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Air pollution observed in many urban areas is commonly referred to as smog. Originally
identified with smoke from coal fires mixing with low-lying fogs, the term smog is derived from
a combination of the words “smoke” and “fog”. Smog has historically been described as two
types named after the places where they were first observed, London and Los Angeles. The
London smog has been called reducing or sulfurous smog. This type is identified by high
concentrations of sulfur dioxide (SO2) and particulate matter. London smog is therefore
composed of air pollutants that are emitted directly by combustion processes and are called
“primary pollutants”. The most severe episodes of London smog occur in urban areas when low
winds and a shallow boundary layer of air act to concentrate the pollutants in a relatively small
air volume. The meteorological conditions that enhance this type of smog are usually observed in
winter months during the early morning hours. This type of smog, which is characterized by high
aerosol loadings and high levels of sulfur dioxide occurs in many cities that are burning coal
today. Beijing and Shanghai, China, Cairo, Egypt, Belgrade, Yugoslavia, and Calcutta, India are
current examples of urban centers with London type smog. The Los Angeles smog is an
oxidizing smog formed from the photochemical reactions of nitrogen oxides and volatile organic
hydrocarbons, which are primary pollutants released from the combustion of fossil fuels in
automobiles, power plants, etc. Therefore, the Los Angeles smog, also known as photochemical
smog, is identified with high oxidant levels (e.g., ozone) and haze from aerosols formed in the
smog chemical reactions. 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 hydrocarbons 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. 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 and
of meteorology, 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.
Because the species responsible for photochemical smog are created in the atmosphere by
photochemical reactions of the primary combustion pollutants, they are called “secondary
pollutants”. The Los Angeles type smog is therefore dependent on the daytime intensity of solar
radiation, which promotes the formation of the secondary oxidants and aerosols. In contrast to
London smog, Los Angeles smog is formed during summer months and later in the day, after the
solar radiation has had time to produce the secondary chemical air pollutants. The trace gas
species formed in photochemical smog include the secondary oxidants ozone, PANs, and
inorganic sulfuric and nitric acids. These oxidants and acids play important roles in the effects of
smog on agriculture and ecosystems, in human health, and in materials damage on urban,
regional, and global scales. Most major cities in the world today suffer from some form of
photochemical smog, with some important examples being Mexico City, Mexico, Rio de Janeiro
and Sao Paolo, Brazil, Houston, Texas, USA, and Santiago, Chile. Smog then consists of
aerosols and trace gas species that are of concern due to their potential impacts on human health
and biota (e.g. agricultural damage, etc.). Both aerosols and trace gas species present in smog are
also important in determining the radiative balance of the troposphere, a property known as the
greenhouse effect. These species can heat the atmosphere by absorbing infrared and solar
radiation, trapping it in the troposphere. Aerosols can also contribute to cooling of the
atmosphere, both directly by scattering incoming solar radiation back to space and indirectly by
enhancing cloud formation. The net effect of aerosols on the radiative balance of the atmosphere
depends on the types of aerosols present, their chemical compositions, and where in the
atmosphere they are formed. Thus, the impacts of smog formation on urban, regional, and global
scales are a cause for concern with regard to overall ecosystem well-being as well as human
health.
The formation of photochemical smog in the tropospheric layer of the atmosphere is a complex
process involving the reactions of hundreds of primary precursors in the presence of ultraviolet
sunlight to generate ozone (O3), the principal compound we associate with smog. A new
approach to the study of the chemistry of smog formation has been made possible through the
development of high-speed computers and modern mathematical methods. Computer modeling
is the central technique of this new approach; however, limits and standards for this technique
have not yet been clearly defined. This review is meant both to describe our current knowledge
of smog chemistry, and to help formulate and describe this new approach to elucidation of a
complex scientific phenomenon. Two other advances in the study of smog formation are the
development of smog chambers for experimental purposes and of sophisticated analytical
capabilities with which to assess their results. These tools allow us to perform experiments that
range from simple to extremely complex, under realistic conditions, because smog episodes
generally have a duration of only l or 2 days. In contrast, conditions in the stratosphere limit the
use of controlled laboratory experiments for ozone similar to those performed in smog chambers,
because some important stratospheric chemistry occurs at time scales much longer than a day.
Although the methodology used to study stratospheric chemistry differs from that used to study
smog chemistry, many of the reactions are the same in both parts of the atmosphere; therefore,
stratospheric studies and smog chamber experiments that attempt to replicate the conditions of
the troposphere are complementary. Problems with smog chamber wall effects currently exist;
however, these problems are being addressed. As discussed below ("A Methodology for the
Validation of Smog Chemistry").
It is generally accepted that, under clear sky conditions, the atmospheric oxidation of SO2 to SO4
proceeds mainly via hydroxyl radical (HO) addition. Since the HO radical is the main chain
carrier in photochemical smog, the effect of the HO-SO2 reaction on this chemical system is of
great interest. Furthermore, an understanding of this reaction is important to the development of
effective control strategies to reduce ambient sulfate levels. Most atmospheric modelers have
assumed that SO2 is an HO chain terminator and thus summarized the overall oxidation by the
chemical equation
SO2 + HO4 → H2SO4 (a)
If SO2 is assumed to be an HO chain terminator, then model calculation predicts a high degree of
non-linearity between SO2 control and SO reduction (Meagher and Luria, 1982). In addition, the
assumption of chain termination led these authors to suggest that SO2 control could enhance
NO3- production. On the other hand, if HO radicals are regenerated, then a more linear
relationship between SO2 control and SO4 formation would be expected with little or no effect on
NO3- formation. Recently, Stockwell and Calvert (1983) studied the HOSO2 reaction mechanism
by photolyzing mixtures of HONO in the presence of SO2, NO, N02, H20 and CO. By
extrapolating their data to atmospheric conditions, they concluded that SO2 is not an HO chain
terminator. On the basis of their data, they suggested that the overall oxidation process can be
summarized in one equation
HO + SO2 ( +O2 , H2O) 4 → H2SO4 +HO2. (b)
Although this reaction is thermochemically favourable by 53 kcal mole-1, Stockwell and Calvert
were unable to prove the elementary reactions which result in this overall equation. A series of
smog chamber experiments was performed by scientists to further explore the role of SO2 in
atmospheric photochemical reactions.
