Journal of the Air Pollution Control Association

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Chemistry and Meteorology in an Air Pollution

Episode

Edgar R. Stephens

To cite this article: Edgar R. Stephens (1975) Chemistry and Meteorology in an Air
Pollution Episode, Journal of the Air Pollution Control Association, 25:5, 521-524, DOI:
10.1080/00022470.1975.10470108

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 CHEMISTRY AND METEOROLOGY IN AN
AIR POLLUTION EPISODE

Edgar R. Stephens
Statewide Air Pollution Research Center, University of California

Strikingly sharp vertical boundaries occasionally develop between Occasionally, perhaps a dozen times per year, the demar-
marine air polluted with photochemical smog and clean, dry air. cation between the polluted marine air and the clean desert
Records of a particular incident which occurred in Riverside, or upper atmospheric air becomes very sharp.2'3 One such
boundary was photographed as it passed across Riverside
Calif., shed some light on the role of wind and temperature struc-
in the early afternoon of March 16,1972. A black and white
ture in creating this unusual condition. print of one of these photos is shown in Figure 1. The cam-
era was pointed toward the northwest for these pictures as
shown in Figure 2. The highest parts of the San Gabriel
The study of air pollution encompasses a wide variety of mountains are readily visible from this viewpoint on a clear
technical fields. The interaction between two fields, chem-
istry and meteorology, is strikingly evident in inland areas
of Southern California. Riverside, Calif., for example, is
about 60 miles east of the giant coastal megalopolis of Los
Angeles and Orange counties. Under typical sea breeze con-
ditions a shallow layer of cool, moist marine air flows in-
land over this urban area and becomes heavily contaminat-
ed with the ingredients of photochemical smog.1 As it pass-
es inland this air is warmed enough to prevent the forma-
tion of clouds and so plenty of sunshine is available to pro-
mote photochemical reactions among these pollutants.
With low wind speeds plenty of time is also available for
the reaction and so Riverside and nearby communities ex-
perience many days of moderate to heavy photochemical
smog with the maximum oxidant often occurring in the late
afternoon.

Dr. Stephens is Professor of Environmental Sciences and

Chemist, Statewide Air Pollution Research Center, Univer-
sity of California, Riverside, CA 92502. Figure 1. Smog bank approaching Riverside campus of the University of Cali-
fornia.

