LECTURE 3

URBAN AIR
POLLUTION

Noni/FSG/UITM PHG
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LEARNING OUTCOMES;
• Definition of urbanization
• Explain pollutants formation in combustion
processes
• Discuss emission inventory and emission factor
• Describe the types of smog and formation of
photochemical smog
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What is urbanization?

Urbanization is a process of relative

growth in a country’s urban population
accompanied by an even faster increase
in the economic, political and cultural
importance cities relative to rural area.
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Urban air
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Urban air
• Air pollution was first perceived as a local problem in
urban industrialized areas.

• Taller smoke-stacks for industries and power plants

were a ready solution.

• However, taller stacks merely transported the problem

elsewhere and soon regional problems such as acid rain
were recognized.

• For example, in Scandinavia, the acidification of lakes

was found to result largely from industrial emissions of
sulfur dioxide from tall stacks located in central
European countries such as Germany.
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Urban air
• Most recently, global problems such as climate change and
stratospheric ozone depletion have been widely publicized.

• Obviously, laws and regulations to correct and control local,

regional and global environmental threats require progressively
more cooperation; starting from city ordinances, through state
laws (or, in Europe, individual country statutes) and finally
requiring full participation in international agreements.

• Unlike forest and mineral resources, the atmosphere is truly a

shared resource that respects no man-made boundaries.
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POLLUTANTS FORMATION IN
COMBUSTION PROCESSES
 Basically under three mechanisms (ways):
NOX FORMATION

 Thermal
 Fuel
 Prompt

• Thermal
 Formed when nitrogen and oxygen in the combustion air
combine with one another at the high temperatures.
 Makes up the majority of NOx formed during the combustion of
gases.
 The reactions are described as follows:
N2 + O NO + N
N + O2 NO + O
N + OH NO + H
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 Fuel NOx

 Formed by the reaction of the organically bound

NOX FORMATION

nitrogen in the fuel with oxygen in the combustion

air.

 The process is complex but can be simply

expressed as follows:

Fuel-N thermal N-intermediates

decomposition (HCN, NH , N, CN)

N-intermediates + O2 oxidation NOx

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 Prompt NOx
 Formed by the rapid reaction of hydrocarbon radicals with
NOX FORMATION

atmospheric nitrogen to produce HCN, hence NOx via a complex

series of gas phase reactions.

 The process can be simply expressed as follows:

CH + N2 HCN + N

N + O2 NO + O

HCN + OH CN + H2O

CN + O2 NO + CO
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 The combustion of methane gas

COX FORMATION

(CH4 + 2O2 CO2 + 2H2O)

 produces an undesirable product, namely the "global warming
gas" carbon dioxide.

 Carbon monoxide is oxidized to CO2

CO + H- + O2 CO2 + HO-
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 SO2 is almost exclusively formed during the combustion

of fossil fuels with relevant sulfur content (coal)
SOX FORMATION

CH3-SH +3O2 SO2 + CO2 + 2H2O

 During the combustion and in exhaust channels, the SO2

can be oxidized to SO3
2SO2 + O2 2SO3
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Mobile Sources
• Emissions from an individual car or passenger truck are
generally low, relative to smokestack plumes that many people
associate with air pollution.

• But in numerous cities across the country, the personal

automobile is the single greatest pollution category, as
emissions from millions of vehicles on the road add up.

• Driving a private car is probably a typical citizen’s most

“polluting” daily activity. The power to move a car comes from
burning fuel in an engine.

• Pollution from cars comes from by-products of this

combustion process (exhaust) and from evaporation of the fuel
itself.
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What are the emissions of concern that come from cars

and trucks?
HYDROCARBONS

• HCs emissions result when fuel molecules in the engine do not burn or
burn only partially.

• HCs react in the presence of NOx and sunlight to form ground-level

ozone, a major component of smog.

- Ozone irritates the eyes, damages the lungs, and aggravates respiratory
problems. It is our most widespread urban air pollution problem.

• VOCs are the most commonly tracked HCs and are emitted from the
tailpipe, by the evaporation of fuel and refuelling.

- About 31 percent of anthropogenic VOC emissions are from cars and

trucks. An exhaust HCs are also toxic, with the potential to cause cancer.
 14

What are the emissions of concern that come

from cars and trucks?