In these experiments, the efficiency of SO2 as an HO chain terminator is evaluated by
monitoring steadystate HO levels. Pollutant levels were maintained as low as practical to provide
a realistic data set against which the various mechanistic options could be tested.
Nitrogen dioxide is one of the most important pollutants in urban air. At elevated concentrations
it is directly toxic to humen, and in the UK ambient concentrations widely exceed the EC guide
value of 26 ppb (50 percentile), and at some sites approach the limit value of 105 ppb expressed
as a 98 percentile of hourly average concentrations over 1 year. It is of particular concern that
whilst annual average concentrations of nitrogen dioxide have remained constant at most central
urban sites, peak and 98 percentile concentrations have tended to increase. There are few sources
of primary nitrogen dioxide and the major part of NO2 in urban air is formed from oxidation of
nitric oxide within the atmosphere. In most urban areas motor traffic is the predominant source
of nitric oxide emissions. During summer months, elevated concentrations of NO2 can arise due
to atmospheric photochemistry producing peroxy radicals which accelerate the conversion of NO
to NO2. However, the highest concentrations of NO2 in UK urban areas typically occur in the
winter. Most notably, in the December 1991 air pollution episode in London, a UK site of 423
ppb was measured in central London. The pathways for NO2 formation from NOx are complex,
as exemplified by Figure.a which shows the relationship of hourly mean NOx to hourly NO2 for
the months January, February, November and December 1991 at a busy roadside site in central
London. The Figure is divided into three regimes; in the region marked A, concentrations of both
NOx and NO2 are low and NO2 increases as a relatively constant proportion of NOx. As NOx
exceeds approximately 75 ppb, the graph enters section B in which there is a plateau of near
constant NO2 concentrations with little change in NO2 as NOx continues to increase. Both
sections A and B may be explained by oxidation of nitric oxide by ozone. In section A this
reaction is not consuming all ambient ozone, whilst in section B the process is oxidant limited
and virtually all ozone is destroyed. Section C, however, which occurs with NOx concentrations
above about 600 ppb shows rapidly increasing NO2 with further increases in NOx. It is this
section of the graph which is associated with chemical reactions are occurring as this stage and
the NO plus O2 reaction begins to play a role. However, the analysis of the London December
1991 episode showed that inclusion of this reaction could not explain the rapidity of rise of NO2
during episodic conditions.
Fig.a. Hourly NO2 and NO, concentrations at a busy roadside (Cromwell Road) in London in
January, February, November and December 1991.
Brief History of Smog
Air pollution has been recognized for some time as an urban problem. Moses Maimonides
(1135-1204 A.D.) noted in his writings:
“Comparing the air of cities to the air of deserts and arid lands is like comparing waters that are
befouled and turbid to waters that are fine and pure. In the city, because of the height of its
buildings, the narrowness of its streets, and all that pours forth from its inhabitants and their
superfluities . . . the air becomes stagnant, turbid, thick, misty, and foggy. . . . If there is no
choice in this matter, for we have grown up in the cities and have become accustomed to them,
you should . . . select from the cities one of open horizons . . . endeavor at least to dwell at the
outskirts of the city.”
His description and discussion clearly indicate that in the twelfth century air pollution was
already associated with urban environments and their higher population densities. During the
fourteenth century, coal burning had become such a problem in London that King Edward I
passed a law banning the burning of coal when the English Parliament was in session. This was
the first known legislation aimed at reducing air pollution and human exposures to smog. During
the seventeenth century, after the Restoration, John Evelyn, Esquire, was commissioned by King
Charles II to write for the crown concerning London’s environmental quality and public health
status. He wrote Fumifugium or The Inconveniencie of the Aer and Smoak of London Dissipated
in 1661 A.D. Commenting on the air quality in London due to the combustion of coal, he wrote:
“This horrid Smoake which obscures our Church and makes our Palaces look old, which fouls
our Cloth and corrupts the Waters, so as the very Rain, and refreshing Dews which fall in the
several seasons, precipitate to impure vapour, which, with its black and tenacious quality, spots
and contaminates whatever is exposed to it. . . . It is evident to every one who looks on the yearly
Bill of Mortality, that near half the children that are born in London die under two years of age.”
He further noted in his work that a child born in a country village had an even chance of living
40 years. These early works indicated the severity of the problem of air pollution in urban
centers, even in pre-industrial times. In 1775 A.D., English scientist Percival Pott observed that
chimney sweeps were at risk to contract cancer due to their professional exposures to coal tars,
ash, and combustion products. Thus, the long-term exposure to high levels of coal combustion
products was linked to human health as early as the eighteenth century.
Overview of the Smog Formation Process
The key elements of smog chemistry Haagen-Smit, a plant biochemist studying flower essences
in Los Angeles after World War II, originally identified oxygenated hydrocarbons as a key
element of smog through a comparison of odors (Haagen-Smit, 1952). From a 1937 Swiss
patent, he learned that hydrocarbons and nitrogen oxides could be used to generate oxygenated
hydrocarbons in the presence of ultraviolet light (Pitts and Metcalf, 1980). In what can be termed
the first smog chamber experiments, Haagen-Smit was able to generate the "smell" of Los
Angeles air by irradiating parts per million quantities of heptanes and nitrogen oxides. Although
we now know that ozone is also generated in this process, and that oxygenated hydrocarbons
play a key role in its chemistry, the main elements of smog formation are those demonstrated by
Haagen-Smit (1952):
hydrocarbons, nitrogen oxides, and ultraviolet sunlight. The fundamental chemistry of ozone
formation was reviewed by Leighton (1961). However, the key pathways of the system were not
made clear because computer models and smog chamber experiments that could define these
pathways among the many possibilities had not yet been developed. Also the rate and photolysis
constants of many of the key steps were either unknown or roughly estimated. The first major
review involving computer models and smog chamber validation was done by Demerjian, Kerr,
and Calvert (1974). Their review identified and verified the key hydrocarbons and nitrogen oxide
cycles. Some further refinements made during the last decade are reviewed below ("A
Methodology for the Validation of Smog Chemistry"). The primary benefits of refinements in
basic chemistry have been the development of condensed chemical schemes or mechanisms and
an enhanced knowledge of the key overall processes. Condensed mechanisms are important in
atmospheric modeling because they keep overall numerical problems at a tractable size;
enhanced knowledge of the primary overall processes and smog formation allows us to make the
simple tutorial explanations presented here. Although smog chemistry at the detailed level
studied by chemical kinetists is complex, its key elements can be explained using a minimum of
chemistry.
