stations, and since plots were usually prepared only when data were
available, many fewer than 15x6x5 plots were needed.)  Tables 5 to 7
indicate the pollutant/station/day combinations for which plots were pre-
pared.  The plots may be found at the end of this report, following the
text.

     Predictions, of pollutant concentrations are also displayed on maps
in grid form, that is, as a function of  x  and  y   (or for the grid square
designated by (x,y)).  Grid plots are generated for each pollutant (1) at
each time step and (2)  at hourly intervals (i.e., hourly averages).  Examples
of plots exhibiting hourly averages for the period 11 AM to noon on 29
September are given in Figures 14 to 19.  Similar plots have been prepared,
at individual time steps and as hourly averages, for all pollutants for all
six validation days.  However, we have not included them here.

     Air quality data for 29 September and 30 September are described in
detail in Appendix E of Roth et al.  (1971).  Data for the remaining four days
were supplied to us by EPA.  Most of the air quality data were collected by
the Los Angeles and Orange County Air Pollution Control Districts which to-
gether operate a total of thirteen monitoring stations in the modeling region.
However, as we have mentioned earlier, Scott Research Laboratories collected
air quality data at two additional sites during this period.  We refer the
reader to their report, "1969 Atmospheric Reaction Studies in the Los Angeles
Basin", Vol. I-IV  (1970), describing the data collection program.

     Air quality data are corrected in accordance with the procedures describ-
ed in Section IIC and are displayed in the Figures in corrected form.  Special
attention, however, must be given to the comparative presentation of hydro-
carbon concentrations.  Total hydrocarbon measurements were made on a regular
basis at four locations in the Basin—Downtown L.A., Azusa, Pasadena,  and
Anaheim.  Methane is monitored at three of these stations, the exception being
Anaheim.  In addition, Scott Research Laboratories measured hydrocarbons
using both flame ionization and gas chromatographic methods at El Monte and
Commerce.  As we treat unreactive (U) and reactive (R)  hydrocarbons separately
in our model, measured and predicted concentrations must be placed on the
same basis for the purpose of comparison.

     As most data are reported as ppm carbon (ppm C), we have converted pre-
dicted hydrocarbon concentrations, for both reactive and unreactive groupings,
to ppm C in the following manner.  For the Scott GC measurements, we have
computed the average number of carbon atoms per molecule for both unreactive
and reactive classes of hydrocarbons (NCy and NCR respectively) using
                              NC  = -
                              NCU
                                 59

-------
              TABLE 5.   MONITORING LOCATIONS AT WHICH PLOTS OF CARBON MONOXIDE
                        PREDICTIONS AND MEASUREMENTS WERE PREPARED FOR THE SIX
                        VALIDATION DAYS
^~~7~~~-~^pay
Station" -»»^_
Reseda
Burbank
Pasadena
Azusa
El Monte
Downtown LA
Pomona
West LA*
Commerce
Lennox*
Whittier*
La Habra
Long Beach*
Anaheim
Santa Ana
29 Sept.
X
X

X
X
X
X
X
X
X
X

X


30 Sept.
X
X

X
X
X
X
X
X
X
X

X


29 Oct.
X
X

X

X
X
X
X
X
X

X
X

30 Oct.
X
X

X
X
X
X
X
X
X
X

X
X

4 Nov.
X
X
X
X
X
X
X
X
X
X
X

X
X

11 £
X
X

X

X
X
X
X
X
X

X
X

* Local corrections made for this station.
                                        60

-------
TABLE 6.  MONITORING LOCATIONS AT WHICH PLOTS OF NITRIC OXIDE, NITROGEN DIOXIDE,
          AND OZONE PREDICTIONS AND MEASUREMENTS WERE PREPARED FOR THE SIX
          VALIDATION DAYS*
         Day
29 Sept.   30 Sept.   29 Oct.    30 Oct.    4 Nov.
11 Sept.
Station"**""*.
Reseda
Burbank
Pasadena
Azusa
El Monte
Downtown LA
Pomona
West LA
Commerce
Lennox
Whittier
La Habra
Long Beach
Anaheim
.Can-t-a Ana

