User's Guide for Executing OZIPR

by

M.W. Gery
R.R. Crouse

Atmospheric Research Associates, Inc.

729 Boylston Street
Suite 403
Boston, Massachusetts 02116

Order No. 9D2196NASA

Project Officer
Marcia C. Dodge

Chemical Processes and Characterization Division

Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711

ATMOSPHERIC RESEARCH AND EXPOSURE ASSESSMENT LABORATORY

OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711

i
 DISCLAIMER

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

ii
 ABSTRACT

In this study a new trajectory-type, air quality simulation model called OZIPR was
developed. OZIPR is based on EPA's Ozone Isopleth Plotting Program (OZIPP) Model, but
contains improved and expanded capabilities that make the model useful for research
purposes. OZIPR serves the dual purpose of providing: (1) a simple trajectory model
capable of utilizing complex chemical mechanisms, emissions, and various meteorological
parameters, and (2) procedures through which the Empirical Kinetics Modeling Approach
(EKMA) can be implemented for calculation of emission reductions needed to achieve
compliance with the National Ambient Air Quality Standard for ozone. While these
capabilities were included in earlier versions of OZIPP, the new OZIPR contains major
improvements that increase the program's ability to input, utilize, and output a much larger
range of information.
The Project Report serves as a user's manual for OZIPR. It contains a description of
the model, along with input and output requirements and options. The input and output files
for nine examples are included. These examples employ three different chemical kinetics
mechanisms and most of the major options available in OZIPR.

iii
 Contents

1 Introduction . . . . . . . . . . . . . . . .
1

. . . . . . . . . . . . .
Description of OZIPR 1

2 General Overview of OZIPR . . . . . . . . . .

3

. . . . . . .
Running OZIPR on a Personal Computer 3
. . . . . . . . . . . . . . . .
Limits to Input 4
. . . . . . . . . . .
VOC, NMOC, and NMHC 5

3 User's Guide to Command Options . . . . . . .

6

. . . . . . . . . . . . . . . . . . .
ECHO 6
. . . . . . . . . . .
MODIFICATION of Program 7
. . . . . . . . . . . .
MECHANISM LISTING 7
. . . . . . . . . . . . .
MECHANISM INPUT 7
. . . . . . . . . . . . . . . . . .
ZENITH 11
. . . . . . . . . . . . . . . . . . .
TIME 12
. . . . . . . . . . . . . . . . . . .
TITLE 12
. . . . . . . . . . . . . . . . . .
PLACE 12
. . . . . . . .
METEOROLOGICAL CONDITIONS 13
. . . . . . . . . . .
BOUNDARY CONDITIONS 14
. . . . . . . . . . . . . . . .
EMISSIONS 16
. . . . . . . . . . . .
SINGLE CALCULATION 18
. . . . . . . . . . . .
EKMA CALCULATIONS 21
. . . . . . . . . .
ISOPLETH CALCULATIONS 23
. . . . . . . . . . .
TERMINATION OF INPUT 24

4 The ISOPLOT Program - Drawing Isopleth Plots . .

25

iv
 . . . . . . . . . . . . . . .
Running ISOPLOT 25
. . . . . . . . . . . . . .
ISOPLOT Commands 26
. . . . . . . . .
Diagram Problems and Improvements 28

5 Examples . . . . . . . . . . . . . . . . .
29
. . . . . . . . . . . . . . .
OZIPR Examples 29
. . . . . . . . . . . . . .
ISOPLOT Examples 35

6 References . . . . . . . . . . . . . . . . .
36

v
 Acknowledgements

We thank Professor Harvey Jeffries of the University of North Carolina for providing
guidance concerning computer program design.

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vii
 1 Introduction

OZIPR is a research-oriented version of EPA's OZIPP (Ozone Isopleth Plotting

Package) computer modeling program. The OZIPR and OZIPP programs employ a
trajectory-based air quality simulation model, in conjunction with the Empirical Kinetics
Modeling Approach (EKMA), to relate ozone concentrations to levels of organic and
nitrogen oxide (NOx) emissions. While the aim of earlier OZIPP versions was to provide a
rigid structure within which State Implementation Plans could be formulated, the goal of
OZIPR is to furnish a comprehensive research tool that is of use to Agency planners and
model developers.
This version, called OZIPR (R for research), is specifically enhanced to provide input
of more parameters, but in a less rigid format. Output has been expanded and there are also
significant improvements to all facets of the computer program. The structure of the
program is similar to OZIPM-4, however, so the published user's guide (Hogo and Gery,
1988) for that program serves as a reference for the previous development and inherent
structure of OZIPR.

Description of OZIPR

OZIPR simulates complex chemical and physical processes of the lower atmosphere
through use of a trajectory model. The physical representation is a well-mixed column of air
extending from the ground to the top of the mixed layer. This idealized air column moves
with the wind (along the wind trajectory), but cannot expand horizontally. Emissions from
the surface are included as the air column passes over different emission sources, and air
from above the column is mixed in as the inversion rises during the day. Very complex
chemical mechanisms may be input into OZIPR to describe the chemical processes that occur
within the modeled air mass.
Besides individual trajectory simulations, the program can use the EKMA procedure
to automatically estimate the amount and type of precursor emission reductions required to
achieve a specified ozone level. The ozone level currently defaulted in EKMA is a one-hour

1
average maximum concentration of 0.12 ppm, the national ambient air quality standard. In
the EKMA procedure, OZIPR performs multiple simulations with different levels of organic
and NOx precursor emissions to estimate the effect of reduced emissions on maximum ozone
concentrations.
OZIPR can also perform a specified set of simulations to calculate ozone levels at
fixed intervals. This allows for the plotting of fixed ozone concentration lines (isolines) as
a function of initial precursors. A post-processor program called ISOPLOT is used to control
isopleth dimensions, plot options, display results, and provide output to printers and data
files.
Although the basic structure of the program is similar to earlier versions of OZIPP,
OZIPR was enhanced in this study to provide expanded yet simpler input capability, more
calculation options, greater calculation speed, and enhanced output options. These
improvements are described in the following sections. The next section provides an
overview of OZIPR usage, Section 3 serves as a user's reference for the OZIPR commands
and options, and Section 4 describes the ISOPLOT program and options. The fifth section
provides examples of nine input files and the resulting output.

2
 2 General Overview of OZIPR

Running OZIPR on a Personal Computer

The program is started by typing "OZIPR filename" for an input file called
filename.INP. For this example, the program (ozipr.exe) and the input file are in the same
subdirectory. However, it is also possible to use other directories as long as the path is
designated. For example:

c:\ozipm\pgm\ozipr c:\ozipm\input\test1,

runs the OZIPR program in subdirectory c:\ozipm\pgm, using the input file test1.inp in
subdirectory c:\ozipm\input.
Output files are created in the same sub-directory as the input files, if needed, using
filename with different extensions. They are:

filename.OUT The standard output file

filename.PRN An ASCII file of selected time/concentration data

suitable for importing into commercial spreadsheet
programs.

filename.ISO Output of isopleth results

The input file is a text file consisting of a series of OPTIONS and COMMANDS.
In addition, the input file can contain the names of commonly used "include" files that are
inserted into the text of the input file. This is done by inserting the character "@", followed
by the complete filename of an include file at the location in the input file where the text of
the include file is desired. More than one include file may be used, and they can also be used
within the include files.
The general rules for the format of the input file and include files are:

1) The first 4 letters of a command are usually significant (in the following text, the
actual significant letters are underlined);

2) Top level commands must be followed by ">", and commands end with a "<";

3
3) Upper case is currently mandatory;

4) Comments are allowed between { } and ( ), or on lines where the first character is "!";

5) The main input file (filename.INP) must terminate with "END."