The nitrogen cycle and the steady-state relationship for ozone:
The formation of ozone in the lower atmosphere (i.e., troposphere) stems from only one reaction:
the addition of oxygen atoms to-oxygen molecules in the presence of a third body:
0 + 02 + M → 03 + M (2)
The oxygen atoms are known to stem from principally the photolysis of nitrogen dioxide (NO2);
this reaction has traditionally been called reaction (1):
NO2 + hv → NO + O (1)
The addition of one reaction completes a cycle that we shall call the "nitrogen cycle," which has
considerable heuristic value. This reaction is the molecule-molecule exchange between ozone
and nitric oxide:
O3 + NO → NO2 + O2 (3)
The photolysis reaction (1) is usually the rate-limiting reaction of the nitrogen cycle, and the
photolysis constant for this reaction is typically between 0.25 and 0.5 per min during most days.
Hence the cycle time for these three reactions is only a few minutes. Ozone accumulation takes
several hours; therefore, the nitrogen cycle "spins" fast enough to maintain a close approximation
to the following photostationary-state equation derivable from these three reactions:
(O3)ss = (k1 / k3) x [NO2] / [NO].
The rate constant ratio (k1/k3) is about 1/100, so a NO2/NO ratio of 10/1 is needed to generate 0.1
ppm of ozone. Note that Reaction (3) converts NO to NO2, but that an ozone molecule is
destroyed. Reaction (1) produces the oxygen atom leading to a new ozone molecule, but NO2 is
converted to NO at the same time. Hence, the nitrogen cycle does not generate or destroy a net
ozone molecule. An additional path of conversion from NO to NO2 is needed that will not
destroy 03, in order for it to accumulate according to the photostationary-state relationship of the
nitrogen cycle. This alternate NO-to-NO2 conversion pathway is provided by the atmospheric
photochemical oxidation of reactive organics such as hydrocarbons. The key type of reaction in
hydrocarbon oxidation, which converts NO to NO2, is the fast radical transfer reaction with NO:
. .
RO2 + NO → RO + NO2 (4)
where R is virtually any organic moiety, or fragment, and can also be hydrogen. There is
considerable evidence to support the nitrogen cycle and the photostationary-state equation for
ozone concentrations in both urban atmospheres and smog chambers. Calvert (1976) analyzed
detailed data obtained in the Los Angeles Reactive Pollutant Program (LARPP) and concluded
that the data and the theory (photostationary-state equation) were consistent. However, since its
early prediction by Cadle and Johnston (1952), there has been some controversy concerning the
accuracy limits of this relationship. A recent study by Shetter et al. (1983) suggests that Reaction
(4) should be included, but even without such a correction, the photostationary-state equation
appears to be valid to within a factor of 2 for urban atmospheres. When computer models are
used to stimulate either smog chamber data or atmospheric situations, the photostationary-state
equation appears to hold somewhat better than the data of Shetter et al. (1983) suggest.
Table 1 presents typical smog chamber modeling results. The comparison with actual
observations is not relevant and is not shown; what is shown is the comparison between the
numerical integration (based on a recently developed detailed chemical mechanism for the smog
chemistry of propene using 110 reactions) and the values of the photostationary-state equations
at the times shown. The photostationary-state equation appears to hold to about 35% even though
NOx varies by a factor of 80, simulated ozone by a factor of nearly 2400, and the light intensity
(k1) by a factor of 25. Thus, the heuristic value of the photostationary-state equation is assured;
ozone formation in urban smog occurs via the simple nitrogen cycle, as NO is converted to NO2
by other reactions outside the nitrogen cycle [such as RO2 plus NO, through Reaction (4)]. Given
the current limits of our analytical capabilities and of our knowledge of detailed chemistry the
differences between the photostationary-state equation and the exact values of ozone seem small.
However, further comparisons are warranted, especially for rural areas with high hydrocarbon-
to-NOx ratios; for these conditions, the equation would not be expected to be valid because the
low NOx concentrations could not sustain a photostationary-state relationship.
The oxygenation cycle for formaldehyde can be written by the following sequence of reactions:
. .
OH + HCHO → H2O + HCO (5)
. .
HCO + O2 → HO2 + CO (6)
. .
HO2 + NO → NO2 + OH (7)
Note that the essential peroxy radical is generated by Reaction (6) and the hydroxyl radical (OH)
returns in Reaction (7) to complete the cycle. In addition, Reaction (7) accomplishes the NO-to-
NO2 conversion central to ozone formation in the nitrogen cycle just discussed. Also note that
the carbon monoxide (CO) generated by Reaction (6) can react like an organic to yield a peroxy
radical:
. .
OH + CO → H + CO2 (8)
. .
H + O2 → HO2 (9)
. .
HO2 + NO → NO2 + OH (7)
However, CO does not have the second essential element for smog formation-a source of
hydrogen-containing radicals-which formaldehyde has:
. .