X
X
X
X
X
X
X
X
X
X
X
X
X
X


X
X
X
X
X
X
X
X
X
X
X
X
X
X


X
X
X
X
only
NO and 0
X
X
X
X
X
X
only NO
X
X


X
X
X
X
only
°3
X
X
X
X
X
X
only
NO and NO
X
X


X
X
X
X
X
X
X
X
X
X
X
X
X
X


X
X
X
X
only
°3
X
X
X
only NO
and 03
X
X
X
X
X

*Mark (X) indicates all three pollutants measured at station for the particular
 day.  For each station, nitric oxide and nitrogen dioxide are plotted on a
 single figure, while ozone is plotted on a second figure.  Each set of two
 figures are presented on one page.
                                        61

-------
      TABLE 7.  MONITORING LOCATIONS AT WHICH PLOTS OF TOTAL HYDROCARBON
                PREDICTIONS AND MEASUREMENTS WERE PREPARED FOR THE SIX
                VALIDATION DAYS
         Day      29 Sept.      30 Sept.   29 Oct.     30 Oct.     4 Nov.      11 Sept.
Station
Pasadena
Azusa
El Monte
Downtown LA
Commerce
Anaheim
X
X
X
X
X
X
X
X
X
X
X
X
XXX
XXX
X
XXX
X
X
X
X

X


                                          62

-------
FIGURE 14.
•
!

AVERAGE GROUND LEVEL CONCENTRATIONS (PPM i OF co BETWEEN THE HOURS OF 1100. AND 1200. PST ' >

yy
ft 74 ?S

25
24
23
22
21
20
19
1 8
17
1 16
i
15
14
13
12
11-,-
10.
9
a
7
6
_5
4
3
Z
_l
46888776555
5 8 10 10 10 9 H 8 7 6 6
SAN GABRIEL MTNS
5899 10 99988777
• RESEDA
456667888888888 7
BURBANK
PASADENA AZUSA
22 3 3 3456 7 88 8 8 ~ 9 10 10 9 98 77
SANTA MONICA MTNS
EL MONTE
DOWNTOWN LA
2222-34444455555 578887
WEST LA
233333444444567887
CCMMERCE
2 3 3 3 3 3 33 4 4 5 6 7 88 7
LENNCX
HHtTTIER LA HABRA
223333344 457899
223333344 5679 10 10




6
6


6
6
6
5
6
7
. 8
9
\



666
66 6


POMONA
55 4
54 4
544

544
554
765
766
LONG BEACH ANAHEIM
2223334445667B8
PALOS VERGES

22345
PACIFIC OCEAN
2234
223
2 2
2
8


5
SANTA
4
3
3
2
B ._ 7 '7


5 5 5 !
ANA
555
444
33 4
i
233



-------
FIGURE 15.

AVERAGE GROUND LEVEL CONCENTRATIONS (PPHM) OF NO BETWEEN THE HOURS OF 1100.
1

25 1
24 1
23 1
22 2
21 2
20 1
19 ).
IB '
17 ).
16
15
14
13
12
11
10

8
7
6
5
4

2
1

2 3 4 5 67 B 9 ip 11 12 13 14 L5 16 17 18

1111122233
1111112222
SAN
111111222222
RESEDA
2223322222211 11
8UR6ANK
PASADENA
1 1 2 33 2 2 2 22 2 1 1 I 1 11
SANTA MONICA MTNS
1122322222222 lilt
EL MONTE
DOWNTOWN LA
1111333345665 4321
WEST LA
1 122233 56 66 5321
COMMERCE

LENNCX
125556666 7753
19



20



GABRIEL


1
1
1
I
1
I
1
2
WHITTIER
44567766 67632
12787556 7753
12544578 8853
LCNG BEACH
1122 3 10 11 9 8765
11 122776 57 12 10
PALOS VERDES
11111222 2345
11111111 1111
1 1
PACIFIC OCEAN
1




