Smog

 Term ‘smog’ is derived from the words ‘smoke’ and ‘fog’.

 Is often used as a generic term for any kind of air pollution that reduces
visibility, especially in urban areas.

However, it is useful to distinguish two broad types:

 industrial smog
 photochemical smog.

Industrial Smog / Classical (‘London-type’) smog.

 Industrial smog—also called gray or black smog— develops under cold and
humid conditions.
 Cold temperatures are often associated with inversions that trap the
pollution near the surface.
 Events like the London smog of 1952 are often referred to as industrial
smog because SO2 emissions from burning coal play a key role.

Fog
Is the dispersed water drops. Fogs can be viewed as clouds that are in
contact with the Earth’s surface. Fogs are created during cooling of air next
to the Earth’s surface either by radiation to space (radiation fogs) or by a
contact with a surface (advection fogs).

 The typical London smog results from the accumulation of smoke from coal
burning, which has a high sulfur content. It leads to the production of high
concentrations of sulfuric acid in fog droplets. These acidic particles, along
with high densities of smoke, inhibit the normal functioning of the lungs and
can cause death.
Burning of coal produces sulfur dioxide, soot and other gases and
particulates, which are called smoke.
 Typically high humidity allows for rapid oxidation of SO 2 to form sulfuric
acid and sulfate particles.
 Events similar to the 1952 London smog occurred in the industrial towns of
Liege, Belgium, in 1930, killing more than 60 people, and Donora,
Pennsylvania, in 1948, killing 20.
 Today coal combustion is a major contributor to urban air pollution in China,
especially from emissions of SO2 and aerosols (footnote 2).
Occurs in the regions where:

1) Emission of the sulfur-containing compounds is high (due to burning of

coal to generate heat and energy);
2) Air contains high liquid water contents (e.g., fogs).

In the atmosphere, sulfuric acid particles can be formed in two

ways:
 Direct dissolution of SO2 into water drop and subsequent aqueous-phase
oxidation to sulfate (will be discussed in Lectures 22-23 on acid rain
formation);

Gas-phase conversion of SO2 to sulfuric acid gas (H2SO4), which has a low
surface vapor pressure, and therefore, easily condenses onto particles. The
gas phase conversion requires three steps:

SO2 + OH + M HSO3 + M

HSO3 + O2 SO3 + HO2

SO3 + H2O H2SO4

Photochemical smog.

 Air pollution regulations in developed countries have reduced industrial smog

events, but photochemical smog remains a persistent problem, largely driven by
vehicle emissions.
 Photochemical smog was first described in the1950s.
 Photochemical smog forms when NOx and VOCs react in the presence of solar
radiation to form ozone. /
It is the result of chemical reaction of sunlight, nitrogen oxides and volatile
organic compounds in the atmosphere. All of these chemicals are usually highly
reactive and oxidizing.
 The solar radiation also promotes formation of secondary aerosol particles from
oxidation of NOx , VOCs, and SO2 and sunlight to form ozone.
 Photochemical smog typically develops in summer (when solar radiation is
strongest) in stagnant conditions promoted by temperature inversions and weak
winds.
 Photochemical smog is a ubiquitous urban problem in the developed world with
sunny, warm, dry climates and a large number of motor vehicles. It often
blankets large populated regions such as the eastern United States and western
Europe for extended periods in summer.
Photochemical smog is therefore considered to be a problem of modern
industrialization.
It is present in all modern cities, but it is more common in cities with sunny,
warm, dry climates and a large number of motor vehicles.
Because it travels with the wind, it can affect sparsely populated areas as well.

 Ozone and aerosols are the two main health hazards of photochemical smog.
 Ozone is invisible, but aerosol particles scatter sunlight , and are responsible for
the whitish haze associated with smog.
 Because ozone is created in the atmosphere, concentrations are often higher
downwind of urban areas than in the urban areas themselves. Figure 9 shows
 counties in the United States that currently fail to comply with the national
standard for ozone levels over an 8-hour period (nonattainment areas). These
cover much of California and the eastern United States on a regional scale.
 This mixture of air pollutants can include the following: aldehydes; nitrogen
oxides, especially, nitrogen dioxide; peroxyacil nitrates; tropospheric ozone;
volatile organic compounds.
Occurs in the regions where high emissions of automobiles; large concentrations
of reactive hydrocarbons (RH) (from automobile exhaust or from other natural or
anthropogenic sources); 3) plenty of sunlight (high level of UV radiation).

