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LECTURE 3

URBAN AIR POLLUTION

What is urbanization?
Urbanization is a process of relative growth in a countrys urban population accompanied by an even faster increase in the economic, political and cultural importance cities relative to rural area.

Urban air

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.

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.

POLLUTANTS FORMATION IN COMBUSTION PROCESSES

NOX FORMATION

Basically under three mechanisms:


Thermal Fuel Prompt

Thermal
Produced by the reaction of atmospheric oxygen and nitrogen at elevated temperatures. The reactions are described as follows:

N2 + O = NO + N N + O2 = NO + O N + OH = NO + H

Fuel NOx

NOX FORMATION

From the reaction of the organically bound nitrogen in the fuel with oxygen. The process is complex but can be simply expressed as follows:
Fuel-N
thermal decomposition

N-intermediates (HCN, NH , N, CN)


oxidation

N-intermediates + O2

NOx

Prompt NOx

NOX FORMATION

Formed by the reaction of hydrocarbon radicals with 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
N + O2 HCN + OH CN + O2

HCN + N
NO + O CN + H2O NO + CO

COX FORMATION

The combustion of methane gas (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 + HO2-

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SOX FORMATION

SO2 is almost exclusively formed during the combustion of fossil fuels with relevant sulfur content (coal)
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 citizens 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.

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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.

CONTROL OF POLLUTION FROM AUTOMOBILES


Important points requiring control:

Evaporation loss from fuel tank

Evaporation of HCs from carburetor Emission of unburned gas and partially oxidized HCs from crankcase NOx. HCs, and CO in the exhaust

CONTROL OF THE POTENTIAL EMISSION POINTS


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.

Crankcase emissions have been eliminated by recycling crankcase gases into the intake manifold and the installation of the positive crankcase ventilation valve (PCV).

The toxicity of emission from exhaust can be reduced by applying the catalytic converter.

Exhaust Emissions
60% of the HCs 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.

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 HCs 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.

EXHAUST EMISSION CONTROL TECHNIQUES


Tuning the engine to burn fuel efficiently Installation of catalytic reactors Engine modifications

Engine Tuning

A well tuned engine is the first line of defense for controlling automobile emissions

CATALYTIC CONVERTERS
Oxidize CO and HCs 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

Limiting Vehicle Emissions


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

Conversion of carbon containing gases to CO2 and H2O (in other words, completing the oxidation!) 2 CO (g) + O2 (g) Pt-Rh catalyst 2 CO2 (g) CO2 (g) + H2O (g)

hydrocarbons + O2 (g)

Pt-Rh catalyst

REDESIGN OF INTERNAL COMBUSTION ENGINES


Fuel injector Cylinder configuration

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
Time Pollutants Fuels Season Temperature Humidity Sunlight O3 conc. Time of event Visibility Toxicity 1873 PM, SO2, H2SO4 Coal, fuel oils Winter Low (<40C) High Weak Low Day-night cont. Very low Irritate to respiratory

Los Angles
1946 HC, NOx, O3, PAN, aldehyde, ketone Gasoline, gas, petroleum Summer & Fall High (240C) Low Strong High Day Low (half-mile) Eye, respiratory irritation, O3 damage

Reducing smog

Oxidizing smog

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INDUSTRIAL SMOG

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)

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

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

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

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FORMATION OF PHOTOCHEMICAL SMOG

Nature of Photochemical Smog


Species CO NO HC (excluding CH4) O3 PANs Polluted Area Unpolluted Air (g/m3) (g/m3) 10,000-30,000 100-400 600-3,000 50-150 50-250 <200 <20 <300 <5 <5

Most values are estimates based on data in Air Quality in Ontario 1991, Environment Ontario, Queens Printer for Ontario; 1992

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Photochemical smog

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.

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

Photochemical Smog

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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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Photochemical Smog
Why does the atmospheric concentration of nonmethane hydrocarbons peak at 8:00 a.m., and then decrease throughout the day? Why does the atmospheric concentration of aldehydes peak at 1:00 p.m., and then decrease throughout the afternoon? Why does the atmospheric concentration of oxidants (PAN) peak at 3:00 p.m.?

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

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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)

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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)

Nitrogen Dioxide is corrosive and reacts rapidly with water vapor

Nitrogen dioxide also forms ozone

Formation of nitrous acid and nitric acid 2NO2(g) + H2O(g) -HNO2(g) +HNO3(g)

Atomic oxygen also generates the hydroxyl radical by reacting with atmospheric water vapor Ozone (oxidant) concentration doesnt increase until most of NO is converted to NO2. This is due to the following competing atmospheric chemical reaction:
NO+O3 NO2 +O2
O(g) + H2O (g) 2OH(g)

Sunlight necessary to supply enough energy to break one of the nitrogen-oxygen bonds NO2 NO+O O+O2O3

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

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REACTION CYCLES INVOLVING ORGANIC OXIDATION OF NO2 WITH OZONE BUILDUP


O2 + O O3

Ozone O3
O3 + NO NO2 + O2

+O2

Oxygen Atom O

Nitrogen Dioxide NO2


NO + RO2 NO2 + RO

+Light NO2 + h NO + O

Nitric Oxide NO

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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.