Limits to Input

In previous versions of OZIPP, a fixed amount of input was allowed for a certain
option, such as 20 photolysis reactions, or 24 hours of temperature, etc. These numbers were
deeply buried in the computer code and could not be changed. One result of this study was
to uncover these numbers and bring them to the top of the program so that they may now be
easily changed if the user wishes to expand the program's capabilities.
In the following section many options allow up to n hours, species, reactions, etc. If
the user attempts to input more than n values, the program will print a message and stop.
The value n can be increased with minor alteration of the program, but possession of the
source code and knowledge of FORTRAN compilation is required.
The parameters that can now be easily varied and their current limits are:

Simulation Hours = 24
Total Reactions = 160
Photolysis Reactions = 23
Reaction Products = 12

Total Species = 65
VOC Species = 20
Emitted Species = 10
Isopleth Species = 12
Deposition Species = 10

Print Species Names = 20

Average Species Names = 10
Dump Names = 12
Dump Rates = 12
File Species Names = 20
VOC, NMOC, and NMHC

4
 Over the years a number of seemingly ambiguous methods to group volatile
hydrocarbons have developed. In OZIPR any organic compound, including methane, may
be entered as a species by including it in at least one reaction in the MECHANISM option.
In addition, OZIPR and OZIPM allow grouping into one unique set of organics, the group
named VOC (volatile organic compounds, which is usually used to describe those classes of
anthropogenic emitted organics that are subject to control).
The group of individual organic species that comprise VOC is defined within the
MECHANISM option; the species are named and the number of carbons in each is given.
The BOUNDARY/REACTIVITY option allows the user to list the fractions of each species
included in the VOC group that constitute emitted VOC, surface transported VOC, and aloft
transported VOC. These three sets of information allow OZIPR to account for emissions and
transport of the mass in the group VOC.
Most important, however, is the fact that this specific method of grouping facilitates
the EKMA and ISOPLETH options. By lumping all organic species subject to emission
control as VOC, it is a simple function for OZIPR to diminish VOC emissions in ozone
attainment calculations. [Similarly, NOx and CO are controlled in EKMA calculations,
where NOx is a combination of NO and NO2 and CO represents carbon monoxide.]
Therefore, VOC is a specialized OZIPR subset of often-used organic compound
groupings called non-methane organic compounds (NMOC) and non-methane hydrocarbon
compounds (NMHC). VOC is reported in ppmC. The ratio of VOC to NOx is not
necessarily the ratio of all NMOC to NOx. No effort is made in any OZIPP version to
combine and count all organic species as NMOC.

5
 3 User's Guide to Command Options

This section contains a list of the available command options that can appear in the
input file. As noted, format is no longer column-oriented, but the conventions noted in the
previous section must be followed. The options are first listed to indicate proper format. A
brief discussion of each option follows this listing. The default values for each command are
listed as "DF =". Most options are similar to those implemented in previous versions of
OZIPP, and the reader should consult the most recent OZIPM-4 report (Hogo and Gery,
1988) for more detail concerning the basis of various options.
Many options in OZIPR require data from a previous option. Therefore, the ordering
of the options in the input file is important. In many cases, the program will terminate with
a notice to check input if improper ordering could cause an otherwise undetectable error. It
is suggested that the following order be maintained as the order of all input streams.
However, note that it is possible to stack successive commands in one input stream. For
instance, after input of various meteorological and boundary conditions, one can perform a
CALC and EKMA, then change some earlier meteorological conditions and perform another
EKMA.
The OZIPR options are:

ECHO of input file:

ECHO; or NOECHO;

ECHO allows the user to list the input file as it is read by the program. The NOECHO (or
OFF) command terminates echoing of input (DF = NOECHO). These commands may
appear anywhere in the input stream.

6
Program MODIFICATION commands:

MODIFY >
WIDTH = number;
ACCURACY = number;
TENSION = number;
< (MODIFY)

WIDTH is the column width of the device upon which the output file will be printed. The
present options are for 80 or 132 columns (DF = 80).

ACCURACY is the error tolerance of the numerical integration routine, from 0.1 to 0.00001.
Smaller values require more calculations at greater accuracy (DF = 0.003).

TENSION is the factor for the hyperbolic spline functions used in the EKMA routine when
two ozone maxima occur in a single simulation (DF = 2) . If convergence is not achieved,
changing this factor may help. However, the default is usually the best value and it is not
recommended that this be to changed unless necessary.

Chemical Mechanism Listing command:

MLIST/(NOMECHLIST);

MLIST provides a listing of the chemical mechanism used, a list of rate constants at standard
conditions, and a list of the kinetic expressions and rate parameters used (DF =
NOMECHLIST).

NOMECHLIST disables chemical mechanism listing.

Chemical MECHANISM input:

MECHANISM [units] >

CNUMBERS = vocspecies1, C#,
vocspecies2, C#,
.
.
vocspeciesn, C#;

7
 REACTIONS = (see below)
< (MECH)

MECHANISM is the mandatory, user-supplied chemical kinetics mechanism. Input is

relatively free-format, although a certain order must be maintained as discussed next. Units
refers to the type of units that the kinetic expressions and rates utilize (also below). At
present, the default is "PPM" (ppm-min units) with the only option being "CM" (molec-cc-
sec units). One unit format must be chosen per simulation. As noted, the previous top-level
command, MLIST/NOMECHLIST can be used to provide a listing of the reactions and
kinetic expressions in the output file.

CNUMBERS allows the mandatory naming of the non-methane organic species

included in the "VOC" mixture, and tells OZIPR the number of carbon atoms in each
species. The species named in CNUM must match the VOC species listed in the
BOUN/REAC option. Also, this option must precede the REACTION listing on
input.

The REACTION LISTING format follows these rules:

Immediately after the CNUM option, the text string "REACTIONS =" designates the
beginning of free-format reaction listing input. This is followed by a listing of each
consecutive reaction as described next. Species names have up to 4 significant
characters, any extra are truncated. Legal characters to use in naming species are "A-
Z", "a-z", "0-9", and ":". Tabs are not allowed (the space bar must be used to insert
blank spaces).

Each reaction begins with the reactants (if there are any). Zero to 3 Reactants may
be included, separated by "+". No stoichiometry is allowed for reactants. After the
reactants, a "=" indicates that a list of products will follow. M, N2 and O2 may be
used as reactants. The concentrations of these species have been coded into OZIPR
and do not need to be specified by the user (DF: O2 = 209,460 ppm, N2 = 780,840
ppm, and M = 1,000,000 ppm). The rate constants given will be appropriately
multiplied by the concentrations of these species to produce rate expressions.

Even if there are no products or no reactants, a "=" is mandatory for each reaction.
Zero to twelve products and product coefficients are allowed. Products and their
stoichiometric coefficients are joined by a "*". Products, or coefficient*product
pairs, are linked by a "+". In the event of a negative coefficient, the "+" is still
required prior to the "-" of the coefficient ("+" is a symbol linking entities while "-"
is part of the coefficient).

After listing the reactions, a rate expression, initiated by either "#" or "%", must be
included. There are many types of rate expressions, which are described below.

8
Further, the rate expression may be modified by a number of options, including
dependence on the solar zenith angle (photolysis reactions) and dependence or
equilibrium with other rates or reactions. These modifiers begin with the symbols
"*" and "/", followed by symbolic language as described below.