2
7
3
7
5
2
1
1
1




1
1
1
1
1
	 L
1
1
1
AND 1200. PST
21



MTNS

1
AZUSA
1
1
1


1
1
1
LA HABRA
1 1
1
2
2
4
4
2
2
I
4
1


1
1
22





1
1
1
1
1
1
1
1
1
1
1
1
ANAHEIM
2 2
3
4
3
2
2
6
1
1

3
3
3
3
SANTA
3
7
2
1

23





1
1
1
1
1
1
1
1
2
2
2
2
2
2
3
3
3
ANA
3
7
2
1

24





1
l_
1
1
I
1
1
1
1
2
2_
2
2
i
2_
3
3
3
5
3
1

25 !





1
1
1
1
POMONA
1
1
1
1
1
1
t
2 i
2 •
2
2 !
2 •
2
2 i
2 !
i
3 '
3 i
1
2 i
!

.
'

-------
FIGURE Ib.




AVERAGE GROUND LEVEL CONCENTRATIONS { PPHM ) OF
CTi
Ul
1

13













NC2 BETWEEN THE HOURS OF 1100. AND 1200. PST
14
15
16
17
18
19
20
21
22
23
24
25
•

25 7
24 8
23 9
22 7
21 4
20 3
19 3
18 4
17 *
16
15
14
13
12
11
10
9
a
7
6
5
4
3
2
1
11 13 15 16 17 17 17 17 16 15
14 17 18 20 20 21 21 21 20 It
16 19 20 22 22 23 24 23 23 22 21
RESEDA
13 15 15 18 20 - 22 23 23 24 23 22
RURB1NK
7 9 10 12 13 15 18 21 23 23 23
4 5 6 7 9 12 16 20 21 23 22
SANTA MONICA MTNS
4 5 6 B 10 13 17 21 .71 21 20
5 6 7 8 11 14 16 17 17 16 16
DOWNTOWN
4 5 f> 7 10 11 12 12 12 13 13
WEST LA
4 67 9 9 9 10 11 12
4 5 6 8 9 11 11 11
4 5 9 11 11 11 11
LENNCX
3 T 10 11 11 12 11
.9 9 10 11 12 11
3 7 11 11 11 10
3 6 9 88 9


PALOS VERDES
334677


PACIFIC OCEAN































SAN GABRIEL KTNS
21
22
22
20
17
LA
14
12
20
22
22
21
18
15
14
CCMKERCE
11 12
11
11
10
9
9
LONG
10
10
7






12
11
10
9
10
18
21
15
20
PASAOESA
23 22
22
20
17
15
15
14
12
10
10
It
BEACH
11 12
10
8






11
8






22
21
18
IB
18
18
16
14
14
15
15
15
11







18
21
21
EL
21
19
20
22
23
23
21
21
22
22
22
14

5





16
19
20
MONTE
20
20
20
22
25
27

15
18
19
20
19
19
20
23
25
WHITTIER
27 26
27
29
31
30
17
8
6
5



28
.32
37
37
21
in
7
6
6

•

14
16
17
18
18
18
18
20
21

12
AZUSA
14
16
17
16
16
16
16
17
LA HABRA
22 17
24
29
36
38
23
12
9
8
15
4

20
24

12
13
14
14
14
14
14
13
14
15
17
20
ANAHEIM
31 23
34
24
13
11
11
18
7
4
28
24
15
12
SANTA
13
20
10
5

11
_!?_
13
12
11
11
U
a
11
13
15
18
18
21
22
16
13
ANA
14
21
12
7

10
11
11
10
9
9
a
8
9
11
13
16
15
17
19
16
13
14
21
15
8

10
11
11
10
POMONA
8
7
7
7
8
9
U
14
14
15
15
13
12
14
19
16
10









1
1













i


-------