Mathl. Cornput. Modelling Vol. 21, No. 9, pp.

111-117, 1995
Pergamon Copyright@1995 Elsevier Science Ltd
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Modelling Photochemical Smog

in the Perth Region
P. J. RYE
Department of Environmental Protection
141 St. Georges Terrace, Perth, W.A. 6000, Australia

Abstract-A three-year study of the occurrence of photochemical smog in the vicinity of Perth,
Western Australia is being conducted by the State Energy Commission (“SECWA”) and the W.A. De-
partment of Environmental Protection (“DEP”). The project, termed the Perth Photochemical Smog
Study (“PPSS”) includes extensive monitoring of smog components and meteorological variables, de-
velopment of an inventory of emissions of smog precursors, and modelling of the combined effects of
smog chemistry and meteorological transport.
The Urban Airshed Model (“UAM”) has been used for initial photochemistry studies. Input data
have been obtained from surface measurements and the author’s own mesoscale meteorological model.
While the Urban Airshed Model has proved to have limitations in its application to the Perth region,
model results have highlighted a number of issues. These, and implications for further work, are
described.

Keywords-ozone, Photochemical smog, Sea breeze.

1. INTRODUCTION
The term “photochemical smog” refers to a combination in the atmosphere of chemical species,
each of which is the product of reactions involving initially a mix of nitrogen oxides and hydro-
carbons with normal atmospheric gases. The principal components of concern are ozone and a
range of oxidated nitrogen species, which are significant bronchial irritants, some of which are
corrosive to materials.
Since late 1989, the Department of Environmental Protection has monitored the concentration
of ozone at Caversham (see Figure 1). High values were recorded at this site, but these could not
show the extent of the region affected. When the State Energy Commission of Western Australia
proposed to expand a gas turbine power station to the north of the city, this lack of knowledge of
the affected region meant that the potential effect on ozone concentrations was uncertain. The
proponent, therefore, agreed to support a study of the region’s photochemical smog, with the
commitment that, if the turbines were shown to contribute to photochemical smog pollution,
low-emission technology would be retrofitted.
The major components of the study include the monitoring of photochemical smog species (at
sites in Figure 1 denoted TR, QR, SW, RI, KE, CU, CA, RG) and of meteorology (at all sites
in Figure l), the development of an emissions inventory, and adaptation of existing computer
models to represent the transport and photochemistry of smog in the region.
The aim of the model developments is to represent a set of periods giving rise to high ozone
concentrations. Using this set, the effects of population growth and various control strategies
may be tested.

The Urban Airshed Model was developed for the U.S. EPA. and IS made available at nominal charge to any air
quality investigator. It was installed by M. Cope, of the Victorian EPA.

Typeset by d&-‘&X

111
 112 P. J. RYE

0 Q’
‘RH

0 5 10 15 20 HV

Figure 1. Monitoring sites used m the Perth Photochemical Smog Study. Caversham
is the site denoted “CA,” to the north east of the city.

This paper describes the progress of the modelling work. Emphasis is placed on the features of
Perth’s climate which contribute to the smog levels encountered, and on the modelling problems
which they produce.

2. PHOTOCHEMICAL SMOG PROCESSES

Ozone is produced naturally in the atmosphere by the action of ultraviolet light on nitrogen
dioxide, generating activated oxygen atoms and nitrogen oxide. The atomic oxygen quickly
combines with oxygen molecules to produce ozone, and the nitrogen oxide is reoxidised slowly
by oxygen, or more rapidly by ozone, to nitrogen dioxide. These processes normally maintain an
equilibrium which leads to a low background of ozone of about 15-30ppb (parts per billion).
The rate of nitrogen dioxide regeneration, and consequently ozone production, is accelerated by
the presence of reactive volatile organic compounds, and by the presence of nitrogen oxides from
anthropogenic sources. In these circumstances, the progress of photochemical smog reactions in
strong sunlight leads to a significant increase of ozone concentrations, peaking typically in the
mid-afternoon period.
Inventories generally show motor vehicle emissions to be the most important single source of
volatile organic compounds. Industrial and biogenic sources (the latter due to evaporation from
vegetation) are also of significance. While mass emissions from the biogenic sources may be less,
the species emitted can be of high reactivity, making a disproportionate contribution to the rate
of smog formation.