Each reaction is terminated by ";".

Rate Expressions are of two types, standard and special. Most standard expressions,
with the exception of falloff expressions, can be used when rate constants are
expressed in either CM or PPM units. The input of standard rate expression
parameters begins with "#". Following this, the "@", "^", and "&" are used to allow
input of various parameters as follows:

Standard Expression Input Form

k=A #A

k = A x (T/300)B #A^B

k = A x e(-C/T) #A@C
(where C=Ea/R)

k = A x (T/300)B x e(-C/T) #A^B@C

The falloff expression listed below requires the values of A, B, and C to be input in
CM units even if all other reactions are listed in PPM units.

ko[M]
k = (-----------------) FG #Ao^Bo@Co&Ai^Bi@Ci&F&n
1+ko[M]/ki
where:

ko and ki are of the form A x (T/300)B x e(-C/T), or any other standard format.

and,

G = {1+[log(ko[M]/ki)/n]2}-1

[M] is known and automatically included in the falloff rate constant calculations. Ea
is the activation energy in kcal/mole. The value included on input is C = Ea/R, where
R is 0.0019872 in these units. Be careful of the sign of C.

9
The falloff parameters ko and ki are input in one of the standard formats given above.
ko always precedes ki on input. F and n need not be included. If not specified, the
defaults of 0.6 for F and 1.0 for n are used. Units of these falloff reactions are
always CM.

Special rate expressions are fixed algebraic expressions of a non-standard type.

These expressions begin with the character "%".

Special Expression Input Form

k = A x (1.0 + 0.6*Pressure) %1 #A

k3[M]
k = ko + (----------------) %2 #Ao@Co&A2@C2&A3@C3
1+k3[M]/k2

where, ko, k2, and k3 are of the form A x e(-C/T), as in the standard expression above.

Special rate 1 is used for the OH + CO reaction where pressure is in atmospheres and
the value for A is either in CM or PPM depending on the main units in the MECH
option.

Special rate 2 is a Lindemann-Hinshelwood expression, primarily used for the OH

+ HNO3 reaction. These parameters must always be in CM units.

Modifiers of rate expressions provide (1) dependence on another rate, (2) reverse
equilibrium with a second-order forward reaction, or (3) dependence on a value that
varies with zenith angle of the sun.

Linear dependence on another rate is of the form:

Expression Input Form

k = A x Kn #A *Kn

where A is a linear factor and Kn is the nth reaction listed in the MECH option.
This expression can be used in either rate format (CM or PPM).

A reverse equilibrium rate (only for first-order decomposition) can be calculated

directly from the equilibrium constant (Keq) by including the equilibrium constant
data and the reaction number of the forward equilibrium reaction.

Expression Input Form

10
 kr = kf / A x e(-C/T) #A@C *En

where A@C is the equilibrium constant and n is the reaction number of the forward
reaction. This expression can be used in either rate format (CM or PPM), with any
type of forward rate expression, but the equilibrium expression must be in the
"A@C" format and the reverse reaction must be a first-order process.

Photolysis reaction indicators follow the kinetic expressions for each reaction. The
format is either "/Ln" or "/Rn", where L refers to a specific table (Ln) of absolute
reaction rate factors vs. solar zenith angle in the ZENI option and R refers to table Rn
of relative reaction rate factors in ZENI. The relative factors will be multiplied by
the absolute factors listed for L1 in the ZENI option, after which, all relevant factors
will be multiplied by the calculated rate of reaction. For this reason, in both the
REACTION listing and the ZENI option, the listing of L1 should precede the
listing of any relative (R) reaction rates. Note that first-order reaction rates are in
min-1 for PPM units and sec-1 for CM units.

The rate modifiers operate under the following restrictions: (1) "*K" and "*E"
cannot be used in the same reaction, (2) any "*" modification must precede "/" if in
the same reaction, and (3) photolytic ("/L" or "/R") reactions are allowed with falloff
rate expressions.

ZENITH Angle Dependence of Photolysis Rates

ZENITH >

L1: za0, za10, za20, ...... za70, za78, za86,

R or Ln: za0, za10, za20, ...... za70, za78, za86,

R or Ln: za0, za10, za20, ...... za70, za78, za86,
R or Ln: za0, za10, za20, ...... za70, za78, za86;

< (ZENI)

ZENITH allows the user to vary the rates of photolytic reactions relative to the angle of solar
elevation (which is related to the spectral distribution of actinic flux). The values in these
tables are input for 10 zenith angles (0 through 70 in increments of 10, and 78 and 86 degrees
from zenith). A cubic spline interpolation is performed to find the factor value for the
current zenith angle. The tables in this option are accessed by including "/Ln" or "/Rn" at the
end of a reaction in MECH. Since all relative ("/R") factors are multiplied by the current
value of L1, the L1 listing must precede all R listings.

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Simulation TIME command:

TIME > number1, number2 <

TIME controls the start and end times of simulations. Number1 is the start time and
number2 is the end time. Both numbers are required (DF = 800 to 1800). The opening ">"
may be substituted for by an "=" and the closing "<" may be substituted for by a ";".

TITLE of simulation:

TITLE > text(up to 72 characters) <

TITLE allows the user to insert a text string defining the simulations. The opening ">" may
be substituted for by an "=" and the closing "<" may be substituted for by a ";".

PLACE of simulation

PLACE >
CITY = name;
LATITUDE = number,
LONGITUDE = number,
TZONE = number,
YEAR = number,
MONTH = number,
DAY = number;
< (PLACE)

PLACE is necessary to determine the zenith angle of the sun throughout the day.

CITY is the name of the location for the particular simulation. The city name can be
up to 24 characters (DF = Los Angeles, CA).
LATITUDE is the latitude in degrees north (DF = 34.058).
LONGITUDE is the longitude in degrees west (DF = 118.250).
TZONE is the local time zone, Eastern Daylight Time = 4, Pacific Daylight Time =
7 (DF = 7).
YEAR is the year (DF = 1990).
MONTH is the month (DF = 6).
DAY is the day (DF = 21).

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METEOROLOGICAL conditions:

METEOROLOGY >
DILUTION =
MHINIT = number,
MHFINAL = number,
TINIT = number,
TFINAL = number;
MIXING [nmix] = mh1, mh2, mh3, ........ mhnmix;
TEMPERATURE [ntemp,tunit] = t1, t2, t3, ... tntemp;
PRESSURE [punit] = number;
WATER [wnum] = w1, w2, w3, ... wwnum;
RH [wnum] = w1, w2, w3, ... wwnum;
< (MET)

The METEOROLOGY command allows the user to input mixing heights, temperature,
pressure and water vapor concentrations. This option must precede EMIS and MASS, as
well as CALC, ISOP, and EKMA.

DILUTION activates the characteristic mixing height curve based on the following
input information:

MHINIT is the initial mixing height in meters (DF = 510m).

MHFINAL is the final mixing height in meters (DF = 630m).
TINIT is the starting time of mixing height increase (DF = 800).
TFINAL is the ending time of mixing height increase (DF = 1500).

MIXING allows input of mixing height values (in meters) at the beginning and end
of each simulation hour. nmix is the number of values input, if dilution occurs for
n hours, the number of mixing height inputs should be n+1. (DF is to use DILU).

TEMPERATURE allows input of average column temperature values at the

beginning and end of each simulation hour. ntemp is the number of values input,
which is usually the number of hours+1 (DF = 303 K constant). tunit specifies the
temperature scale used on input (DF = "K" for Kelvin; other options are "C" for
Centigrade and "F" for Fahrenheit).