NITROGEN OXIDES (NOx)

• Under the high pressure and temperature conditions in an

engine, nitrogen and oxygen atoms in the air react to form
various nitrogen oxides, collectively known as NOx.

• Nitrogen oxides, like hydrocarbons, are precursors to the

formation of ozone. They also contribute to the formation of acid
rain.

• About 30 percent of NOx emissions are from cars and trucks.

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What are the emissions of concern that come

from cars and trucks?
CARBON MONOXIDE

• Carbon monoxide (CO) is a product of incomplete combustion

and occurs when carbon in the fuel is partially oxidized rather
than fully oxidized to carbon dioxide (CO2 ).

• Exposure to carbon monoxide reduces the flow of oxygen in the

bloodstream and is particularly dangerous to persons with heart
disease.

• About 60 percent of CO emissions are from cars and trucks.

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What are the emissions of concern that come

from cars and trucks?
PARTICULATE MATTER

• Particulate Matter (PM) includes both fine and coarse particles.

- Fine particles (PM2.5) result from fuel combustion including cars
and trucks.
- Coarse particles (PM10) generally result from vehicles traveling
on unpaved roads with a small amount caused by combustion.
- These particles can accumulate in the respiratory system and
are associated with numerous health effects.

• Exposure to coarse particles is primarily associated with the aggravation of

respiratory conditions, such as asthma.

• Fine particles are most closely associated with heart and lung disease,
increased respiratory symptoms and disease, decreased lung function, and
even premature death.

• About 25 percent of anthropogenic PM10 emissions are from cars and trucks.
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What are the emissions of concern that come

from cars and trucks?

GREENHOUSE GASES

• Greenhouse gas emissions are primarily carbon dioxide (CO2),

which is a product of fuel combustion.

• CO2 does not directly impair human health, but it is a

"greenhouse gas" that traps the earth's heat and contributes to
the potential for global warming.

• About 26 percent of anthropogenic greenhouse gas emissions are

from cars and trucks.
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EMISSION INVENTORY

a detailed listing of pollutant emissions,

and their calculated emission rate
estimates, as identified from specific
sources
• Accounts for the mixture of emissions and
predicts future air quality.

• Air quality is the result of a mixture of pollutants

added by many different sources.
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What pollutants are in the emission

inventory?

• Includes data about :

▫ Total organic compounds
▫ Reactive organic compounds
▫ Oxides of nitrogen
▫ Particulate matter
▫ Carbon monoxides
▫ Sulphur dioxide
▫ Ammonia
▫ Lead
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EMISSION FACTOR

Representative value that attempts to relate

the quantity of a pollutant released to the
atmosphere with an activity associated with
the release of that pollutant.

• Usually expresses as weight of pollutant

unit weight, vol, distance, duration of activity

• Example : kg of particulate emitted / megagram of coal burned

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• The general equation for emissions estimation is

E = A x EF x (1 – ER/100)

Where :
▫ E = emissions
▫ A = activity rate
▫ EF = emission factor
▫ ER = overall emission reduction efficiency, %
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Emission inventory & emission factor

• Fundamental tools for air quality management

• Emission estimates are important for developing emission

control strategies, determining applicability of permitting and
control programs, to figure out the effects of sources and
appropriate mitigation strategies.

• The inventories used for ambient dispersion modeling and

analysis, control strategy development, and in screening
sources for compliance investigations.

• may also use in some permitting applications, such as in

applicability determinations and in establishing operating
permit fees.
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CONTROL OF POLLUTION FROM

AUTOMOBILES
Important points requiring control: Evaporation loss of fuel
(petrol/diesel) from fuel
tank

Evaporation of HC’s from

carburetor

Emission of unburned gas

and partially oxidized HC’s
from crankcase NOx.

HC’s, and CO in the

exhaust

CONTROL OF THE POTENTIAL EMISSION
POINTS
• Crankcase emissions have been
eliminated by recycling crankcase
gases into the intake manifold and
the installation of the positive
crankcase ventilation valve (PCV).
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• Evaporation from the gas tank
can be eliminated by use of gas
tank caps that prevent vapor
escaping
• Losses from carburetors can be
reduced by using activated
carbon canisters that adsorb
vapors emitted when the engine
is turned off and hot gasoline in
the carburetor vaporizes.
• The vapors are purged from
the canister by air when the car
is restarted and burned in the
engine.
• The toxicity of emission from
exhaust can be reduced by
applying the catalytic converter.
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Exhaust Emissions

60% of the HC’s and almost all of the NOx, CO, and lead come
from the exhaust.
The quantity of emissions changes with the operating
conditions of the vehicle.
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When the car is accelerating the combustion is efficient (low

CO and HC), but high amounts of NOx are produced.