May 1975 Volume 25, No. 5 521

day. These photographs were taken in color with a Polaroid
film in front of the lens to darken the sky and thereby in-
crease its contrast with the cloud of polluted air. Scaling
the photographs indicates the smog bank to be 1000 meters
thick. These photographs, along with records from a vari-
ety of air monitoring instruments (Figures 3 to 9) form a
fascinating illustration of the interaction of meteorology
with atmospheric chemistry. The visible part of the smog
cloud was of course the aerosol; that this was not fog is
clear from the fact that the relative humidity was only
about 30%.
Oxidant and PAN
The characteristic feature of photochemical smog is its
oxidizing power. The oxidant record for this day, as shown
by the solid line in Figure 3, was obtained from a Mast cou-
lometric potassium iodide recorder. When the smog front
passed the air monitoring station the rise in oxidizing
power was so rapid as to be limited by the response time of
the instrument. The peak value of 0.43 ppm was reached at
about 1500 PST, well after the peak sunlight intensity.
This is in reasonable agreement with the value of 0.36 ppm
reported by the Riverside County Air Pollution Control
District on this date. Several other features of this oxidant
record are noteworthy:
1. The clean air just prior to the front's arrival had an oxi-
dant significantly greater than zero. In fact it was 0.04-
0.06 ppm which is just below the federal air quality stan-
dard of 0.08 ppm (160 njg/m3). That this is not zero error
in the instrument is shown by the fact that readings of
0.01 ppm or less were indicated both on the preceeding
and following nights. Oxidant records from several simi-
lar pollution front incidents have shown the same 0.05
ppm of oxidant in pure air. The concentration is unusu-
ally constant compared to polluted air oxidant. The
purging with clean air which occurred between 1030 and
1100 was a much slower process than the sharp arrival of
polluted air at 1400 PST.
2. Oxidant levels above 0.10 ppm were recorded in the
mid-morning. This is presumed to be locally generated
pollution.
3. Oxidant levels dropped to zero at night probably be-
cause the ozone was scavenged by the nitric oxide from
auto exhaust.
4. Also shown in Figure 3 is a record of peroxyacetyl ni-
trate (PAN) concentration obtained by an automated
electron capture chromatograph.4 This instrument will
Photo
Los Angeles \ 1 5 mile arrow
UCR
Rivers
i d e County
Pacific
Ocean
San Diego County
Figure 2. The Riverside campus is inland from the major met-
ropolitan area of Los Angeles and Orange Counties and from
the Pacific Ocean.
522
PPM
0.5
0.4
0.3
0.2
0.1
"PANx 10 •_Oxidant
0
0800 0900 1000 1100 1200 1300 1400 1500
0.5
0.4
0.3
-PAN x 10
0.2
Oxidanf
0.1
1500 1600 1700 1800 1900 2000 2100 2200
Pacific Standard Time, 16 March 1972
Figure 3. Oxidant and peroxyacetyl nitrate (PAN) both increased abruptly at
frontal passages.
detect PAN down to 1-2 ppb and shows informative dif-
ferences from the oxidant record:
a) Levels of about 10 ppb were present at dawn and
they persisted after sundown clearly showing the
carry-over of photochemical products from one day
to the next.
b) The PAN dropped to undetectable levels between
1100 and 1400 PST showing the good purging of the
air at that time. None of the clean air oxidant can be
ascribed to PAN.
5. The PAN quickly appeared when the front passed the
instrument and its concentration rose to 0.04 ppm, i.e.,
about 10% of the total oxidant at maximum.
Hydrocarbons
An automated flame ionization gas chromatograph pro-
vided information about the smog "precursor" during this
interesting episode. Single injections at 15 min intervals
showed peaks due to methane, ethane, ethene, and acety-
lene. Methane always equals or exceeds the wordwide back-
ground of 1.39 ppm5 and so gives a big peak. The additional
methane contributed by leaks in natural gas supply pipes
pushed this peak off scale much of the time. The other
three peaks (two carbon hydrocarbons) were much smaller
and represented concentrations of 10-30 ppb. A good cali-
bration was not available and the peaks for these concen-
trations are small so only acetylene and methane are plot-
ted in Figure 4. These are both unreactive so they represent
the primary contamination level with natural gas and auto
exhaust respectively. When the O3 and PAN were purged
at 1100 PST the methane dropped to a constant level (pre-
sumably equal to the background level of 1.39 ppm) and
the ethane, ethene, and acetylene became immeasurable.
Natural gas is probably the principal source of the ethane
as well as the methane while auto exhaust is undoubtedly
the source of the ethene and acetylene. It is noteworthy
that the acetylene was actually higher in the morning hours
than after the afternoon frontal passage even though the
oxidant and PAN were appreciably higher in the afternoon.
This is probably due to the longer time of irradiation of the
marine air which arrived at 1400 PST.
Temperature and Humidity
March 16, 1972, was quite a hot day; the maximum was
33°C (Figure 5). The arrival of the smog front was marked
by a small but sharp drop in the dry bulb temperature and
a simultaneous increase in the wet bulb temperature. This
Journal of the Air Pollution Control Association
 Off scale Off scale Water
1 "^ ^ .n.i-ii. torr g / m 3
80
12>12
70
60
1 jMethane
RH
%
*^ CH 4 100
40
90
Acetylene 80
20
70
10
60
0, \ pi ^"Y*W"""" 50
0600 0800 1000 1200 1400 1600 1800 2000 2200 40
Pacific Standard Time, 16 March 1972
30
Figure 4. The clean air present from 1100 to 1400 contained a steady back-
20
ground level of methane and no measurable acetylene.
1 10

