Photochemical Smog

Air Pollution in Megacities

 Not just Los Angeles
What’s the most common sight when you approach a large city by airplane?
 Urbanization and Air Quality
 Urbanization high concentration of people,
industries and automobiles.
 Exhaust gases from internal combustion engines: CO, CO2,
HC (hydrocarbons), and nitrogen dioxide (NO2).
 NO2 is the precursor of photochemical smog.
 In the presence of sunlight, photochemical reactions occur
that produce smog. (Photochemical reactions are chemical
reactions that involve light photons).
 Local climate can make the problem worse.
 Photochemical Smog
The Case of Los Angeles Air Quality
 Three main ingredients of photochemical smog:
 high automobile traffic volume

 plenty of sunlight

 very stable atmosphere

 Eastern Pacific High –

 Subsidence produces inversion, resulting in an absolutely stable condition.

 Subsidence also produces clear condition and hence more sunlight.

 Topography – basin helps trapping pollutants

 Chemical Reactions of Smog
A few important reactions:

(1) NO2 + h (photon)  NO + O (h represents a photon)

fast (2) O + O2 + M  O3 + M (M represents a neutral molecule)
(3) O3 + NO  NO2 + O2
(4) O + HC (hydrocarbon) S.P. (stable product) + F.R. (free radical)
slow (5) O3 + HC  S.P. + F.R.
(6) F.R. + HC  S.P. + F.R.
(Being a stable product doesn’t mean it is pleasant! It can be irritating to our body.)
(7) F.R. + NO  F.R. + NO2
fast (8) F.R. + NO2  Stable Product (PAN-Type, Peroxyacetyl Nitrate )
(9) F.R. + F.R.  Stable product
Typical Daily Concentration Variation of Smog Chemicals
 Static Stability of the Atmosphere
controls the local air quality
 Actual lapse rate < the dry adiabatic lapse rate → stable.
 Actual lapse rate = the dry adiabatic lapse rate → neutral.
 Actual lapse rate > the dry adiabatic lapse rate → unstable.

 In the following charts, the red dashed lines represent the dry adiabatic lapse rate and solid black lines represent the actual lapse rates of the air
 You only need to compare the “slope” of the lines to determine the stability.
You can tell the air stability by watching the
motion of the chimney smoke
So what is the atmospheric
condition here?
 Photochemical Smog and Weather
 Whereas the photochemistry produces smog, the severity of
smog pollution is largely controlled by the weather conditions.
 In a local scale, the air stability controls the pollution as we
described above. In a larger scale sense, it is the weather
systems that determine the air stability.
 The following slides show the close relationship between the air
quality and meteorological conditions.
•Surface high – sinking air, dry, clear, stable air, may
cause upper level inversion
•Surface low – rising air, cloudy or rainy, unstable air
West Los
Angeles
We see that there was a low pressure system out in the Pacific . The whole
California was controlled by a high pressure system. Near Southern California, the
weather was clear and the air was stable. This usually implies that air quality
would be poor.

Saturday
We can use the ozone level s a general air quality index. On this day, the
peak ozone level at Pasadena was nearly 200 units while it was about 80
units in West LA. High ozone level indicates poor air quality.
A low pressure system was
moving closer to the west
coast and a cold front was
approaching Southern
California. The weather was
expected to become cloudier
and the air less stable. Usually
the air quality can be expected
to improve under such weather
condition.
This is the satellite image
of the day showing the
approaching cold front
system. The sky over S.
California was still clear
but the vertical motion of
air was stronger than before
and the air quality should
improve somewhat.

Sunday
And indeed the air quality was improved. The peak ozone level in
dropped to ~ 100 units in Pasadena and ~ 70 in WLA.
On the next day the cold
front was right over the west
coast.Southern California
weather was cloudy. The
atmosphere was unstable
and air quality should be
improved further.

Monday
Look at the remarkable improvement of ozone levels at Pasadena and W.
LA! The above series of slides show clearly the intimate relation between
local air quality and weather.
How about this? 10/31/2006 1930UTC
Air Stagnation due to High Pressure Systems

Source: Williamson, 1973.

 Source: National Park Service

During the life cycle of plants, some organic particles (such as turpanoids)
are ejected. Due to the high frequency of air stagnation these particles tend
to stay in the air for a long time and hence the hazy look. This is of course a
natural phenomenon and not a man-made pollution, but it is another good
example of the close relation between particle concentration and weather.
 Emission Control

 Because of the photochemical smog problem and its relation with

automobile emissions, California has enacted a series of regulations
purported to cut down the emissions.
 Two specific actions are of interest in this regard:
 (1) The installation of catalytic converter to reduce then amount of

NOX emitted.
 (2) The designation of ‘diamond lanes’— only cars with two or

more passengers can use these lanes, so as to encourage

carpooling.

 The problem, however, will stay as long as the traffic volume is large.
One really needs to develop an efficient public transportation system
in a city like that.
 Vacuum-Insulated Automotive Catalytic
Converter

Converter Basics:
Variable-conductance vacuum
insulation and phase change
material (heat storage) are used to
keep catalytic converters hot for up
to 24 hours.
By having a hot (> 250oC)
converter at the start of a trip, auto
emissions can be reduced by up to
80%.
NREL developed and patented this
concept, and has worked with
Benteler Industries of Grand
Rapids, Mich., to commercialize it
under a Cooperative Research and
Development Agreement
(CRADA).