PRESSURE is the constant pressure to be used throughout the simulation. punit

specifies the pressure scale used on input (DF = "AT" for atmosphere). Other options
are "TO" for Torr (mm of Hg) and "IN" for inches of Hg (DF = 1 atm.).

WATER [wnum] allows input of average column water concentration in ppm at the
beginning and end of each simulation hour. wnum is the number of values input,

13
 which is usually the number of hours+1. If no water or RH values are input, DF =
20,000 ppm.

RH [wnum] allows input of relative humidity values at the beginning and end of each
simulation hour. wnum is the number of values input, which is usually the number
of hours+1. Because TEMP and PRES values are needed to calculate water
concentrations from RH, this option must follow the TEMP and PRES options or an
error will occur. There is no default for RH. If no option is used for water, water
concentration is defaulted as described in the WATER option.

If the simulation time extends past the number of values entered for TEMP, WATER, or RH,
the last value listed is extended to the end of the simulation. This makes it possible to
perform simulations with constant values by merely including one initial value in a table.

BOUNDARY Conditions:

BOUNDARY >
REACTIVITY =
vocspecies1, init_reac, aloft_reac, surf_reac,
. . . .
. . . .
vocspeciesn, init_reac, aloft_reac, surf_reac;
IFRACTION NO2 = fraction;
EFRACTION NO2 = fraction;
TRANSPORT =
O3SURFACE = concentration,
O3ALOFT = concentration,
VOCSURFACE = concentration,
VOCALOFT = concentration,
NOXSURFACE = concentration,
NOXALOFT = concentration,
COSURFACE = concentration,
COALOFT = concentration;
ALOFT CONCENTRATIONS =
specie1 = concentration,
. .
. .
specien = concentration;
INITIAL CONCENTRATIONS =
specie1 = concentration,

14
 . .
. .
specien = concentration;
DEPOSITION RATE PROFILES [numhours] =
specie1 = ratehour1, ratehour2, ... ratehournum,
. . . .
. . . .
specien = ratehour1, ratehour2, ... ratehournum;
CONSTANT DEPOSITION RATE =
specie1 = rate,
. .
. .
specien = rate;
< (BOUNDARY)

The BOUNDARY option controls the various concentrations, reactivities, and deposition
rates that occur at the boundaries of the reacting column. This option must precede EMIS
and MASS, as well as CALC, ISOP, and EKMA. It should be noted that the NO2/NOx
fraction for transported surface and aloft NOx is defaulted to 1.00 and cannot be changed.

REACTIVITY is mandatory. For each species of the VOC group listed in the
MECHANISM option, the user must include the species name and the fraction of
total VOC that each species represents in the initial mixture (resulting from
controllable emissions), the aloft VOC, and the transported surface-layer VOC.
These fractions should sum to 1.0 across all VOC species for each category. If this
is not the case, the program assumes any missing mass is in non-reactive species, or
stops with an error message if the total fraction exceeds unity.

IFRACTION is the NO2/NOx fraction for the NOx that is present due to controllable
emissions at the start of the simulation (DF = 0.25).

EFRACTION is the NO2/NOx fraction for the NOx emissions throughout the
simulation (DF = 0.05).

TRANSPORT controls the initial concentrations of O3, NOx, VOC, and CO in the
surface and aloft layers that are due to transport. The SURFace concentrations are
used to account for the initially present mass in the surface layer that is due to
transport. In the simulation, this is added to the initial mass resulting from
controllable emissions (input with the CALC, EKMA or ISOP options) and the non-
controllable mass input with INIT option. The ALOFT mass is added into the
surface layer as the mixing height rises. Default values are all 0.0.

15
 ALOFT CONCENTRATIONS are constant upper-layer concentrations of species
other than the TRAN species. Mixing height rise will entrain ALOFT
concentrations into the surface layer. Only H2O will not be diluted or enhanced with
mixing height rise.

INITIAL CONCENTRATIONS are initial surface-layer concentrations of species

(other than the specific groups noted in the TRAN option) at the start of a
simulation. However, additional NO, NO2, or specific VOCs can be added here. If
specific VOCs are added, their concentration should be given in ppmV. Note that the
INIT concentrations are not controlled in EKMA calculations. If a non-controlled
species is emitted, which is only possible if the MASS option is used, the initial
surface concentration from the MASS option is added to any INIT concentration to
determine the total initial mass. Therefore, if the MASS option is being used, INIT
should only be used for the same species if additional mass is needed. H2O cannot
be initialized with INIT. MET/WATER or MET/RH must be used for H2O.

DEPOSITION allows input of hourly deposition velocity (cm/s) profiles for up to

10 species (the limit of 10 also includes the constant deposition velocity below).

CONSTANT DEPOSITION (or CDEP) allows the input of constant deposition

velocities (cm/s) for up to 10 species (the limit of 10 also includes the species in the
DEPOSITION option; thus, if DEPO is used for 6 species, only 4 species can be
input using the CON option.)

Input of hourly EMISSIONS:

EMISSIONS [numhrs] >

VOC =
em1, em2, .... emnumhrs,
NOX =
em1, em2, .... emnumhrs,
CO =
em1, em2, .... emnumhrs;
or
MASS [numhrs] >
VOC [mw] = conc,
em1, em2, .... emnumhrs,
NOX [mw] = conc,
em1, em2, .... emnumhrs,
CO [mw] = conc,
em1, em2, .... emnumhrs,
specie3 [mw] = conc,
em1, em2, .... emnumhrs,

16
 specien [mw] = conc,
em1, em2, .... emnumhrs;
< (MASS or EMIS)

To input emissions, the user has two optional methods: EMIS or MASS. Only one method
may be used with each simulation. This option must follow MET and BOUN, and precede
CALC, ISOP, and EKMA. Only 3 species (VOC, NOx and CO) are allowed for EMIS but
up to 10 may be used with the MASS option.

The differences between EMIS and MASS are described next. These options have in
common the following:

In the option command line, the user must include the number of hours that values
will be given for. All species must use the same number of hours.

VOC, NOX and CO are unique groups because the emissions of these species are
varied in EKMA and ISOP calculations. The species included in the VOC group and
the fraction of total VOC that each comprises are input using the BOUN/REAC and
MECH options. NOx consists of NO and NO2 and the ratio of NO-to-NO2 for both
the initial surface layer and the emissions can be given in BOUN/REAC.

An emission ratio table will be printed on output. Regardless of the method used, the
output will show the ratio of emissions to initial concentration for all emitted species
or groups. These ratios are calculated at the initial mixing height, a temperature of
298.15 K, and the specified simulation pressure. During simulation the program
continuously accounts for changes in the volume of the column (changing mixing
height) and air density (temperature) before the mass of emissions is added to the air
column. A second table is also printed showing mass emission rates (kg/km2 / hour).

EMIS allows the user to input hourly emission fractions that are directly ratioed to the initial
surface concentrations of controllable VOC, NOx and CO emissions (the initial
concentrations are input in the CALC, EKMA or ISOP options). The emission fractions
should be calculated at the same mixing height as the initial, controllable surface
concentrations; the program will automatically account for later changes in mixing height.
Since this is a direct ratio to initial values given elsewhere, conc is not used and mw is not
needed for conversion.