3. OBSERVATIONS
Ozone measurements at Caversham have shown many peak hourly averages over 80ppb, with
the highest level measured of 132 ppb. These values were marginal when compared to the
U.S. Environmental Protection Agency and 1979 Victorian Environmental Protection Authority
hourly-average standards of 120 ppb, but are more significant in comparison to newer standards.
Recently, a review conducted for the National Health and Medical Research Council has rec-
ommended a standard of 80ppb [l]. Bases for the reduced limit have also been reviewed by
Streeton [2].
 Photochemical Smog 113

w
Wind direction

Figure 2. Ozone concentrations and wind direction at Caversham from lgth to 20th
January 1991

Figure 3. Ozone concentrations measured at Caversham over the period 20th to 22nd
February 1991.

Peak concentrations were found to occur immediately after the arrival of the sea breeze. Fig-
ure 2 shows data for three representative days. The first two experienced light sea breezes, shown
by the early afternoon change of wind direction to southwesterly, while the third received winds
persistently from southwest. The lack of any rise in ozone levels on the third day illustrates the
significance of the process of sea breeze formation, and not just wind direction, in the arrival of
elevated ozone concentrations at Caversham.
Review of periods leading to the highest concentrations of ozone showed peak days to occur at
the end of a sequence with elevated ozone levels. Figure 3 shows the three-day sequence leading
to the highest hourly average ozone level measured since 1989. Over the three days concerned,
there was a rise not only in the peak ozone measurement, but also in the background level before
the arrival of the sea breeze. From such events, and the associated meteorology, it was concluded
that one factor contributing to photochemical smog episodes was the return of photochemical
smog species generated on the previous day.

4. MODELLING DEVELOPMENTS
To model ozone concentrations, the rate of emissions of chemical species involved in photochem-
ical smog reactions, the wind fields which transport them as they react, and the smog-producing
reactions which occur within the atmosphere must be included.

4.1. Emissions

Each emissions source contributes a range of species of varying reactivity, so that a detailed
speciation is required on a source-by-source basis. This makes the emissions inventory the most
time-consuming component of a regional smog study, and also the one most subject to unde-
tectable errors.
The design and management of the emissions inventory have been contracted to Frank Carno-
vale from the Victorian EPA. The collection of the required information is being performed by
 114 P. J. RYE

staff of the W.A. EPA, using industry questionnaires, site visits, and base data provided by
several government departments.
Initially, the sole available inventory component has been a vehicle emissions inventory for
Perth compiled by Lyons et al. [3]. There is no equivalent inventory for industry or vegetation
emissions. A general observation that vehicle emissions comprise typically half of the total urban
output (Cope, personal communication) has, therefore, been used. The preliminary emissions
inventory is, therefore, the total vehicle output, doubled.

4.2. Meteorology

There are two basic sources of the required meteorological data, measurements, and model
calculations. Measurements include not only surface values gathered across the study region,
but also the vertical profile of wind and temperature. The latter, while expensive to gather on
a regular basis, are particularly crucial in the Perth study, because of the vertical recirculations
which occur in sea breeze flows.
A meteorological model can calculate, using physical laws, the time and space evolution of
both wind and temperature over a three-dimensional grid. Two meteorological models are being
employed, one the Regional Atmospheric Modelling System (“RAMS”), a widely used program
from ASTeR, Inc. in the U.S.A., the other a three-dimensional development of a two-dimensional
model used by the author for several years [4].
RAMS is a sophisticated model of general applicability, including the capacity to represent
processes irrelevant to the present study, such as rainfall and cumulus convection. It is capable
of including the effects of surface topography, and may be operated in a nested mode, handling
broad scale features at low resolution, but still representing processes in fine detail about locations
of particular interest.
The author’s model, on the other hand, was developed explicitly to represent the sea breeze.
Moisture is only included because of its effect on heat transfer in the atmosphere. The model
grid is of fixed size, although one run may be initialised using data from a previous, lower-
resolution simulation. But as a benefit of these simplifications, the model runs several times
faster than RAMS.
In the initial phase of the study, model calculations are a preferable source, because a range
of conditions can be readily set up for comparison of their effect on smog concentrations. In
addition, it is likely that the density of upper-level measurements, both in space and time, will
be less than that needed for accurate modelling. In this context, measurements may have a
primary role in meteorological model validation, and in “nudging” model calculations to match
real winds and temperatures more closely.

