Air Pollution

and
Gaseous Pollutants
 Air Pollution
• Air pollution is the atmospheric
condition where air pollutants are
present in concentrations that are a
concern, or even an immediate
danger, for human health,
ecosystems, or infrastructure.
Exposure refers to the condition
when air pollutants reach individuals
(e.g. through breathing), while the
dose is the actual amount taken up
by the human body (e.g. mass of a
pollutant that reaches the blood
vessels of an individual in a given
time).
• Air pollutants are substances which, when
present in the atmosphere in sufficient
concentration, may harm human, animal, plant,
or microbial health, or damage infrastructure or
ecosystems. The most common air pollutants
found in urban air are listed in Table 1 along with
their potential impacts on human health and
ecosystems. Air pollutants occur in all states
(gaseous, dissolved in droplets, liquid or solid
particulates). In all cases, they are transported
by the airflow and mixed by turbulence.
Table 1 Selected major chemicals that are medium to long-lived air pollutants emitted in cities (in alphabetical order).
Compound Major emission sources in Impact on human health Impact on environment
urban areas and infrastructure
Carbon dioxide (CO2) The major product emitted during Even high concentrations are not Most important long-lived
all fuel combustion. Also released toxic, but high density can greenhouse gas–alters
by the respiration of humans, accumulate in basements and global radiative forcing and
animals, vegetation, and soils. poorly ventilated rooms and therefore driver of
reduce/displace oxygen. anthropogenic climate
change.
Carbon monoxide (CO) A primary pollutant from oxygen- Interferes with absorption of Affects animals the same
limited (incomplete) combustion oxygen by haemoglobin resulting in way as humans.
in motor vehicles, industrial oxygen deprivation. Low-to- Contributes to formation of
processes and domestic heating. moderate dosages cause the greenhouse gases CO2
headaches, impair brain functions, and O3 when oxidized.
and reduce manual dexterity. At
high concentrations, death
ensues. Heavier than air.
Halocarbons and A class of inert gases including Halocarbons and
Halogenated gases CFC-11, CFC-12, and SF6. Used halogenated gases
as insulating gases, fillings, or contribute to O3 depletion
refrigerants in consumer goods, in in the stratosphere. Many
the electrical, polymer, and metal are very long-lived (and
industry. hence effective) greenhouse
gases.
Lead (Pb) A toxic metal used as Affects nervous system, Persistent when deposited on
petroleum additive in certain kidneys, liver, and blood- terrestrial or aquatic
countries and released during forming organs. Increases ecosystems. It affects
combustion. Also industrial blood pressure and disturbs ecosystem functioning, and
sources. kidney and reproductive animal reproductivity and
functions. It can cause brain accumulates in food chains.
damage, impaired mental
development, and reduced
growth.
Methane (CH4) The by-product of fuel The second most important
combustion, and fugitive long-lived greenhouse gas.
emissions from leaking of
natural gas pipes and
pipelines. Anaerobic
decomposition (e.g. sewage,
landfills)
Nitrogen oxides (NO, NO2) Primary and secondary Acute exposure causes Contributes to the
pollutant resulting from fuel respiratory diseases (coughs, eutrophication of aquatic
combustion in motor vehicles, sore throats) and at high ecosystems.
coal-, oil-, and gas-fired power concentrations inflames
stations, industrial boilers and airways and reduces lung
waste incinerators. Minor functioning. Can aggravate
emissions occur naturally bronchitis, asthma, and
from soils. emphysema.
Nitrous oxide (N2O) Minor combustion by-product of Important long-lived
fuel combustion, emitted from greenhouse gas.
soils, primarily managed
(fertilized) greenspace.
Non-methane Gasoline vehicle exhausts, leakage Some compounds are carcinogenic. Selected compounds damage
volatile organic at fuelling stations, paint, Selected VOCs cause eye and mucous vegetation.
compounds (VOC) manufacturing, solvents. Biogenic membrane irritation, others may cause
emissions from trees. fatigue and difficulty concentrating.