shows the cool, moist nature of this marine air. The con- 0600 0800 1000 1200 1400 1600 1800 2000
trast between the two air masses is even more striking Pacific Standard Time, 16 March 1972
when the partial pressure or concentration of water is plot- Figure 6. The contrast between the polluted marine air present before 1100
ted as in Figure 6. The clean air present from about 1100 to and after 1400 and the clean desert air in the interim period is shown better
1400 had only about one half the water content of the pol- by this plot of water concentration and relative humidity.
luted marine air present both before and after this time in-
terval.
Midday temperature and dew point soundings at Los
Angeles Airport (on the coast) and at El Monte, Calif,
(midway between Riverside and the airport) are shown in
Figure 7. They show a strong inversion at the coast and a
weaker one in El Monte; both having a temperature of Meters (MSL) Millibars
about 24°C at 730 meters at the top of the inversion. Sur- v
700
3000 ^
face temperatures at Riverside (300 m above mean sea
level) are also plotted for 1000 PST and 1300 PST. The dry
adiabat from the 1000 PST temperature shows that this air
was nearly warm enough to destroy the inversion and the
1300 temperature would permit mixing to nearly 3000 m -800
2000
(assuming that these upper atmosphere temperatures
could be extrapolated to Riverside from Los Angeles and El
Monte).

Wind Speed and Direction 1000 -900

The winds throughout March 16 were weak and predom-

inantly from the west (Figure 8). No appreciable change in
either speed or direction was evident when the purging oc- 140 1000
curred between 1000 and 1100 PST. In the hour before
front passage at 1400 the speed increased and the direction -20 -10 0 10 30
Temperature, °C
Figure 7. Temperature and dew point soundings at Los Angeles and at El
C Monte near noon on March 16, 1972.
°F -35
Temperature
90
-30
80
•25

70 Miles/hour
•20

60
•15

50 -10

0600 0800 1000 1200 1400 1600 1800 2000

0900 1000 1100 1200 1300 1400 1500 1600
Pacific Standard Time, 16 March 1972 16 Mar. 1972 PST
Figure 5. The lower temperature and higher moisture content reflect the ma- Figure 8. The wind was consistently from the west during the morning, while
rine origin of the polluted air which arrived at 1400 PST. the clean air was present, and after frontal passage.