When the car is decelerating there are low amounts of NOx

produced but high amounts of HC’s due to partially burned
fuel.
This makes it difficult to determine how much pollution a
particular engine design produces. The EPA has developed a
standard test to make this determination. The test includes a
cold start, cruising with a simulated load, and a hot start.
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EXHAUST EMISSION
CONTROL TECHNIQUES

• Tuning the engine to burn fuel

efficiently
• Installation of catalytic converters
• Engine modifications
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CATALYTIC CONVERTERS

• Oxidize CO and HC’s to CO2 and H2O

• Most common catalyst - platinum

• Problems:
•Fouled by some gasoline additives like lead
(this is why lead has been eliminated from
gasoline)
•Sulfur in gasoline converted to particulate
SO3
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Limiting Vehicle Emissions

• Catalytic Converter
▫ Platinum-Rhodium catalyst
▫ Accomplishes the following reactions
 Conversion of Nitric Oxide to original reactants
Pt-Rh catalyst
2 NO (g) N2 (g) + O2 (g)

 Conversion of carbon containing gases to CO2 and H2O

(in other words, completing the oxidation!)
Pt-Rh catalyst
2 CO (g) + O2 (g) 2 CO2 (g)
Pt-Rh catalyst
hydrocarbons + O2 (g) CO2 (g) + H2O (g)
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REDESIGN OF INTERNAL
COMBUSTION ENGINES

•Fuel injector
•Cylinder configuration
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QUIZ TIME!!!
1. What are the pollutants of concern that come
from vehicle?
2. How to control exhaust emission?
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Smog
• There are two types of smog:
▫ Industrial
▫ Photochemical
• These pictures are of Los Angeles on a clear day
and on a smoggy day
 Two Types of “Smog”
London Los Angles
Time 1873 1946
Pollutants PM, SO2, H2SO4 HC, NOx, O3, PAN, aldehyde,
ketone
Fuels Coal, fuel oils Gasoline, gas, petroleum
Season Winter Summer & Fall
Temperature Low (<40C) High (240C)
Humidity High Low
Sunlight Weak Strong
O3 conc. Low High
Time of event Day-night cont. Day
Visibility Very low Low (half-mile)
Toxicity Irritate to respiratory Eye, respiratory irritation, O3
damage
Reducing smog Oxidizing smog

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INDUSTRIAL SMOG
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Industrial Smog
• Occurs from oil or coal combustion
• Combustion products contain particulates
(soot, fly ash) with absorbed SO2
▫ SO2 is a main ingredient in industrial smog
▫ Promotes aerosol formation
▫ Characterized by high humidity and low
temperatures.
• In aerosol droplets:
▫ 2SO2(g) + O2(g) ------>2 SO3 (g)
▫ SO3(g) + H2O (l) --- H2SO4 (aq)
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• Sources of SO2
▫ Sulfur containing compounds in coal and oil
▫ Non-ferrous smelters
 Smelters convert metal sores to free metals

- Example: Nickel sulfide ores

- 2NiS(s) + 3O2(g) - 2 NiO (s) + 2SO2 (g)
- Instead of releasing SO2 in form of aerosol
droplets:
- 2SO2(g) +O2(g) --- 2SO3 (g)
- SO3(g) +H2O (l) H2SO4(aq)
- SO2 (g) can be captured, catalytically converted
to SO3 (g) and reacted with water to form
concentrated sulfuric acid

Industrial smog
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Primary and Secondary Pollutants

• Primary Pollutants: Pollutants emitted directly into a
biogeochemical reservoir, such as the atmosphere

• In the case of an industrial smog, SO2 is the primary

pollutant

• In aerosol droplets:
▫ 2SO2(g) + O2(g) -- 2 SO3 (g)
▫ SO3 (g) + H2O (l) -- H2SO4 (aq)