HCHO + hv → H + HCO (10)
where hv denotes the absorption of light, ultraviolet in this case. The hydrogen atom (H) and
formyl radical (HCO) generated by this photolysis reaction produce two hydroperoxy radicals
via reaction with oxygen molecules, as shown in Reactions (6) and (9).
The NOX and radical sink reaction:
There remains only one more reaction that is central to our basic understanding of smog
photochemistry- the NOx plus radical sink reaction that forms nitric acid (HONO2 or HNO3):
.
OH + NO2 → HONO2 (11)
Fig. 1. Typical smog chemistry evolution profiles for NO, NO2, and ozone.
Responsiveness to precursor changes:
We can now also explain some of the essential effects of control strategies on the overall
chemical process of smog formation. If NOx emissions are held constant and organics are
reduced,ewer radicals are available, there are fewer organics to cycle through the hydrocarbon
oxidation cycle, and the entire smog process slows down, as shown in Fig. 2. If organic
emissions are held constant and NOx emissions are reduced, there is less of a sink for the same
number of radicals, and the entire process speeds up, as shown in Fig. 3. Whether ozone
increases or decreases with NOx control depends on the original organic-to-NOx ratio, as will be
explained later. Figure 3 shows the effect of NOx control on a moderately high organic-to-NOx
ratio. If the smog chamber type of result illustrated by Fig. 3 were an air parcel traveling along a
trajectory, then either time or distance along the trajectory path could be the abscissa. Note that
observers located at different points along the path in Fig. 3 would report different results from
NOx reduction. The NO2 observers would report virtually no change if they were located before
the original NO2 peak, whereas observers located near and just after the original peak would
report very large reductions. Those farther downwind would report little change, since
concentrations of NO2 would already be low and would probably be dominated by local
emissions. Similarly,on the downwind distance of the observer and the source distribution.
Fig. 2. Typical smog chemistry profiles after reducing hydrocarbon emissions at constant NOx.
Fig.3. Effects of reduced NOx emissions on the time dependence of NO2 and ozone
concentrations.
Types
Following are two major types of smog
London Type Sulfurous Smog:
John Evelyn’s comments in Fumifugium were prophetic. During the continuing expansion of the
use of coal and fossil fuels in the nineteenth and twentieth centuries, the air pollution problem
continued to increase in major European cities. In London, the smoke that Evelyn referred to in
his writings to the King was enhanced by meteorological conditions conducive to fog formation.
This combination of smoke and fog led to the commonly used term smog. Smog in London and
many of the major cities in England during the first part of the twentieth century consisted of
high levels of sulfur dioxide mixed with carbonaceous soot and fly ash from coal use in homes
and from industrial emissions. The pollutant levels during intense fog conditions led to such
serious problems that during the winter of 1952, over 4000 excess deaths were observed due to
pulmonary and cardiovascular stress associated with killer smog events. This mortality led to the
passage of the British Clean Air Acts of 1956, aimed at reducing the emissions that produce
London type smog events. due to pulmonary and cardiovascular stress associated with killer
smog events. This mortality led to the passage of the British Clean Air Acts of 1956, aimed at
reducing the emissions that produce London type smog events. Europe was not alone in this type
of problem. On October 26, 1948, a killer smog event occurred in the United States. In Donora,
Pennsylvania, a smog cloud formed, consisting of a poisonous mix of sulfur dioxide (SO2),
carbon monoxide (CO), and metal dust from the smokestacks of the local zinc smelter where
most of the town worked. Over the next five days, twenty residents died and 7000 people, half
the town’s population, were hospitalized with difficulty breathing after being exposed to the
cloud. This type of smog is still quite common in many urban centers of the world, particularly
in China, India, the Middle East, and Eastern Europe.
Los Angeles Type Photochemical Smog
At about the same time that the London smog conditions were being described, a different type
of smog was observed in the United States, in Los Angeles, California, and surrounding areas.
This smog was not reducing in nature like the SO2-filled smoky air of London. Rather, this was
an oxidizing gas cloud filled with nitrogen dioxide (NO2) hydrocarbons, and their photochemical
product, ozone. The first major photochemical smog event, observed in June of 1943, and was
initially thought to be a “gas attack” by the Japanese, as World War II was in full swing. Later,
the event was recognized to be a cloud produced by the photochemical reaction of emissions
from automobiles and industrial plants in the Los Angeles air basin. The contributors to
photochemical smog are primary pollutants (carbon monoxide and carbonaceous soots, nitrogen
oxides, sulfur dioxide, and volatile hydrocarbons) and secondary pollutants formed in the
troposphere during photochemical reactions that are driven by sunlight (ozone, PANs, sulfate
aerosols, nitrate aerosols, organic aerosols, etc.). Note that the secondary pollutants formed in
photochemical smog are produced at higher concentrations during the summertime because of
the higher solar radiation. Atmospheric ozone levels typically reach their highest in the early
afternoon due to the sunlight driven chemistry of this type of smog formation. In contrast, the
London and Donora type smog events typically occurred during winter periods, when high
emissions of the primary pollutants sulfur dioxide and soot combined with low boundary layer
inversions leding to high concentrations near the surface. Thus, conditions are typically right for
primary pollutant fumigations in the winter and early morning. Similarly, the primary pollutant
carbon monoxide has been a major concern in a number of areas during winter months when the
emissions from mobile sources and from residential wood burning, together with the lower
wintertime boundary layer height, can lead to high levels of this toxic gas in the troposphere. In
contrast, the Los Angeles photochemical smog has the highest concentrations of oxidants and
secondary pollutants formed during the summertime in the early afternoon.
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.