Ozone (O3) Secondary pollutants formed in Damages respiratory tract and impairs Higher concentrations can
urban, areas primarily from VOCs lung function. Physical activity damage vegetation leading to
and NOx but also CH4 CO can play increases the dosage. Long-term reduced plant growth. O3 is a
a role in the formation O3 at larger exposure may result in decreased lung short-lived greenhouse gas
scales. capacity and premature mortality. changing radiative transfer in
the troposphere.
Polycyclic aromatic Benzene (C6H6) and Benzo(a)pyrene PAHs irritate the eyes, nose, throat, and Many PAHs have acute toxic effects
hydrocarbons (PAH) (BaP) are the most relevant PAHs and bronchial tubes (BaP). Benzene and BaP are on aquatic life and birds and
are emitted during incomplete carcinogenic for humans, and harm the damage the leaves of plants.
combustion in vehicles, domestic immune system and central nervous Selected PAHs bio-accumulate in
heating, organic material (wood), and system, blood production. Can cause food chains.
oil refining. leukemia and birth defects.
Sulfur dioxide (SO2) Primary pollutants are emitted during Exacerbates asthma causing wheezing, Damages buildings. Causes
the combustion of sulfur-containing shortness of breath and coughing, and acidification of soils and aquatic
fuels (coal, diesel, fuel oil), and in inflammation of the respiratory tract. ecosystems downwind of
industrial processing. Synergistic effects with exposure to O3 and emissions, can damage forest
particulate matter. ecosystems. Contributes to the
formation of particulate matter.
Indoor & Outdoor Air Pollution
• Indoor Air Pollution • Outdoor Air Pollution
For a great deal of urban living, an indoor Compared to indoors, air pollution climatology in
environment represents ambient conditions. outdoor urban spaces between buildings is more
In fact, indoor air pollution could be of complex for several reasons. Firstly, emission
greater concern than outdoors, simply sources in an urban system are in multiple
locations. For example, emissions could originate
because most dwellers spend substantially from buildings, and mobile vehicles near ground
more time inside buildings and vehicles and level and even from sources above roof level (e.g.
in many activities (domestic and chimneys) that might be drawn down into the
occupational) the emission of air pollutants urban canopy layer (UCL), in addition, there could
first occurs within a confined indoor setting. be biological contributions by plants and trees.
However, the health consequences of Secondly, airflow itself follows a complex pattern.
exposure to many of the air pollutants found Thirdly, the movement of people (i.e. the
indoors have not been examined to the same ‘receptors’) through a street system exposes them
extent as the common outdoor air to an extraordinary variety of transitory ambient
conditions.
pollutants.
 Gaseous Pollutants
• Gaseous pollutants include primary pollutants,
secondary pollutants, and precursors of
secondary pollutants. Some chemical species
may belong to more than one category. The
main gaseous pollutants that are regulated or
are precursors of regulated pollutants are
briefly presented in the following sections.
• Primary pollutants are those directly emitted
into the atmosphere and retain their chemical
character.
• Secondary pollutants are those formed in the
atmosphere from primary pollutants
 1. Sulfur Dioxide
• Sulfur dioxide (SO2) is a primary pollutant. SO2 is the main pollutant of air pollution
episodes such as that of 1952 in London. It is regulated because it leads to
respiratory problems. As a primary pollutant, its impacts occur near its sources. In
North America and Europe, those impacts are now mostly limited to some
industrial sites and maritime traffic, because sulfur content in fuels used by road
traffic is now regulated.
• SO2 is oxidized to sulfuric acid in the atmosphere. Sulfuric acid contributes to fine
particle air pollution because its low volatility implies that it is preferentially present
in the particulate phase, typically as ammonium salts. In addition, sulfuric acid is
an important component of acid rain. SO2 is slightly soluble in water, and it may be
removed from the atmosphere by dry and wet deposition.
 2. Carbon Monoxide