May 1975 Volume 25, No. 5 523

 stabilized from the west. Surprisingly, the clear air and the
polluted air arrived from nearly the same compass point.
Very similar behavior was observed during another frontal
episode on May 27,1973. It may be that, roughly speaking,
the clean air came from above the inversion and the pollut-
ed air from below it. It is difficult, from the data available,
to understand exactly why the front should be so sharp, or
to judge the relative importance of horizontal and vertical
air motions. These wind observations are somewhat at vari-
ance with the "convergence zone" model described by
Edinger and Helvey6 for fronts observed in the San Fer-
nando Valley. One difference is that the polluted air in this
case reached the San Fernando Valley from the east south-
east after a detour through central Los Angeles and the
clean air arrived from the west.
A time-lapse film taken for Kaiser Steel Corporation7
about twelve years ago showed a similar front in the Fonta-
na, Calif., area (northwest of Riverside). Visually it ap-
peared to fit Edinger's description of such fronts but it dif-
fered from the March 16 front in that it did not appear to
move significantly.
Solar Radiation
Total solar radiation as measured by a Pyroheliometer is
given in Figure 9. Most striking is the sharp fluctuation;
first upward when the smog front passed, then downward
for an average attenuation of about 20%. Although the sun-
light intensity was about half of its maximum value by
0830, when the oxidant first started to increase, the inte-
grated energy up to that time was a small fraction of its
ultimate value for the day. Presumably if the pollution
present in the morning had not been ventilated it too
would have developed 0.4-0.5 ppm of oxidant when
subjected to sunlight.
The still pictures (Figure 1) give no hint of the complex
and interesting motions involved in this pollution front.
The front was first sighted in the west at about 1300 PST
at which time it was about seven miles away. In one hour it
arrived at the camera location. On a previous occasion3 the
velocity of a similar boundary was estimated to be 16-24
mph and it was argued that the boundary need not move at
the same velocity as the wind. Wisps and eddies breaking
away from the main smog bank were visually evident (espe-
cially when viewed through Polaroid) and they can be dis-
cerned by careful examination of the photograph. The
time-lapse film previously referred to 7 suggests that these
eddies were at the front and moving backward away from
the boundary. This is not consistent with the present wind
observations, but was, of course, a different occasion. Ef-
forts are underway to obtain additional time-lapse pictures
of these sharp fronts.
Front CAL/cm 2
0600 0800 1000 1200 1400 1600 1800
Pacific Standard Time, 16 March 1972
Figure 9. Total solar radiation showed a surprising upward excursion just at
frontal passage. Radiation was only a small proportion of its maximum value
when oxidant formation began.
524
Discussion
In the past fourteen years, sharp boundaries like the one
discussed here have been seen in Riverside on the average
of perhaps a dozen times each year. They seem to be most
common in October. In fact, for a long time it appeared
that such boundaries only occurred in that month. Their
prevalence in October may reflect the strength of the ma-
rine airflow in that month. In winter months when solar
heating is weaker the marine layer is shallower and fre-
quently does not penetrate as far as Riverside. In late after-
noons in December and January it can often be seen about
10 mi to the west of Riverside, thinner than the front
shown here and it usually does not penetrate to Riverside.
Perhaps the March episode and the more frequent October
episodes both represent stages intermediate between these
winter and summer extremes. Boundaries have been seen
once in early June and once in late May.
The small (0.05 ppm) but analytically significant oxidant
measured in the clean air prior to the front's arrival re-
quires an explanation. This air is clean because PAN and
C2 hydrocarbons were too small to be measured and be-
cause there was no aerosol visible. The oxidant cannot be
NO2 or PAN because 0.5 ppm would be required to give
such a reading, since they give only about a 10% response
on the Mast analyzer. This argument probably also rules
out any other oxidant such as hydrogen peroxide. The oxi-
dant is therefore believed to be O3, and in the absence of
other pollutants (HC, NOX, PAN) it can hardly be attrib-
uted to polluted air photochemistry. Since the sounding
(Figure 7) suggests that the inversion was broken during
the clean air interval, downwind transport from the ozono-
sphere is believed to be the source of this O3. There is, of
course, substantial literature on this subject. Regener8 for
example, measured up to 0.05 ppm at ground level and esti-
mated the downward flux at 1.2 X 10" molecules/cm2 sec.
Other sources give background ground level O3 values as
low as 0.01 ppm (Tebbens9) and as high as 0.07 ppm (Hesk-
eth10).
Acknowledgments
I thank Professor J. G. Edinger of UCLA for helpful re-
view of the manuscript, Melvin Zeldin of the San Bernardi-
no Country Air Pollution Control District and Donald Lust
of the National Oceanic and Atmospheric Administration
for temperature sounding data, and Professor O. C. Taylor
for the use of air monitoring data.
References
1. J. G. Edinger, Jr., Appl. Meteoroi, 2: 706 (1963); J. G. Eding-
er, Watching for the Wind, Doubleday, New York, 1967.
2. E. R. Stephens, Weatherwise, 18:172 (1965).
3. E. R. Stephens, Atmos. Environ., 2: 393 (1968).
4. E. R. Stephens, Advances in Environmental Science and
Technology, VoL I, Ed. J. N. Pitts and R. L. Metcalf, John
Wiley & Sons, Inc., 1969. pp. 119-146: E. R. Stephens and M.
A. Price, J. Chem. Ed., 50: 351 (1973). R. G. Smith, et al, in
Methods of Air Sampling and Analysis, M. Katz, Ed., Amer.
Pub. Health Assoc, Washington, D.C., 1972. p. 215.
5. E. R. Stephens and F. R. Burleson, J. Air Poll. Control Assoc.
19: 929 (1969).
6. J. G. Edinger and R. A. Helvey, Bull. Amer. Meteoroi. Soc, 42:
625 (1961).
7. Kaiser Steel Corp., Fontana, California, Public Relations Film.
8. V. H. Regener, J. Geophys. Res., 62: 221 (1957).
9. B. D. Tebbens, Air Pollution, Vol. I, 2nd Ed., Ed. A. Stern,
1968. p. 27.
10. H. E. Hesketh, Understanding and Controlling Air Pollution,
Ann Arbor Science Publ., 1972. p. 6.
Journal of the Air Pollution Control Association