OH + CO → H + CO2 (17)
H + O2 → HO2 (18)
HO2 + NO → NO2 + OH (19)
NO2+ sunlight → NO + O (20)
Reaction (20) provides the starting materials for the formation of ozone via reaction (13). Note
that the OH acts to oxidize CO via reaction (17) and is reformed during the oxidation of NO to
form NO2 in reaction (19). For the case of a simple hydrocarbon, ethane ( CH3CH3 ), the reaction
scheme is:
•
OH + CH3 CH3 → H O + CH3 CH2 (21)
• •
CH3 CH2 + O2 → CH3 CH2 O2 (22)
• •
CH3 CH2 O2 + NO → NO2 + CH3 CH2 O (23)
•
CH3 CH2 O + O2 → CH3 CHO + HO2 (24)
•
The HO2 formed from the reaction of the ethoxy radical ( CH3 CH2 O ) and molecular oxygen
(O2) can, in turn, react with NO via reaction (19) and reform OH again, initiating a chain
reaction. This catalytic cycle will continue until the volatile hydrocarbons are depleted or chain
termination reactions occur stopping the chain.
Sulphur Dioxide:
Any impression that the mineral extraction techniques of today have reduced the minimum is
immediately banished repugnant fact that sulphur production, sulphuric acid and all other forms
are produced by the chemical industry) is exceeded by the amount of sulphur poured into the
atmosphere as sulphur dioxide waste from burning fuel. This sulphur dioxide is produced almost
entirely by the burning of fuel, predominantly coal and coke, and to a lesser extent automobile
fuels. Sulphur dioxide then react to form sulphurous smog in the atmosphere.
Role Of SO2 on Hydroxyl Smog Chemistry:
To investigate the role of SO2 on hydroxyl smog chemistry , a series of chamber experiments
was carried out under the experimental conditions presented in Table 2.
Fig. 6. The effect of SO2 on the rate of NO loss and on the rates of NO2 and O3, formation in
smog chamber experiments with low H2O content ; SO2 concentrations 0 (-), 4.51 (----) and 5.87
(-‘-‘-‘) ppm.
Fig. 7. The effect of SO2 on the rate of NO loss and on the rates of NO2 and O3, formation in
smog chamber experiments with moderate H2O content; SO2 concentrations 0 (---), 3.07 (-----)
and 6.38 (-.-.-.) ppm.
Nitrogen dioxide
Nitrogen dioxide is one of the most important pollutants in urban air.
Measurement of the NO2/NOx ratio in road traffic emissions:
NO and NO2 concentrations were measured in a road tunnel (Queensway Tunnel) on 31st
October 1992; 26th January and 11th February 1993. The Queensway tunnel is located in
Birmingham city centre and has dimensions of approximately 5 m in height and width for each
of the two cardividing wall) and 600 m in length. There are a total of 18 ventilation sites in the
tunnel which are switched on when the levels of CO in the tunnel exceed 50 ppm. The flow of
traffic through the tunnel is of the order of 20-45 vehicles/min in each direction. Diesel vehicles
accounted for approximately 5% of this total at the time of the measurements. A
chemiluminescence analyser (Environnement AC 30 M) was employed to measure NO and NO2
concentrations in the tunnel. The precision of measurements was greater than 3% for NO and 5%
for NO2. The sampling site was in the emergency bay near the half-way point of the tunnel. The
inlet of the NO-NOx analyser was located approximately 0.5 m from the kerbside and at about
1.8 m height. Results of the measurements of NO and NO2 concentrations and NO2/NOx ratios
on 26th January 1993 are presented in Fig.9 . The meteorological conditions were as follows:
relative humidity ranged from 51 to 81%, temperature from 6.8 to 9.40C and it was raining in
the afternoon. Nitric oxide varied from 1280 to 1780 ppb, nitrogen dioxide from 104 to 175 ppb
and NO2/NOx ratio from 6.3 to 8.1% in the tunnel. It should be noted that a traffic jam occurred
from 17:46 to 18:0l (shown in Fig. 9). During this period nitrogen dioxide increased from 121 to
152 ppb and the ratio from 6.8 to 8.1%, while nitric oxide increased only slightly. The
concentrations of total oxidants (NO2 + O3) at a background site in the city kept steady at a level
of approximately 40 ppb during the three sampling days. Because of high concentrations of NO
in the tunnel and low light intensity, it is reasonable to assume that the ozone concentration was
zero and about 40 ppb NO2 was contributed from background ozone. Compared with the high
NO concentration in the tunnel, background NO was negligible. Subtracting the NO2 formed
from background ozone, the NO2/NOx ratios would be 3-5.5%, 4-6% and 5-7.5%, respectively
on three sampling days. Clearly, these ratios should be reflective of those in the actual vehicle
emissions .It appears that idling vehicles give higher NO2/ NOx ratios, as shown in Fig. 9, which
is consistent with the results of Lenner and Lindqvist, but even the maximum ratio during the
traffic jam was only 8.5%.
Aerosol Formation
Over the past fifty years, knowledge of the incredibly complex chemistry involved in the
formation of smog has increased significantly. Besides the oxidants formed from the chemical
reactions described in sections above, three other sets of reactions involve chain termination
steps. The first of these is the reaction of hydroxyl radical (OH) with nitrogen dioxide ( NO2 ) to
form nitric acid ( HONO2 ):
OH + NO2 →HONO2 (34)
Nitric acid formed in this way removes both chain-carrying OH and NO2 , which forms ozone
via photolysis. However, nitric acid is very soluble in water and is a strong acid, and it thus
ammonia ( NH3 ) to form ammonium nitrate ( NH4 NO3 ), an important contributor to secondary
aerosol formation in urban and regional settings:
HONO2 + NH3 → NH4 NO3 (35)
The second reaction involving a chain termination step is the reaction of HO2 with itself to form
hydrogen peroxide (H2 O2)
HO2 + HO2 →H2 O2 + O2 (36)
This reaction removes HO2 and therefore is important when NO concentrations are lower.
Reaction 36 can then compete with reaction 19. Hydrogen peroxide is very soluble in water and
can react very rapidly with sulfur dioxide ( SO2 ) in cloud droplets or on wet aerosol surfaces to
form another important strong acid, sulfuric acid ( H2 SO4 ).