4.3. Photochemistry

The initial transport and photochemical modelling have been performed using the Urban Air-
shed Model (UAM), which has a long history of application and development in photochemical
smog studies [5]. Such models represent dozens of species, tracking their reactions and move-
ment within a three-dimensional grid. In its Perth application, UAM employs 24 species and
94 reactions, in a grid of size to 50 x 50 x 6 and of 3 km horizontal resolution.

5. MODEL RESULTS
Initial model calculations were based on representations of the meteorology of a normal sea
breeze, developing against an initial northeasterly wind. Discrepancies in these calculations led
to incorporation of the effects of the coastal low pressure trough, which forms along the southern
Western Australian coastline in summer.
 Photochemical Smog 115

Figure 4. Ozone levels (ppb) modelled using meteorology based on data for Sth Jan-
uary 1993, for time 4 p.m.

5.1. Sea Breeze-Originated Events

Several trial calculations have been performed using RAMS and the author’s two-dimensional
and three-dimensional models. Initial comparisons indicated that the differences between the
windfields calculated by RAMS and the author’s model, in two-dimensional form, were small.
For this reason, and given its faster execution time, the author’s own model was used for initial
windfield estimates.
A number of case studies, using the two-dimensional model to provide data for UAM, have
shown peak surface ozone levels in the range 65 to 85 ppb, in fair agreement with measurements
for the conditions modelled. Figure 4 presents surface concentrations for one such study. This
used modelled winds and temperatures, calculated from initial data for Sth January 1993, and
illustrates several issues which have arisen.
The alignment of highest ozone concentrations parallel to the coast is consistent with obser-
vations. The concentration trends of Figures 2 and 3 are found for all other inland monitoring
sites, with high ozone levels limited to a short time after the arrival of the sea breeze. The ob-
served north-south alignment of the sea breeze front matches fully the modelled “wall” of ozone
advancing inland.
The modelled location of the ozone peak is due to the transport of morning peak-hour emissions
offshore on a northeasterly wind, and their subsequent return by the sea breeze in the afternoon,
as photochemical smog. But the modelled peak is located south of the areas where high levels
are generally observed.
The discrepancy is attributed to errors in offshore modelled winds. Observations made at
Rottnest Island on the day modelled showed a southerly wind offshore, due to the proximity
of the coastal trough. Review of earlier sequences of days where ozone levels remained high
(e.g., Figures 2 and 3) showed that they were characterised by a progressive strengthening of
the trough. The days of highest ozone concentrations (over 100 ppb hourly average) were always
characterised by passage inland of the coastal trough.
Also apparent in Figure 4 is a reduction in ozone concentrations as the peak passed over
the central Perth area. The cause, in the model, was an injection of nitrogen oxide emissions,
 116 P. J. RYE

these reacting with the ozone and reducing concentrations of both. However, measurements at
Caversham, close to downwind of the city in relevant sea breeze conditions, have shown that the
concentrations of nitrogen oxides to be low at the time of the ozone peak. The cause for this
difference is not yet apparent, but could potentially involve peculiarities of the wind fields, urban
emissions pattern or the photochemical reactivity of emitted species.
A final issue of current concern is the handling of vertical transport by the model. Considerable
problems were initially encountered in getting the model to generate any increase in ozone levels.
The cause was traced to the inability of UAM to handle the strong vertical velocities which
develop near the sea breeze front. The required response was to smooth variations of horizontal
velocities (and so, by mass conservation, vertical velocities) using a filter of about 10 km radius.
The need for such a filter, and the arbitrariness of the filter radius, remain sources of concern.