MASS allows the user to input hourly emission mass for up to 10 species or groups in units
of kg/km2 per hour. An initial concentration (in units of ppm) that is used by the program
to convert hourly emission densities into emission fractions, must be included on the species
line. For VOC, NOx and CO, OZIPR compares this value to the concentration input in
CALC, EKMA or ISOP for consistency. A warning message will print if there is a
mismatch, but in some cases a different value is useful so the program does not stop. For

17
species other than VOC, NOx and CO, the initial concentration (conc) specified in the MASS
option is used as the initial mass due to emissions and is added to any INIT mass (see
BOUN/INIT). This mass is then converted to ppm ratios. As noted above, because the
calculation of column concentration of emissions also depends on the molecular density of
air and the volume of the column, the ppm emission ratio factors printed on output will differ
if TEMP and mixing height values vary from 298.15 K and the initial mixing height.

conc is used in MASS only. The units are ppmC for VOC and ppmV for all other
species, including individual organics that are part of the VOC group.

mw is the molecular weight of a species used for conversion of MASS units to ppm.
MW is mandatory for all species except VOC, NOx, and CO. Molecular weights for
these species need not be entered if default values are desired; the defaults are: VOC
= 14.5, NOx = 46, and CO = 28. If a different value is desired for VOC, the user
should note that mw is the molecular weight of a carbon unit (CH2.5) since the
calculation is in ppmC. The default NOx is the molecular weight of NO2 because
emission inventories are given as 100% NO2.

Since EKMA does not control species other than VOC, NOx, and CO, any other emissions
input with the MASS option, including specific VOC species, will not be reduced in
attainment calculations.

Individual CALCULATIONS (single simulations)

CALCULATE >
VOC = concentration;
NOX = concentration;
CO = concentration;
PRINT [print control options] =
NAMES [number] = species1, species2, ..... speciesX,
TINIT = number,
TSTEP = number,
AVG [number] = species1, species2, ..... speciesX,
TAVG = number,
CDUMP [number] = species1, species2, ..... speciesX,
RDUMP [number] = rxn#1, rxn#2, ..... rxn#X,
NODUMP;
FILE [number] = species1, species2, ..... speciesX;
< (CALCULATE)

VOC is mandatory. It is the concentration of VOC (ppmC) in the initial surface-layer

mixture that is due to emissions and subject to control. This mass is added to any transported

18
or other uncontrollable VOC sources to total the actual concentration that a simulation will
begin with (DF: VOC = 0.0 ppmC).

NOX is mandatory. It is the concentration of NOx (ppm) in the initial surface-layer mixture
that is due to emissions and subject to control. At the beginning of a simulation this mass
is added to any uncontrollable NO or NO2 (DF: NOX = 0.0 ppm).

CO is the concentration (ppm) in the initial surface-layer mixture that is due to emissions and
subject to control. This mass is added to any transported or other uncontrollable CO sources
to total the actual concentration that a simulation will begin with (DF: CO = 0.0 ppm).

The concentrations listed for VOC, NOx, and CO in the output file represent all the initial
mass of these species that is included in the calculation. That is, the values printed at each
time step in the output file include the VOC, NOx, and CO concentrations listed in the CALC
option as well as any VOC, NOx, and CO transported in the surface layer. In addition, it
includes the initial surface-layer concentration of any individual VOC species specified with
the INIT option. It also includes the concentration of individual VOC species included in
the MASS option.

PRINT controls the standard CALC output.

TINIT is the first time (minutes from the beginning of the simulation) when
concentration and rate information is to be printed (DF = 60).

TSTEP is the time step (in minutes) from TINIT until the end of the simulation that
concentration and rate information is to be printed (DF = 60).

TAVG is the time interval (in hours!) that the running maximum average
concentrations for species in the AVG option are calculated over (DF = 1).

NAMES [number] are the names of up to 20 species for which the concentrations at
each time step will be printed along with information on the instantaneous mixing
height, zenith angle and temperature. The format of the output generated when the
NAME option is used is similar to the format used in the OZIPM-4 program.
Inclusion of a delimiter (comma or semicolon) after the NAMES sub-command will
print all species (DF = all species).

AVG [number] are the names of up to 10 species for which running averages will be
calculated and the highest reported at the end of a simulation. This also controls the
species whose concentration at each time step are listed on the screen during run
time. Concentration-time information for up to 5 species are given on the screen for
the default column width of 80. If the width of output is 132 columns, concentration-
time information for 10 species is listed on the screen (DF = O3).

19
 CDUMP [number] produces a tabular listing of the concentrations for up to 12
species at each TSTEP at the end of the listing (DF=NODUMP).

RDUMP [number] prints a listing of the instantaneous rates for up to 12 reactions at

each TSTEP at the bottom of the listing after CDUMP (DF=NODUMP).

NODUMP disables the CDUMP and RDUMP options.

The print output control options are:

CONC/NOCONC toggles the printing of concentrations for species selected

with the NAMES option and controlled with the TINIT and TSTEP options.
If the CONC option is used without the NAMES option, the concentration of
all species included in the mechanism will be printed (DF = print
concentrations).

NET/NONET toggles the printing of net rates of change of species selected

with the NAMES option and controlled with the TINIT and TSTEP options
(DF = do not print net rates).

HVRATES/NOHVRATES toggles the printing of hourly photolysis rate

information (DF = print the rate information).

RRATES/NORRATES toggles the printing of net rates for each reaction in

the mechanism (DF = do not print net rates).

FULL/BRIEF selects all or none of the above options.

If the only print control option used is BRIEF, the output file will include a concentration-
time listing of each species named in the AVG option. Therefore, under these conditions,
it is not necessary to use the CDUMP option unless a tabular listing of concentration-time
information is desired for species not named in the AVG option.

FILE [number] stores concentration-time information for up to 20 species in an ASCII file

(filename.prn). This file is suitable for importing into LOTUS-123. The simulation time and
the concentration for a maximum of 20 species are output on one line. The LOTUS-123
limit is 240 characters per line for importing.

EKMA Calculations

EKMA >

20
 BASE =
O3 = concentration,
RATIO = number,
CO = concentration,
VOC (or HC) = concentration,
NOX = concentration;
FUTURE =
DELNOX = number,
DELCO = number,
O3SURFACE = concentration,
O3ALOFT = concentration,
VOCSURFACE = concentration,
VOCALOFT = concentration,
NOXSURFACE = concentration,
NOXALOFT = concentration,
COSURFACE = concentration,
COALOFT = concentration;
EXTRA OPTIONS =
VOCMEASURED = concentration,
NOXMEASURED = concentration,
VOCLEVEL = number,
VOCTABLE,
NOXTABLE,
COTABLE,
TRYS = number;
< (EKMA)

BASE controls the base condition simulations. The options are these:

O3 is the mandatory design (base case) ozone concentration.

RATIO is the design VOC/NOx ratio (ppmC/ppm) for the initial controllable
emissions in the base year. If the base year VOC and NOx concentrations have been
previously calculated, RATIO can be substituted for by the following two options.
This eliminates the need to converge on the design O3 along the RATIO (RATIO is
calculated from these two option values).

VOC is the calculated level of controllable VOC (ppmC) emissions that yields the
base case O3.

NOX is the calculated level of controllable NOx emissions that yields base case O3.

CO is the mass (ppm) in the initial surface-layer that is due to emissions and can be
controlled in EKMA. This mass is added to initial transported CO (given in BOUN

21
 for the base case, and in FUTURE for the future case) to total the actual initial
concentration. Surface transported CO (COSURFACE) is not controlled in EKMA
calculations. (DF = 0.0)

FUTURE controls the future condition simulations. The options are these:

DELNOX allows the user to change future NOx emissions by a fixed percent. For
example, a 20 percent reduction would require input of "DELN = - 20" (DF = 0).