H2 O2 + SO2 (aqueous) → H2 SO4 (37)
Sulfuric acid can also react with ammonia to form ammonium bisulfate ( NH4 HSO4 ) and
ammonium sulfate [(NH4)2 SO4] . Sulfuric acid and the associated ammonium salts are
important atmospheric aerosol products. Sulfuric acid is also an important contributor to acidic
precipitation. Larger organic compounds emitted into the air can also be oxidized to form
secondary organic aerosols. Indeed, natural monoterpene hydrocarbons emitted from urban trees
can react with the energy-related pollutants and secondary ozone to form a variety of compounds
found in smog aerosols. Carbonaceous soots can also be emitted directly from automobiles and
diesel engines. These soots contain oily organic coatings and associated polycyclic aromatic
hydrocarbons (PAHs) and have received some attention as air toxics. Road dusts from tire
erosion, road work, and traffic are also a major source of aerosols in many urban areas. Sea-salt
aerosols from surf and wind spray can also add to the aerosol burden near ocean shores. Wind
blown dusts especially in arid (desert) regions can be important and have been found to travel
very large distances including transport across the Atlantic and Pacific Oceans. These
windblown dusts are adding to the background in many cities like Beijing, China and contribute
to the brown clouds in Asia. All of the aerosol species (organic and inorganic) can play
important roles in the radiative balance of the atmosphere on urban, regional, and global scales.
but the radical production rate is exaggerated. Any OH, radicals would react rapidly with the CO,
. .
leading to HO2 radicals [via Reactions (6) and (7)], which regenerate the OH radicals via the
reaction with NO [Reaction (4). Termination of this chain process is also suppressed to some
.
extent since the NO2 termination reaction with OH [Reaction (5)] would be reduced by the OH
reaction with CO. The CO and NO experiment can generate ozone only if the key element-
hydrogen-containing radicals is present. The observation of ozone, or at least the rapid
conversion of NO to NO2, actually provides a measure of the radical source strength. Data
determined from smog chamber experiments is an essential element in the validation of the
processes involved in smog formation. An emerging development in the methodology of
validation involves computer modeling of such experiments using various kinds of chemical
kinetic mechanisms. We now turn to a description of this methodology and of the hierarchical
concept of species considered by explicit mechanisms used in the modeling of photochemical
smog.
Evaluation of chemical reactions:
The evaluation of chemical reactions is also an important element in the new methodology.
Stratospheric chemistry primarily involves the inorganic reactions of oxygen, nitrogen, chlorine,
and hydrogen atoms. Since the early 1970s, considerable effort has been made to expand, refine,
and evaluate these reactions for use in photochemical models of the stratosphere. As noted
earlier, the development of smog chemistry has benefitted from the availability of this high-
quality fundamental information. A problem currently of concern, the potential loss of the
stratospheric ozone layer, has been studied using computers and sophisticated analytical
equipment. The modeling approach to this problem is similar to that used in the study of smog
chemistry; moreover, a significant part of this evaluated data is important and useful to the
development of smog chemistry. Review panels whose purpose is to determine the best available
chemical reaction rate parameters have not been nearly as extensive for smog models as for
stratospheric models, however. There are currently two active evaluation panels for stratospheric
chemistry, the CODATA Task Group on Chemical Kinetics and the NASA Panel for Data
Evaluation (NASA, 1982). The CODATA group is composed primarily of European scientists,
and the NASA group is composed primarily of scientists in the United States. One evaluation of
smog chemistry was funded by the U.S. Environmental Protection Agency.
Both reactions are fast, but the pair produce no net effect. However, if some other source of
HONO is available that does not consume a radical, then such a source, followed by the
photolysis step, could be an important source of radicals in the smog chemistry. Recently
observed the buildup of HONO in a polluted atmosphere at night. The formation of HONO in
smog chambers, presumably heterogeneously, has also been observed. The following sequence
of reactions represent another "do-nothing" cycle:
Note that there is no net loss of ozone or nitrogen oxide species as long as the sun is present.
Therefore, the first reactions become fairly important at night. Also, the NO3 radical can react
with NO2 to form N2O5
NO3 + NO2 → N2O5 (44)
N2O5 → NO3 + NO2 (45)
which is a "do-nothing" subcycle of the original NO2 + O3 (etc.) cycle. Of course, if NO3 or N2O5
react outside these cycles, then the original NO3 + O3 reaction becomes more important. Indeed,
NO3 can react with many organics such as olefins or phenols, whereas N2O5 is known to react
with H2O on surfaces leading to nitric acid. However, all of these effects involving NO3 do not
substantially alter the process of smog production, even though the NO3-related chemistry can
play a measurable role.
Fig.9 . Schematic diagram of hierarchical levels of species in Photochemical Smog.
Formaldehyde chemistry:
Formaldehyde represents one of the simplest precursors of photochemical smog and appears to
be an intermediate product in the oxidation of almost all organics. Current explicit mechanisms
contain four reactions involving formaldehyde: the reactions with hydroxyl, hydroperoxyl, and
oxygen atoms, plus photolysis. The main decay pathway for formaldehyde in typical urban
atmospheres is the reaction with hydroxyl. However, the photolysis of formaldehyde is much
more important to overall smog chemistry because a major photolysis pathway involves the
generation of radicals, which can drive the overall oxidation of all organics. The current status of
formaldehyde chemistry can be summarized by saying that several dozen formaldehyde smog
chamber experiments can be simulated with the current standard formaldehyde mechanism.
However, some of the simulations must invoke a means of simulating the loss and reappearance
of formaldehyde to and from the condensed water (if any) on the chamber walls. In other words,
formaldehyde chemistry seems well established, but the validation experiments are troubled by
physical problems associated with the handling of formaldehyde itself.
Acetaldehyde chemistry:
Acetaldehyde chemistry brings the chemistry of PAN and methylperoxy radicals into the
formaldehyde and NOx chemistry. Methylglyoxyl and biacetyl also require consideration of the
chemistry of PAN and methylperoxy radicals, but a range of experimental conditions with which
to test their chemistry is not as readily available as is the case for acetaldehyde.