5.2. Trough-Originated Events

The complete modelling of the coastal trough was found to require use of the three-dimensional
model. Given suitable initial conditions, the trough formed over a period of a few days, coming
to an equilibrium in which successive 24 hour cycles showed similar wind and pressure fields.
This corresponded well to the normal behaviour of the trough, which is normally stable until the
passage of a cold front south of the state weakens the easterly wind strength.
To replicate the inland advance of the trough a trend with time of the large-scale pressure
gradient may be added to the model. The timing of this change has been found to be crucial,
the highest modelled ozone concentrations arising when the trough axis is close to the coast at
sunrise.
Small adjustments to the timing of the modelled trough motion have shown that extreme results
may be generated. The highest peak ozone concentration so far produced has been 437ppb,
more than three times greater than the highest measurement so far at Caversham. But this case
corresponded to maximum temperatures in the mid-40’C range (about the record maximum for
Perth) when wind speeds during the morning peak hour were 1 to 1.5 m s-l. In the highest
concentration smog events on the Caversham record, actual morning wind speeds were higher, in
the 1 to 3 m s-l range. Modelled mixing depths near the coast were also low, at about 200 metres,
but this appeared to be a direct result of the unusual temperatures.
The combination of extremes which gave rise to the model result mean that it would be partic-
ularly rare. Correspondingly, the benefits of a control strategy aimed exclusively at eliminating
such events might also be rare. Attention will be better devoted to cases of relatively common
occurrence, whose control will have a correspondingly more frequent benefit on Perth’s summer
air quality.
But the winds which contributed to this extreme event are in themselves not rare, occurring
several times each summer. With more normal temperatures about 35°C leading to a slower
reaction rate and higher mixing depths, less extreme ozone concentrations could be occurring in
the outer Perth regions. In addition, in the extreme case, and in other examples so far modelled
(e.g., Figure 5), ozone concentrations at Caversham remained moderate, with the main ozone
mass passing through Perth’s northern suburbs.
These cases demonstrate that the highest measurements at Caversham are not necessarily the
highest for the Perth region. One major role of both measurements and modelling in the study
will be to determine the extent of the region affected by the Perth’s photochemical smog.

6. CONCLUSIONS
The Urban Airshed Model has shown some limitations in application to the Perth Photochem-
ical Smog Study, but with care can be made to represent Perth’s photochemical smog events.
The importance of recirculation of morning peak-hour emissions over the metropolitan area by
the sea breeze has been confirmed. The coastal low pressure trough has been shown to have an
 117

Figure 5. Modelled concentrations of ozone (ppb) at 2 p.m. for a case in which the
main ozone mass was carried to the northern suburbs.

important role, through the high associated temperatures, the light sea breezes and more westerly
wind directions. The highest ozone concentrations so far modelled have developed when light
winds on the trough axis lay at the coast in the morning.

REFERENCES

1. A.J. Woodward, I. Calder, A.J. McMichael, D. Pisaniello, R. Scicchitano and K. Steer, Options for revised
air quality goals for ozone (photochemical oxidants), Project Report to the Commonwealth Department of
Health, Housing and Community Services, (August 1993).
2. J.A. Streeton, Air pollution health effects and air quality objectives, Report to Environment Protection
Authority Victoria, (September 1990).
3. T.J. Lyons, R.O. Pitts, J.A. Blockley, J.R. Kenworthy and P.W.G. Newman, Motor vehicle emission inven-
tory for the Perth Airshed, Jozcr. Roy. Sot. W. AI&. 72, 67-74 (1990).
4. P.J. Rye, Evaluation of a simple numerical model as a mesoscale forecasting tool, J. Appl. Met. 28, 1257-1270
(1989).
5. R.D. Scheffe and R.E. Morris, A review of the development and application of the Urban Airshed Model,
Atmos. Envzron. 27B, 23-39 (1993)

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