How it works:

Primary pollutants NO and reactive organic vapors, RH, are emitted from
automobiles. First, RHs are chemically transformed to radicals, denoted R .

RH + OH R. + H2O

R. + O 2 + M RO2. + M

NOTE: The organic radical, R., can be composed of many atoms and have a
complex molecular structure.
Then organic radicals react with nitric oxide, NO, to form nitrogen dioxide, NO 2:

RO2. + NO RO. + NO2

However, in urban air, the sun breaks NO 2 back to NO and O

NO2 + h NO + O , at wavelength < 0.42 µ m
Atomic oxygen produces ozone, O3, which is of primary concern in
photochemical smog:
O + O2 + M O3 + M
Thus, the overall process of smog formation can be summarized as

RH + HO + NO + h O3 + NO2 + HC

⇒ Most of the world’s energy comes from the burning of organic compounds,

whether they represent the organic matter of wood or the hydrocarbons of

natural gas, coal, petrolium (oil), and other fossil fuels.

Do you know that:

∗ combustion of fossil fuels account for about 85% of all energy consumed in
the United Sates in 1995 and is expected to remain close to this level through
2015;
∗ each year the United States consume about 6 billion barrels of oil, more than
the total used by Japan, Germany, Italy, France, Canada, and Great Britain
combined.
∗ in the United States alone, close to 200 million motor vehicles of all kinds burn
more than 140 billions gallons of gasoline and diesel fuel each year as they
travel about 1012 miles.
Gasoline is a mixture of over a hundred different alkanes, alkenes, and
aromatic hydrocarbons to make an effective fuel for the internal combustion
engine.

NOTE: recall Lecture 8 on classification of organic compounds.

Photochemical smog formation:

Initial stage: NO, CO, RH
Final stage: O3, NO2, PAN (and other hydrocarbons), haze (aerosols)

NOTE: photochemical smog evolves in time (will be discussed in Lecture 20).

NOTE: effects of atmospheric aerosols on regional scale is discussed in Lectures
25-26.
• Many big cities exhibit photochemical smog, including Mexico City, Tokyo,
Johannesburg, and Athens, among others.
Table 19.1 Percent of CO, NOx, SOx = SO2 + SO3, and reactive organic gases
(ROG)
Basic classification of hydrocarbons:

Alkanes (or paraffins) are hydrocarbons with a single carbon-carbon bond.

The general formula for the alkanes is C nH2n+2. Mixture of alkanes are found both
in petrolium and natural gas. Natural gas is 60 to 95% methane (CH 4) and
contains smaller amount of ethane (C2H6), propane (C3H8), butane (C4H10), and
pentane (C5H12). Petrolium is a more complex mixture of alkanes.

Alkenes (or olefins) are hydrocarbons with a double carbon-carbon bond. The
general formula for the alkenes is CnH2n. Alkynes are hydrocarbons with a triple
carbon-carbon bond. The general formula for the alkynes is C nH2n-2.

Aromatic hydrocarbons are hydrocarbons which contain at least one ring of

six carbons (benzene).
The most widely emitted organic species in the Los Angeles basin are methane,
toluene, pentane, butane, and ethane.
Let’s apply ‘How it works’ scheme for a case of ethane:

Ethane is emitted from automobiles.

First, a hydroxyl radical attacks ethane, CH 3CH3, by abstracting a hydrogen atom

to form ethyl radical, CH3CH2. :

CH3CH3 + OH CH3CH2. + H2O

Ethyl radical, CH3CH2., reacts quickly with oxygen in the presence of a third body
to form an ethylperoxy radical via

CH3CH2. + O2 + M CH3CH2 O2. + M

The ethylperoxy radical then reacts with nitric oxide to form nitrogen dioxide
and ethoxy radical, :

CH3CH2 O2. + NO NO2 + CH3CH2 O.

Then NO2 goes to form O3, and ethoxy radical goes into a chain of reactions.

Hundreds of different compounds may be produced by the reactions of RH. One

of the most important is peroxyacetylnitrate (PAN). Thus, secondary
hydrocarbons are important components of photochemical smog.
♦ Along with NOx and organic gases, carbon monoxide is a key

component of smoggy air. However, its atmospheric chemistry is very simple:

CO + OH CO2 + H

Impact of smog
a) aggravates asthma, emphysema, and other respiratory issues
b) air-pollution disaster = when lethal effects are observ

Assignment 5/06/2018
 Discuss the reactions of fog formation
 Discuss the formation and types of ozone