• Carbon monoxide (CO) is an inorganic carbonaceous compound because it does not contain any
hydrogen atoms. CO is regulated because it combines with hemoglobin in the bloodstream and
leads to anoxia (lack of oxygen) when the bloodstream cannot carry enough oxygen. CO is a primary
pollutant, which is mostly emitted by combustion processes, including internal combustion engines.
Historically, CO concentrations were, therefore, high near roadways. CO was the first pollutant to be
regulated for road traffic in North America and Europe, using catalytic converters, which convert it to
carbon dioxide, and CO2. Consequently, ambient concentrations of CO are now fairly low in these
regions.
• CO is oxidized slowly to CO2 in the atmosphere. leads also to the formation of ozone, the main
gaseous pollutant of photochemical smog. However, the contribution of CO to photochemical air
pollution is less than that of other carbonaceous compounds because of its low chemical reactivity
and the fact that its emissions are currently regulated.
 3. Ozone and Gaseous Photochemical Oxidants

• Photochemical pollution is generally called “photochemical smog.” Smog is the contraction of smoke
and fog because its appearance falls between these two phenomena. Arie Haagen-Smit, a
biochemistry professor at the California Institute of Technology (Caltech), was the first to identify the
processes that lead to the formation of photochemical air pollution, and in particular ozone (O3),
which is its main gaseous pollutant. He showed that photochemical air pollution results from
atmospheric chemical reactions occurring among precursor gases including nitrogen oxides
(NOx)and volatile organic compounds (VOC), in the presence of sunlight. Hence, the adjective
“photochemical” was attributed to that form of air pollution, since photolytic reactions induced by
sunlight initiate the set of photochemical reactions that lead to ozone formation.
• Ozone is not emitted into the atmosphere and is, therefore, a secondary air pollutant. Its precursors
are NOx, VOC, and, to a lesser extent, CO. Although O3 is not the only photochemical oxidant, it is the
main gaseous constituent of photochemical smog in terms of ambient concentrations. Therefore, O3
is targeted for regulations pertaining to the gaseous fraction of photochemical smog. Since O3 is
produced by photochemical reactions, its concentrations are highest during spring and summer.
 4. Nitrogen Oxides
• NOx includes by definition nitric oxide (NO) and nitrogen dioxide (NO2). Their emissions result mostly from combustion
processes. These two compounds represent in terms of ambient concentrations the majority of nitrogen oxides present in the
urban atmosphere. However, there are other nitrogen oxides, such as nitrogen protoxide (N2O), which is a greenhouse gas,
nitric acid (HNO3), nitrogen pentoxide (N2O5), the nitrate radical (NO3), and a large number of organic nitrates. By convention,
NOy represents all nitrogen oxides, with the exception of N2O, and NOz represents the difference between NOy and NOx.Thus,
in summary:

• NO2 is the only nitrogen oxide that is regulated in terms of its ambient concentrations. It leads to respiratory problems. NO2 is
both a primary and a secondary pollutant, because (1) it constitutes a fraction of NOx emissions and (2) it is a product of the
atmospheric oxidation of NO.
• NOx is rapidly oxidized in the atmosphere. They are precursors of a large number of secondary pollutants, such as ozone, nitric
acid, and organic nitrates. Nitric acid may contribute significantly to secondary particulate matter formation. It is also a major
constituent of acid rain. Some organic nitrates contribute to the secondary fraction of organic particulate matter. In addition,
inorganic and organic nitrates play a major role in the eutrophication of ecosystems.
5. Volatile and Semi-volatile Organic Compounds