• Secondary Pollutants: Pollutants formed in

biogeochemical reservoir by subsequent chemical
reactions. In this case, sulfur trioxide and sulfuric acid are
secondary pollutants
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Industrial smog
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Photochemical Smog
• Photochemical smog: the primary pollutants of
nitrogen oxides (NOx) and gaseous hydrocarbons
interact in the presence of sunlight, oxygen, and
water vapor to form a hazy cloud, which is a
collection of secondary pollutants
 FORMATION OF
PHOTOCHEMICAL
SMOG
Nature of Photochemical Smog

Species Polluted Area Unpolluted Air

(g/m3) (g/m3)
CO 10,000-30,000 <200
NO 100-400 <20
HC (excluding CH4) 600-3,000 <300
O3 50-150 <5
PANs 50-250 <5
Most values are estimates based on data in Air Quality in Ontario 1991,
Environment Ontario, Queen’s Printer for Ontario; 1992

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Photochemical smog
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MAIN COMPONENTS OF
PHOTOCHEMICAL SMOG FORMATION.
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Photochemical Smog
 Photochemical smog is a type of air pollution produced
when sunlight acts upon motor vehicle exhaust gases
to form harmful substances such as ozone (O3),
aldehydes and peroxyacetylnitrate (PAN).

 Ozone causes breathing difficulties, headaches, fatigue

and can aggravate respiratory problems.

 The PAN (CH3CO-OO-NO2) in photochemical smog

can irritate the eyes, causing them to water and sting.
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3 Ingredients Required for the Formation

of Photochemical Smog

 UV light (temperatures >18° C )

 Hydrocarbons (VOCs)
 Nitrogen oxides
Photochemical pollution level (Stern et al., 1973)
 PPL = (ROG) (NOx) (Light Intensity) (Temperature)
(Wind Velocity) (Inversion Height)
where
 PPL = photochemical pollution level
 ROG = concentration of reactive organic gases
 NOx = concentration of oxides of nitrogen
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Photochemical Smog
 48

• Early morning traffic increases the emissions of both nitrogen

oxides and VOCs as people drive to work.
• Later in the morning, traffic dies down and the nitrogen oxides
and volatile organic compounds begin to be react, forming
nitrogen dioxide, increasing its concentration.
• As the sunlight becomes more intense later in the day, nitrogen
dioxide is broken down and its by-products form, increasing
concentrations of ozone.
• At the same time, some of the nitrogen dioxide can react with the
volatile organic compounds to produce toxic chemicals such as
PAN.
• As the sun goes down, the production of ozone is halted. The ozone
that remains in the atmosphere is then consumed by several
different reactions.

Photochemical Smog
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• During fuel combustion:

▫ Formation of Nitric Oxide:
N2(g) +O2(g) -2NO(g)
▫ Nitric oxide reacts rapidly with atmospheric
oxygen:
 Formation of Nitrogen oxide:
 2NO(g) +O2(g) -2NO2(g)
▫ Nitric Oxide (NO) and Nitrogen Dioxide (NO2)
are both free radicals:
 Possess unpaired electron
 Unpaired electron makes them reactive
 Not every atom has a complete octet
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Photochemical Smog
 51

Photochemical Smog
 First recognized as a problem in the 1940s
in Los Angeles, CA
 Problem in other cities:
 Mexico city, Brazil, New Delhi, India;
Beijing
 Since 1950s automobile is the leading
contributor to air pollution globally
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Ozone Production
 Motor vehicles produce exhaust gases containing
oxides of nitrogen such as nitrogen dioxide (NO2)
and nitric oxide (NO).
 At the high temperatures of the car's combustion
chamber (cylinder), nitrogen and oxygen from the
air react to form nitric oxide (NO):

N2(g) + O2(g) -----> 2NO(g)

 Some of the nitric oxide (NO) reacts with oxygen to

form nitrogen dioxide (NO2):

2NO(g) + O2(g) -----> 2NO2(g)

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• The mixture of nitric oxide (NO) and

nitrogen dioxide (NO2) is sometimes
referred to as NOx.