DELCO allows the user to change future CO emissions by a fixed percent (DF = 0).
This replaces the old credit option used in OZIPM-4. Use of this option assumes that
the user has included CO information in the EMIS or MASS option.

O3SURFACE is the future concentration of surface transported ozone (DF = base

case value).

O3ALOFT is the future concentration of ozone aloft (DF = base case value).

VOCSURFACE is the future concentration of surface transported VOC (DF = base

case value).

VOCALOFT is the future concentration of VOC aloft (DF = base case value).

NOXSURFACE is the future concentration of surface transported NOx (DF = base

case value).

NOXALOFT is the future concentration of aloft NOx (DF = base case value).

COSURFACE is the future concentration of surface transported CO (DF = base case

value).

COALOFT is the future concentration of CO aloft (DF = base case value).

EXTRA allows additional sub-commands that enable the user to control calculations and
output.
VOCMEASURED and NOXMEASURED are used together. These values are the
measured, initial VOC and NOx concentrations. This information can be specified
to allow the program to determine the location of the base year ozone should two
base year ozone values occur along one VOC/NOx design line.

TRYS tells the program how many simulations to attempt when trying to converge
on a base or future year solution (DF = 8).

22
 VOCLEVEL allows the user to specify one level of VOC control to be performed.
The VOC level is expressed as a percent change from the base year level (use a
minus sign for percent reduction, e.g., 60 percent reduction = -60). This calculation
is performed in lieu of an attainment calculation.

VOCTABLE generates a tabular report of change in ozone as a function of change

in VOC emissions. This is done in lieu of an attainment calculation. This
calculation uses the future conditions of surface and aloft transported species,
deltaCO, and deltaNOx, and reduces the final base case VOC in 10 percent intervals.
The ozone calculated for these conditions is compared to the calculated base case
ozone. If base case VOC and NOx are already known, these values are used in lieu
of base case calculations.

NOXTABLE generates a tabular report of change in ozone as a function of change

in NOx emissions. This is done in lieu of an attainment calculation. This calculation
uses the future conditions of surface and aloft transported species and deltaCO, and
reduces the final base case NOx in 10 percent intervals. The ozone calculated for
these conditions is compared to the calculated base case ozone. If base case VOC
and NOx are already known, these values are used in lieu of base case calculations.

COTABLE generates a tabular report of change in ozone as a function of change in

CO emissions. This is done in lieu of an attainment calculation. This calculation
uses the future conditions of surface and aloft transported species and deltaNOx, and
reduces the final base case CO in 10 percent intervals. The ozone calculated for
these conditions is compared to the final calculated base case ozone. If base case
VOC and NOx are already known, these values are used in lieu of base case
calculations.

The concentrations of VOC, NOx, and CO given in the output file for attainment calculations
include only the mass of these species in the initial surface mix that is subject to control; it
does not include any VOC, NOx, or CO transported in the surface layer or any individual
VOC species whose surface transport concentration may be given in the INIT option.

ISOPLETH Calculations
ISOP >
VOCMAX = concentration,
NOXMAX = concentration,
CO = concentration,
MAXT,
PLOT = species1, species2, ... speciesn,
NALR = number;
< (ISOP)

23
The ISOPLETH option performs the 121 CALC simulations necessary to provide data for
constructing an isopleth diagram. The results of the simulations are printed in the output file
and in a file named filename.ISO. The .ISO file is then used as input to the ISOPLOT
program (see below) to draw isopleths of most species included in the .ISO file. Also, if the
.ISO file is renamed filename.ALR, it can be used by OZIPR to save simulation time by
including results of ISOP calculations already performed (see below).

Even though the ISOP option will generate data in a .ISO file for each species, it may not be
possible to draw an isopleth using the ISOPLOT program for some species under some
conditions. Limitations and possible recourse are discussed in the following ISOPLOT
section.

VOCMAX refers to the maximum VOC concentration on the abscissa of the desired
isopleth diagram (the minimum value is always 0). Simulations are performed at
decade percentages of this value (DF = 2.0 ppmC).

NOXMAX refers to the maximum NOx concentration on the ordinate of the desired
isopleth diagram (the minimum value is always 0). Simulations are performed at
decade percentages of this value (DF = 0.28 ppmC).

CO is the mass (ppm) in the 6-9 a.m. surface layer that is due to emissions and can
be controlled. This mass is added to COSURF (the mass due to initial surface
transport) to arrive at the total initial concentration (DF = 0.0).

MAXT is a flag that activates the printing of solar noon and the time of the center of
the maximum average ozone concentration for each simulation.

PLOT designates the names of the species to include in the filename.ISO file. The
ISOPLOT program can then draw isopleths for most of these species. It is not
necessary to include the number of species as in other options (DF = O3 only).

NALR indicates to the program that a file exists named filename.ALR which contains
results from the number of simulations already performed and listed in that file. The
results are read instead of calculations. Note that species to be plotted and plot
scales in filename.ALR must be consistent with the current ISOP options.

Termination of Input

END;

4 The ISOPLOT Program - Drawing Isopleth Plots

24
Running ISOPLOT

Although the ISOP option of the OZIPR program is used to create a file containing
the results of OZIPR isopleth simulations (filename.ISO), the isopleth plotting function has
been removed from OZIPR and placed in a separate program, ISOPLOT. This allows direct
manipulation of plot parameters without the requirement of re-entering the OZIPR program
each time. Besides this data file, the user must also create a plotting information file
(filename.INF) which lists the species to be plotted and other options (described below).
The ISOPLOT program is started by typing:
ISOPLOT filename.INF/s/s/s filename.ISO

The extensions .INF and .ISO may be omitted. The "/s" symbols refer to user-supplied
plotter description switches:
/H Requests all plots to a HP LaserJet Printer
/E Requests all plots to an Epson RX or FX Printer
/11 Requests creation of a M11DRAW File.

If the switches are not used, each isopleth will appear on the screen. The user then has the
option of typing <enter>, "H", or "E". The "H" and "E" commands are similar to those above
for the two specified printers except that only the plot displayed on the screen is produced.
If <enter> is typed the next isopleth appears on the screen.
In this simple example, it is assumed that the required program files (isoplot.exe and
isplt.exe), the information (.INF), and the data (.ISO) files are all in the same directory. It
is also possible to use other directories as long as the paths are correctly designated. For
example:
c:\ozipr\pgm\isoplot info data

runs the ISOPLOT program in subdirectory c:\ozipr\pgm, using the information and data files
in the current subdirectory. However, because the ISOPLOT program calls an intermediate
processing program (isplt.exe) and might be requested to produce M11DRAW files, an
additional configuration file called ISOPLOT.CFG must be created in either the current
directory or the directory with the isoplot.exe file. The ISOPLOT.CFG file designates the

25
location of the intermediate program and the location where the M11DRAW files will be
saved:

ISPLT=pathname

M11FILES=pathname

If the ISOPLOT.CFG file is not in the current directory or the ISOPLOT directory, an
information message is displayed and the program continues.
As already noted, the ISOPLOT program actually calls on a second program, ISPLT
(isplt.exe), that reads the .INF and .ISO files and prepares an output file with a .PRN
extension. Control then reverts back to ISOPLOT for preparation of screen isopleths and
plots. Upon completion, the .PRN file is deleted unless the user requests that it be saved (see
below). The user may execute the ISPLT program directly, for example:

ISPLT TEST.INF EXAMPLE.ISO

Switches are not allowed on the command line. Executing ISPLT generates an
EXAMPLE.PRN file. ISOPLOT can then be run with only the PRN as input:

ISOPLOT EXAMPLE.PRN/s/s/s

This two-step execution involves more work and is not recommended unless the .PRN file
is already created and the user wishes to re-display or print an isopleth.