• Volatile organic compounds (VOC) and semi-volatile organic compounds (SVOC)

are mostly emitted from combustion processes and also from the evaporation of
liquid fuels and some organic-containing products (e.g., some paints, solvents, and
cleaning products). They play a major role in the formation of photochemical smog.
VOC are precursors of ozone. SVOC and some VOC are also important precursors of
the secondary fraction of fine particulate matter. In addition, some VOC, such as
benzene,1,3-butadiene, and formaldehyde, are carcinogenic.
• The ultimate chemical fate of VOC and SVOC is CO2, via atmospheric oxidation.
However, organic compounds may be removed from the atmosphere before being
converted to CO or CO2. Their removal may occur either as gaseous or particulate
compounds, via dry and wet deposition.
 6. Ammonia
• Ammonia (NH3) is the reduced form of nitrogen in the atmosphere.
It is mostly emitted by agricultural activities. NH3 does not present
any adverse health effects at the ambient concentrations usually
observed in the atmosphere. However, it contributes to the
formation of sulfate and nitrate ammonium salts, which may
constitute a significant fraction of fine particulate matter. In
addition, NH3 contributes to nitrogen deposition and, therefore,
may lead to the eutrophication of ecosystems.
 Oxidizing Power of the Atmosphere and
Chemical Reactivity
• The atmosphere is an oxidizing environment because of the presence of 21% of oxygen. However,
oxygen is not the main oxidizing species in the atmosphere and atmospheric oxidation processes are
due mostly to other chemical species that contain oxygen atoms and are formed photochemically in
the atmosphere. The main atmospheric oxidants are:
– The hydroxyl radical, OH
– The nitrate radical, NO3
– Ozone, O3
• The oxidation of chemical species, such as VOC, NOx, CO, and SO 2 by these oxidants can occur more
or less rapidly depending on the oxidant concentrations and the reactivity of the chemical species
toward those oxidants. For a given chemical reaction, two terms are generally used to characterize
this chemical reactivity:
– The half-life
– The lifetime (also called residence time)
• In the case of a reaction with a constant oxidant concentration, the half-life corresponds to the
median of the times needed for all the individual molecules of the chemical species initially present
to react. The lifetime corresponds to the mean of those reaction times.
 Gas-phase Chemistry of
Photochemical Air Pollution
• Oxidants: The reactions leading to the formation of the three main oxidant
species of photochemical air pollution, OH, NO3, and O3, are described in this
section.
• hydroxyl radicals can be formed via the photolysis of ozone:

• In addition to this OH formation pathway, there are two other important

photolytic reactions that lead to OH formation in the troposphere: (1) the
photolysis of hydrogen peroxide (H2O2) and (2) the photolysis of nitrous acid
(HNO2):
The nitrate radical is formed via the reaction of nitrogen dioxide with ozone:

This radical is rapidly photolyzed:

• Its formation does not require any photochemical reaction; therefore, it can be
formed either at night or during the day. However, its rapid photolysis diminishes
significantly its concentration during the daytime. Thus, this oxidant plays a role
mostly at night.
• Ozone is formed in the stratosphere by photolysis of oxygen molecules. Solar
radiation that leads to oxygen photolysis is filtered in the stratosphere and is,
therefore, unavailable in the troposphere to lead to ozone formation there.
However, the photolysis of nitrogen dioxide, which takes place in the visible and
the near ultraviolet (UV) range, takes place in the troposphere:

• Therefore, ozone formation takes place in the presence of sunlight, i.e., during
daytime. However, the lifetime of ozone ranges from several hours to a few days.
Thus, its oxidizing power can also occur at night.
• In summary, the atmospheric gaseous oxidants are the following:
– During daytime: OH and O3
– During nighttime: NO3 and O3
References

➢ Air Pollution. (2017). In Urban Climates (pp.

294–331). Cambridge University Press.
https://doi.org/10.1017/9781139016476.012

➢ Seigneur, C. (2019). Gaseous Pollutants. In Air

Pollution (pp. 146–189). Cambridge University
Press.
https://doi.org/10.1017/9781108674614.008
The End