• When the nitrogen dioxide (NO2)

concentration is well above clean air levels
and there is plenty of sunlight, then an
oxygen atom splits off from the nitrogen
dioxide molecule:

NO2(g)sunlight-->NO(g)+O(g)
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• This oxygen atom (O) can react with oxygen

molecules (O2) in the air to form ozone (O3):
O + O2 -----> O3
• Nitric oxide can remove ozone by reacting
with it to form nitrogen dioxide (NO2) and
oxygen (O2):
NO(g) + O3(g) -----> NO2(g) + O2(g)
 55

OZONE PRODUCTION
- ratio of NO2 : NO is > 3, the formation of
ozone is the dominant reaction.
- ratio NO2 : NO < 0.3, the nitric oxide reaction
destroys the ozone at about the same rate as it
is formed (ozone concentration below harmful
levels)

The reaction of HCs (unburned petrol) with

nitric oxide and oxygen produce nitrogen
dioxide, also in the presence of sunlight,
increasing the ratio of NO2 : NO
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Peroxyacetylnitrate Production

• Nitrogen dioxide (NO2), oxygen (O2) and

hydrocarbons (unburned petrol) react in
the presence of sunlight to produce
peroxyacetylnitrate (CH3CO-OO-NO2):
NO2(g) + O2(g) + HCs + sunlight ---> CH3CO-OO-NO2(g)
(PAN)
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• Nitrogen Dioxide is corrosive and reacts rapidly with

water vapor
▫ Formation of nitrous acid and nitric acid
2NO2(g) + H2O(g) -HNO2(g) +HNO3(g)
• Nitrogen dioxide also forms ozone
▫ Sunlight necessary to supply enough energy to break
one of the nitrogen-oxygen bonds
NO2 NO+O
O+O2O3
• Atomic oxygen also generates the hydroxyl radical by
reacting with atmospheric water vapor
▫ O(g) + H2O (g) 2OH(g)
• Ozone (oxidant) concentration doesn’t increase until
most of NO is converted to NO2. This is due to the
following competing atmospheric chemical reaction:
▫ NO+O3 NO2 +O2
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VOLATILE ORGANIC COMPOUND (VOC)

• The presence of hydrocarbons and hydrocarbon-like
organic compounds called volatile organic compounds
(VOCs) correspond to the Non-Methane hydrocarbons

• Sources of VOCs:
▫ Anthropogenic sources:
 Gasoline pumps
 Cold starts leading to incomplete combustion
▫ Natural sources:
 Trees, plants

• Most reactive VOCs have double bonds

▫ Benzene, toluene
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Several meteorological factors can influence the

formation of photochemical smog. These conditions
include:

• Precipitation can alleviate photochemical smog as the pollutants

are washed out of the atmosphere with the rainfall.
• Winds can blow photochemical smog away replacing it with fresh
air. However, problems may arise in distant areas that receive the
pollution.
• Topography is important factor influencing how severe a smog
event can become. Communities situated in valleys are more
susceptible to photochemical smog because:
- hills and mountains surrounding them tend to reduce the air flow,
allowing for pollutant concentrations to rise.
- valleys are sensitive to photochemical smog because relatively
strong temperature inversions
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• Temperature inversions

- Normally, during the day the air near the surface is heated and as it
warms it rises, carrying the pollutants with it to higher elevations.
- However, if a temperature inversion develops, pollutants can be
trapped near the Earth's surface.
- Temperature inversions cause the reduction of atmospheric mixing
and therefore reduce the vertical dispersion of pollutants.
- Inversions can last from a few days to several weeks.
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FORMATION OF THERMAL INVERSION

 63

REACTION CYCLES INVOLVING ORGANIC OXIDATION

OF NO2 WITH OZONE BUILDUP

O2 + O  O3

Oxygen
Ozone
+O2 Atom
O3
O
O3 + NO  NO2 + O2

Nitrogen
Dioxide +Light
NO2
NO2 + h  NO +
NO + RO2  NO2 + O
RO
Nitric
Oxide
NO
 64

Photochemical Smog - conclusion

Initiated by sunlight

1st step – photochemical

cleavage of NO2  NO
and O

Yellow brown haze reduces

visibility
Irritating substances
(respiratory tract and eye
watering)
Four conditions – NOx,
sunlight, HC temperatures
above 18 degree Celsius.
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1. Differentiate between industrial smog and

photochemical smog.
2. State 2 effects of photochemical smog to human.
3. Answer following questions based on graph at slide 44
a) Why does the atmospheric concentration of non-
methane hydrocarbons peak at 8:00 a.m., and then
decrease throughout the day?
b) Why does the atmospheric concentration of
aldehydes peak at 1:00 p.m., and then decrease
throughout the afternoon?
c) Why does the atmospheric concentration of oxidants
(PAN) peak at 3:00 p.m.?