Paraffin chemistry:
The simplest paraffin is methane (CH4) and it undergoes the smog oxidation cycle very slowly,
since the rate constant for hydroxyl attack is 2 orders of magnitude lower than for most other
paraffins:
. .
CH4 + OH → CH3 + H2O (46)
. .
CH3 + O2 → CH3O2 (47)
. .
CH3O2 + NO → CH3O + NO2 (48)
. .
CH3O + O2 → H2CO + HO2 (49)
. .
HO2 + NO → NO2 + OH (50)
Note that the only new reaction added to the NOx-formaldehyde-acetaldehyde hierarchical
scheme is the first reaction. Although the only significant initial pathway for higher paraffins is
hydroxyl attack, this simple beginning leads to a complicated series of chemical reactions
involving the intermediate species that are formed. In recent years, the development of explicit
kinetic mechanisms for paraffins has concentrated on the chemistry of the intermediate products
such as the alkoxyl radicals (RO), alkylperoxy radicals (RO2), aldehydes (RCHO), and ketones
(R2CO). Several years ago the isomerization reactions whereby a hydrogen atom is transferred
from one end of an alkoxyl radical to the other were discovered. Unfortunately, there has been
little research to date elucidating the chemistry of the many hydroxysubstituted compounds
generated from these isomerizations. Studies that measure the photolysis rates and hydroxyl
attack rates of the hydroxy-carbonyl intermediates have only recently begun. Hence, much of the
modeling of smog chamber data has utilized speculative values for these rate and photolytic
constants. Recent developments concerning paraffin chemistry are contained in studies of alkoxy
radicals. In this last study, a new methodology produced reasonably accurate measurements for
the reactions of the methoxy and ethoxy radicals with oxygen. The new rates are much higher
than previous estimates, the new data have been extended to update the thermochemical kinetic
estimates for alkoxy radicals as large as four carbons. These new estimates support previous
adjustments to obtain closer agreement with observations for smog chamber simulations of
butane experiments.
Olefin chemistry:
Hydrocarbons with a double carboncarbon bond (e.g., olefins) are very reactive in the
atmosphere. More smog chamber experiments have been performed using olefins, particularly
propene, as the sole hydrocarbon than using any other type of compound. The double bond reacts
not only with hydroxyl radicals (OH), but with oxygen atoms, ozone, and the nitrate radical
(NO3) as well. Also, the reactions of olefins tend to be different than those of other
hydrocarbons. For instance, the hydroxyl radical adds to the olefin rather than abstracting a
hydrogen atom, as is the case in Reaction (5) for formaldehyde. Moreover, the olefins tend to
produce two carbonyls per initial reaction rather than the one carbonyl produced from most other
classes of hydrocarbon. For example, the main sequence of reactions, starting with hydroxyl
attack on ethene, is as follows:
Aromatics chemistry:
Toluene, Any discussion of the photooxidation of aromatic hydrocarbons should begin with
toluene, since that compound has received the most attention to date. Toluene accounts for the
highest fraction of aromatics in urban atmospheres. There are three current descriptions of
toluene oxidation. All three descriptions are similiar in their discussion of the ring opening
mechanism, and all derive from the experimental work. However, the mechanistic product yields
differ and the three descriptions have different treatments of radical and nitrogen balance.
Toluene oxidation differs from olefin and paraffin oxidation in several important ways. Three
major differences between the photooxidation of toluene and that of a compound such as
propylene have been observed:
(1) A high photolysis rate for toluene oxidation products. Toluene oxidation products photolyze
at a rate twice that resulting from a 100% yield of formaldehyde from toluene decay. This rate is
probably caused by the formation of methyl glyoxal, which photolyzes at a rate roughly 15 times
that of formaldehyde.
(2) A low rate of peroxyl radical production. The inefficiency of toluene and other aromatic
hydrocarbons in effecting NO-to-NO2 conversions has been observed by other investigators.
Empirically, methyl glyoxal photolysis alone is nearly sufficient to explain the number of NO-to-
NO2 conversions observed in toluene oxidation. Thus, either the other products of toluene decay
are unreactive or there is a mechanism in toluene oxidation that destroys peroxyl or otherwise
prevents the peroxyl radicals from reacting with NO.
(3) A powerful NOx sink mechanism. This seems to occur after the onset of ozone production
and does not seem to consume hydrogen-containing radicals. This sink probably involves NO3
and may result in dinitrate compounds or nitrophenols.
Aromatics chemistry: m-xylene. The next most important aromatics molecule in urban
atmospheres presently appears to be m-xylene. In fact, a recent detailed analysis of Los Angeles
air indicates that the two most important molecules for smog production are first toluene and
then m-xylene . This ordering is quite different from that of a similar detailed analysis reported
in the early 1970s; this analysis showed ethene and isopentane to be the two most important
molecules in Los Angeles smog. Although explicit mechanisms for m-xylene have not yet been
published, available evidence indicates that important mechanistic differences between m-xylene
.
and toluene chemistry exist beyond the factor of 3 increase in OH attack. Notably, the radical
source strength is also higher for m-xylene than for toluene. This higher radical source strength is
consistent with more methyl glyoxal formation from the ring-opened m-xylene, since it has two
methyl groups rather than the one methyl group it has in toluene. The NOx sink strength for m-
xylene is, by contrast, somewhat less than for toluene, suggesting a lower yield of phenolic
compounds in the m-xylene system. Also, the yield of PAN is higher for m-xylene than for
toluene, which is again consistent with the extra methyl group. Preliminary smog chamber
experiments comparing m-xylene with an urban mix by partial substitution (20% carbon) show
an exceptionally high reactivity for m-xylene. Many other hydrocarbons show little change
between full urban-mix experiments and the substitution experiments, e.g., toluene shows only a
small effect, as does the natural hydrocarbon a α-pinene.