ISOPLOT Commands

The information file is a text file containing a series of COMMANDS. The general
rules for the free format input files are similar to those used in OZIPR. The first four letters
are significant and upper case is mandatory. Comment lines start with "!" and in-line
comments can be inserted between "{" and "}". Commands may be given in any order but
must end with a semicolon, and the .INF file must end with the END command. The only
other required command is the PLOT command. Default settings will be used if other
commands are not specified.

PLOT_SPECIES = species1 units1 n1 n2 n3 . . . nn,

species2 units2 n1 n2 n3 . . . nn,
species3 units3 n1 n2 n3 . . . nn;

26
XMAX = xx;
YMAX = yy;
XTIC = nn;
YTIC = nn;
SAVE_PRN_FILE;
ONE_DIGIT;
END;

PLOT_SPECIES designates the species/units/concentrations values to be plotted. Plots can

be requested for up to 12 species. Blank spaces are used to separate values and a comma
appears at the end of each line. A semicolon ends the command. The input values are:

Species must be the name of a species appearing in the .ISO file (i.e., the
species must have been included in the ISOP option in OZIPR).

Units specifies the concentration unit to be used in constructing the isopleth.

The following units are accepted: PPM, PPHM, PPB, PPT, or CMS
(molecules/cc). Default is PPB.

n1 n2 n3 . . . nn list the isopleth line concentrations in the units given. If

default units are used, no concentrations can be specified. Up to 20
concentrations can be requested. If no concentrations are specified, the
program will select default values. Remember to change concentrations if
you change units. If no points are found in a plot region, no line is drawn.

XMAX and YMAX set the abscissa (VOC axis) and ordinate (NOx axis) for the plots.
ISOPLOT will calculate settings, but these options can be used to override calculated values.

XTIC and YTIC set the number of tic marks on the isopleth plots. Defaults are XTIC = 6
and YTIC = 10.

SAVE_PRN_FILE will disable deletion of the .PRN file created by the ISPLT program.

ONE_DIGIT prints one significant digit in line labels (DF=two digits).

END terminates the option list.

Diagram Problems and Improvements

The ISOPLOT graphics output is intended to provide draft quality plots. Some line-
drawing anomalies may occur, and labels may be overwritten at times. High quality graphics
output will usually require importing of either the .ISO or the M11DRAW files into a

27
graphics package. However, it is possible to obtain reasonably good results with ISOPLOT
with some knowledge of the plotting algorithm. The following paragraphs contain
suggestions for improving and interpreting ISOPLOT diagrams.
Because ozone is the principal species for which isopleth diagrams are used, the
isoline generation procedure was optimized to provide smooth ozone lines under a variety
of conditions. This algorithm generally provides adequate diagrams for other species.
However, if anomalous lines (such as spikes or crossed lines) appear on a diagram, the user
should question the result in that portion of the isopleth diagram (see ISOPLOT Example 9
in the following section). It may be possible to improve the diagram by changing the above
options to include more points in the diagram region. In other cases it may be necessary to
change the ISOP options is OZIPR and generate a new .ISO file with a larger data domain.
Another option is to import the .ISO file into a spreadsheet program, or the M11DRAW file
into a graphics package, and attempt to eliminate anomalies and utilize the line drawing
capabilities in those programs.
Some species are very sensitive to VOC and NOx changes and concentrations will
vary over many orders of magnitude in the .ISO file. Peroxides often have such
characteristics. The large differences in concentration cause the plotting algorithm to take
an extremely long time to calculate the location of the proper isoline points and sometimes
there is only one point in the entire diagram domain. This will lead to display of an error
message on the screen (since the program cannot draw a line with only one point). One
solution to this problem is to convert the concentrations in the .ISO file into logarithms,
either by creating a program or importing the .ISO file into a spreadsheet program. The user
can then either use the plotting package in the spreadsheet program or export a second .ISO
file and rerun ISOPLOT.

28
 5 Examples

This section provides descriptions of OZIPR and ISOPLOT examples, along with copies of the
appropriate input and output files. The ISOPLOT examples also display and discuss isopleth diagrams.
{Note to online version: This document does not contain text of the example files. These files
areavailable with the rest of the OZIPR input files.}
OZIPR Examples

Nine example input files that exercise most of the major OZIPR options are discussed. The output files
(.OUT, .PRN., and .ISO) that are generated by OZIPR are also provided. The examples and options used are:

Example 1: Sample Calculation using cm RADM Mechanism

Options Used:

MLIST PLACE
MODIFY/WIDTH=132 MET/DILU
MECH MET/TEMP
ZENI MET/PRES
BOUN/REAC EMIS
BOUN/IFRAC CALC/PRINT[BRIEF]
BOUN/TRAN CALC/PRINT/TINIT
BOUN/DEPO CALC/PRINT/TSTEP
TIME CALC/PRINT/AVER
TITLE

This is an example of an individual calculation using the RADM-II mechanism with rate constants
expressed in CM (molec-cc-sec) units. The mechanism is entered with an include file (@meccm.rad). An
include file (@zen.rad) is also used to provide information on photolysis rates as a function of zenith angle. The
output file includes a listing of the mechanism. The width of the output is 132 columns. The PRINT/BRIEF
option was used so the output file contains a concentration-time dump of the 10 specified AVG species.

Example 2: Test Calculation with Isoprene Emissions using a modified cm CB4 Mechanism

29
 Options Used:

MLIST PLACE
MECH MET/DILU
ZENI MET/TEMP
BOUN/REAC MET/PRES
BOUN/TRAN MET/RH
BOUN/DEPO MASS
TIME CALC/PRINT[FULL]
TITLE CALC/PRINT/AVG

This is an example of an individual calculation using a modified CB4 mechanism with rate constants
expressed in CM units (some inorganic rates are updated). The MASS option is used to input emissions of VOC,
NOx, CO and ISOP. The initial concentration included for ISOP in the MASS option is 0.001 ppmV. Note that
the VOC concentration listed in the output file at the first time step is 0.685 ppm. This includes the 0.680 ppmC
specified for VOC in the CALC option and 0.005 ppmC isoprene (0.001 ppmV x 5). In an attainment
calculation, the ISOP would not be subject to control.

Example 3: Sample Calculation Using a modified cm CB4 Mechanism

Options Used:

NOECHO TITLE
MLIST PLACE
MECH MET/DILU
ZENI MET/TEMP
MODIFY/WIDTH=132 MET/PRES
MODIFY/ACCU=0.001 MET/WATER
BOUN/REAC EMIS
BOUN/IFRAC CALC/PRINT[CONC,NOHV]
BOUN/EFRAC CALC/PRINT/AVG
BOUN/TRAN CALC/PRINT/TAVG
BOUN/INIT CALC/PRINT/CDUMP
TIME CALC/PRINT/RDUMP

This is an example of an individual calculation using a modified CB4 mechanism with rate constants
expressed in CM units (some inorganic rates are updated). Unlike Examples 1 and 2, however, all photolytic
rate constants are expressed as absolute rate factors instead of relative rate factors (i.e., the modifier /L instead
of /R is used for all photolytic reactions). In this example, include files are used for BOUN/REAC (@reac.cb4)
as well as for the MECH and ZENI options. EFRACTion in this example is also changed from its default value

30
of 0.05 to 0.10. The output file includes the 8-hour average maximum concentration for O3. A concentration-
time dump is included for 6 species and a reaction rate-time dump is included for four reactions.

Example 4: CALC and EKMA using cm CAL Mechanism

Options Used:

ECHO PLACE
MLIST MET/DILU
MECH MET/TEMP
ZENI MET/PRES
BOUN/REAC MET/RH
BOUN/IFRAC MASS
BOUN/TRAN CALC/PRINT[CONC]
BOUN/INIT CALC/PRINT/NAMES
BOUN/DEPO CALC/PRINT/AVG
TIME CALC/PRINT/FILE
TITLE EKMA/BASE

This is an example of a single calculation and an attainment calculation using the CAL mechanism
expressed in CM units. Note that reaction 21 in the MECH option contains a product with a negative coefficient
and, therefore, the product is entered as "+ -1 * NO2". The INIT option is used to provide for the surface
transport of HONO. The MASS option is used to input emissions of VOC, NOx, CO and PRPE. The initial
concentration of PRPE included in the MASS option is 0.001 ppmV. Note that the 0.001 ppmV of PRPE and
the emissions of this species added with the MASS option are not controlled in the attainment calculation. The
output file for the CALC simulation lists a value for VOC at the first time step of 0.363 ppmC. This includes
the 0.36 ppmC of VOC that is given in the CALC option and the 0.003 ppmC of PRPE included in the MASS
option. Note that the PRINT/FILE option is used so the output files for this example consist of EX8.out and
EX8.prn, where the .prn file contains the simulation times and concentrations of the named species; this file is
suitable for importing into LOTUS-123. In the EKMA calculation, the future concentrations of surface and aloft
transported species are identical to the base case concentrations and, therefore, it was not necessary to use the
EKMA/FUTURE option.

Example 5: CALC and EKMA using a modified cm CB4 Mechanism

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 Options Used:

ECHO PLACE
MLIST TITLE
MECH MET/MIXING
ZENI MET/PRES
BOUN/REAC MET/RH
BOUN/INIT EMIS
BOUN/TRAN CALC/PRINT[BRIEF,HV]
BOUN/ALOFT CALC/PRINT/AVG
BOUN/DEPO CALC/PRINT/CDUMP
BOUN/CON EKMA/BASE
TIME EKMA/FUTURE

This is an example of an individual calculation and an attainment calculation using a modified CB4
mechanism with rate constants expressed in CM units (some inorganic rates are updated). This example includes
the use of the BOUN/CON option to express constant deposition velocities (i.e., deposition rates that do not
change from hour to hour). Note that RH values are only given for 5 hours although the length of the simulation
is 12 hours. The last value of 50% for the relative humidity is extended to the end of the simulation. The CALC
output is similar to Example 1 except that it includes a listing of the photolytic rate constants (i.e.,
PRINT[BRIEF,HV] in contrast to PRINT[BRIEF] of Example 1). Because this example requested a listing of
photolysis rates, the output file does not include a concentration-time dump of the five AVG species. To obtain
such a dump in this case, the option CDUMP was included. In the EKMA calculation, the FUTURE option was
used to reduce the concentration of VOCSurface, VOCAloft and O3Aloft used in the attainment calculation.

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Example 6: CALC and EKMA using ppm CB4 Mechanism

Options Used:

MLIST MET/DILU
MECH MET/PRES
ZENI MASS
BOUN/REAC CALC/PRINT[NOHV]
BOUN/IFRAC CALC/PRINT/NAMES
BOUN/TRAN CALC/PRINT/AVG
PLACE EKMA/BASE
TITLE EKMA/FUTURE

This example includes an individual simulation and an attainment calculation using the CB4 mechanism
with rate constants expressed in ppm-min (PPM) units. The option FUTURE is used in the attainment
calculation to reduce the concentrations of transported species and to reduce future emissions of NOx and CO
by 10 and 35%, respectively. Note that the concentrations of initial surface-layer NOx and CO that is due to
emissions is also reduced by 10 and 35%..

Example 7: EKMA using Extra Option

Options Used:

MLIST TITLE
MECH MET/DILU
ZENI MET/PRES
BOUN/REAC MASS
BOUN/IFRAC EKMA/BASE
BOUN/TRAN EKMA/EXTRA
PLACE

This example, which is very similar to Example 6, demonstrates the use of the option EXTRA. Note that
the initial conditions are the same as for Example 6. In that example, the initial VOC and NOx concentrations
that generate the base case ozone were determined. These concentrations are entered in Example 7 under
EKMA/BASE in lieu of listing the VOC/NOx ratio. The EXTRA options included here specify generating
VOC, NOx and CO tables and calculating the percent decrease in O3 that would result from a 15% decrease in
VOC. The tables and the VOCLevel calculation are performed in lieu of an attainment calculation.

Example 8: ISOP using a modified cm CB4 Mechanism

33
 Options Used:

MLIST TITLE
MECH MET/DILU
ZENI MET/TEMP
BOUN/REAC MET/PRES
BOUN/IFRAC MET/RH
BOUN/TRAN MASS
PLACE ISOP
TIME

This is an example of the Isopleth option. Execution of this input file generates the output file ex8.iso
which includes the results of the 121 CALC simulations that were conducted to provide the data needed for
constructing isopleth diagrams for O3, PAN, HNO3, FORM, OH, HO2, and H2O2.

Example 9: ISOP using RADM Mechanism

Options Used:

MODIFY/WIDTH=132 TIME
MECH TITLE
ZENI PLACE
BOUN/REAC MET/DILU
BOUN/IFRAC MET/TEMP
BOUN/TRAN EMIS
BOUN/DEPO ISOP

This is an example of the Isopleth option using the RADM-II mechanism with rate constants expressed
in CM (molec-cc-sec) units. The example is similar to Example 1 above. However, execution of this input file
generates the output file ex9.iso which includes the results of the 121 CALC simulations that were conducted
to provide the data needed for constructing isopleth diagrams for O3, PAN, HNO3, HCHO, HO, HO2, and H2O2.
The demonstration of the ISOPLOT program using the ex9.ISO file is given below.

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ISOPLOT Examples

Two examples of the ISOPLOT program are given next. The following examples include the .INF
files and the isopleths drawn from above Examples 8 and 9. The options used are similar, except that the
ONE option was used in Example 8 to provide output with fewer significant digits.
Some plotting amonalies are evident in Example 9. The crossed lines in the HNO3 plot are probably
due to the lack of a low concentration point on the 5 ppb line. That line should be ignored along the straight
line segment that crosses the 10 ppb line. In the HCHO and HO plots, the line labels must be carefully
scrutinized. For HCHO, the 30 and 35 ppb labels are displced from the lines, while for HO the .40 and .45
ppt labels are superimposed. Finally, for the HO2 isopleth, the plotting algorithm could not fit lower left
region with the existing .ISO data. Probably, a smaller plotting range must be given in OZIPR to gererate
more detail in the .ISO file for HO2.

35
 5 References

Hogo, H. and M.W. Gery, Users Guide for Executing OZIPM-4 with CBM-IV or Optional Mechanisms.
Volume 1. Description of the Ozone Isopleth Plotting Package–Version 4, EPA/600/8-88/073a,
U.S. EPA, Research Triangle Park, NC (1988).

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