Surrogate mechanisms:
Surrogate mechanisms are perhaps the easiest to understand. For laboratory smog chamber
experiments involving individual HC species, mechanisms are available that explicitly treat
every compound with a significant role in the chemical process. In the surrogate mechanism
approach, the explicit mechanisms for one or more HCs are added together. The complex urban
mix is then assumed to be represented by some blend of the HCs treated by the explicit
chemistry. The obvious difficulty with this approach is the specification of the surrogate blend.
The mechanism used in the present form of the empirical kinetic modeling approach (EKMA) is
a surrogate mechanism that uses a 25% propane/75% butane mix to simulate automobile exhaust.
The appropriate mix for nonautomotive emissions has not been established. One possible method
for adapting the surrogate mechanism approach to HC mixes other than automobile exhaust has
been offered by the users of the Lawrence Livermore grid model (known as LIRAQ). In the
LIRAQ emission inventory, each individual HC species is represented by "propane/butane
equivalents" the amount of propane and butane that might represent a kilogram of HC emissions,
However, this procedure has not been verified.
Lumped-molecule mechanisms:
The lumped-molecule approach to kinetic modeling is a widely used method of simplifying the
smog chemistry problem. Lumped-molecule mechanisms are based on the approach, in which
molecular species are classified as olefins, paraffins, aldehydes and usually, aromatics. The rate
constant for each generalized HC class should, in theory, be an appropriate average rate of the
individual compounds contained in each class. However, in practice, lumped-molecule
mechanisms usually specify some default value that may or may not approximate the ensemble
average. In general, lumped-molecule mechanisms require noninteger stoichiometric parameters
to describe reaction pathways for the lumped molecular species and the lumped intermediates
generated by the chemistry. Choice of the proper values for the stoichiometric parameters poses
a problem that is initially related to the averaging of rate constants just described; the
stoichiometric parameters usually relate to the average size and distribution of the lumped initial
species. However, the stoichiometric parameters in lumped-molecule mechanisms may also
affect both reactivity and carbon balance. Specification of these parameters to satisfy all of these
constraints simultaneously can be difficult.
Lumped-structure mechanisms:
The lumped-structure approach is an attempt to decouple reactivity and carbon conservation.
The concept is similar to that used by Benson (1968), who calculated molecular reactivity from
submolecular components. Thus, in the lumpedstructure approach, carbon structures within the
HC molecule are the lumping category. In an olefin molecule, for example, the chemistry of the
olefinic group is treated independently from any paraffinic side chains. The lumped-structure
approach offers several advantages over the lumped-molecule approach. Because similar
structures have similar reaction rate constants, the averaging problem is minimized. Carbon
conservation can be expressly maintained, and carbon balance during the simulation can even be
monitored. The principal disadvantage is that intramolecular processes such as decomposition
and side-chain activation may require adept treatment. Also, because the lumped-structure
approach is often less intuitive than the lumped-molecule approach, the documentation
requirements may be higher.
Reactivity considerations in chemical mechanisms:
Given our previous basic description of smog chemistry, we can identify three factors that
influence the production of O3. The first is the radical sources needed to maintain the
.
concentration of hydroxyl (OH ) radicals required to initiate the HC oxidation process. The
second is a concentration and species mix of HCs; the reaction of OH with HCs produces the
peroxy radicals that enhance the oxidation of NO to NO2. The final factor is the presence of NOx,
which reacts with peroxy radicals and generates O3. The first two factors-radical sources and HC
concentrations and species mix-comprise what is generally referred to as "reactivity." The effects
of NOx are more complex. Although it is true that NOx is necessary for the generation of O3,
NO2 also serves as a principal radical sink in smog chemistry. Thus, as noted in the discussion of
the EKMA isopleths, increasing NOx serves to reduce the radical concentration, to reduce the
rate of HC oxidation, and thus to slow the production of O3. Given a particular level of HC,
increasing NOx slows the O3 formation rate, but increases the peak O3 until a particular HC:NOx
ratio is reached (the "ridge line" ratio on an isopleth diagram). Additional increases in NOx levels
further slow O3 production and reduce peak O3, though this reduction depends greatly on factors
such as total allowed reaction time, dilution rate, and heterogeneous 03 destruction. Because the
basic reactions of smog formation have been studied intensively in laboratory experiments, most
current chemical kinetic mechanisms treat NOx chemistry in a similar fashion. The treatment of
N2O5 chemistry is an area of uncertainty that has led to minor differences among mechanisms;
the major differences, however, are found in the treatment of HC oxidation behavior. The
oxidation reactivity of the precursor HC mix appears to be similar in most current mechanisms;
the principal difference occurs in the HC lumping procedure. For example, many mechanisms
lump ethane along with the other olefins, yet ethene has an OH reaction rate constant of less than
one-third that of propene. If the propene rate constant is nevertheless used for all olefins, the
reaction chemistry of olefins may be dominated by an erroneously high value for all ethene-OH
reactions. Since ethene typically comprises 50% of olefins, the error in overall mechanism
performance may be large. The effect of the error is too much reactivity early in the day and too
little reactivity later in the day. A more important difference in mechanism behavior results from
assumptions concerning product yields. Subsequent to the initial reaction step, HC oxidation is
dominated by the reactions of oxygenated products:
. .
HC + OH → RO2
. .
RO2 + NO → NO2 + RO
. .
RO → HO2 + aldehyde
. .
Aldehyde + OH → RCO3
. .
RCO3 + NO + O2 → NO2 + CO2 + R’O2
The R'O2 at the end of this cycle is not the same as the initial RO2; it contains one less carbon
atom. Lumped mechanisms tend to treat all RO2 radicals as being similar. To terminate the
reaction chain, some kind of chain-length parameter is required. Aldehydes react rapidly with
OH, and they also photolyze to generate radicals. After a period of time, the balance of aldehyde
production and aldehyde loss will dominate the behavior of a chemical kinetic mechanism.
Current mechanisms are sufficiently dissimilar in their treatment of aldehyde formation and loss
that disparities in calculations caused by this feature will become significant in less than one day
of simulation time.