12-02-2020

EV20001: ENVIRONMENTAL SCIENCE

Lecture #4

Understanding Air Pollution

Dr. Shamik Chowdhury

School of Environmental Science and Engineering
E-mail: [email protected]

12 February 2020

Air pollutants
 Any substance found in the ambient air that is not part of its natural composition
or any substance whose concentration is higher than the concentration found in
the air’s natural composition.

 Air pollutants come from natural activities, such as volcanic eruptions, or human
activities, such as burning of fossil fuels.

 Can be in the following two physical forms:

‒ particulate matter (e.g., ash, dust, smoke, etc.)

‒ gases (e.g., sulfur dioxide, carbon monoxide, etc.)

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Classification of air pollutants

 Primary pollutants

‒ Found in the atmosphere in the same chemical form as when it was

emitted from its source.

‒ Example: carbon monoxide, nitric oxide, nitrous oxide, hydrogen sulfide,

sulfur dioxide, halogen compounds such as chlorides, fluorides,
bromides, particulate matter.

 Secondary pollutants

‒ Not directly emitted into the atmosphere but formed in the air as a result
of chemical transformation of other primary pollutants.

‒ Example: nitrogen dioxide formed from nitric oxide, ozone formed from
photochemical reactions of nitrogen oxides and volatile organic
compounds, sulfuric acid droplets formed from sulfur dioxide.

Sources of air pollutants

 Human inputs of air pollutants come from mobile sources (such as cars) and stationary
sources (such as industrial and power plants).

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Anthropogenic sources of air pollution

Example 4.1: CO2 emissions from coal combustion

Calculate the CO2 emissions from bituminous coal on the basis of emissions per unit
of energy released, assuming that the coal contains 67% C by weight with an
energy content of 28,400 kJ/kg.

Solution:

The overall reaction is the oxidation of carbon to CO2, where air is the usual source
of O2.

C + O 2  CO 2

Thus, 12 g of C produces 44 g of CO2.

Because the coal contains 67% C by weight, there is 670 g of C in 1 kg of coal.

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Thus, 1 kg of coal produces

 44 g CO 2   1kg 
 CO 2 coal  (670 g C)   
 12 g C   1000 g 

 2.46 kg CO 2 / kg coal burned

Each kg of coal burned releases 28,400 kJ of energy. Hence, CO2 emitted per unit
of fuel energy is given by

2.46 kg CO 2 / kg coal
 CO 2 coal   8.66 ×10 -5 kg CO 2 / kJ fuel energy
28, 400 kJ / kg coal

Example 4.2: SO2 emissions from a coal-fired power plant

A 500 MW power plant burns 2  108 kg coal per year. Calculate the annual
emission of SO2 from the power plant, assuming that the coal contains 1.5% sulfur
by weight and that 97% of the sulfur is converted to SO2.

Solution:

The relevant chemical reaction is

S + O 2  SO 2
Thus, 32 g of S produces 64 g of SO2.

The mass ratio of SO2 to S is therefore

Mass SO 2 64 g
= =2
Mass S 32 g

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Because the power plant burns 2  108 kg coal per year, the total mass of S
entering the plant is

msulfur = (0.015)  2 × 10 8 kg / year  = 3 × 10 6

kg / year

Of this, 97% is converted to SO2.

The total annual mass of SO2 is therefore

 kg SO 2 
mSO 2  (0.97) (3  10 6 kg S / year)  2 
 kg S 

 5.82 × 10 6 kg SO 2 / year

Example 4.3: NOX emissions from a coal-fired power plant

Assume that the power plant in Example 4.2 emits NOX at a rate of 0.260 g NO2/MJ
of fuel energy input to the plant. Estimate the total amount of NOX emitted per year
by this power plant if the annual energy input is 5.68  109 kJ.

Solution:
Annual energy input = 5.68  109 kJ/year

Thus, the annual mass of NOX emitted is

 g NO 2   kJ   1 kg   1 MJ 
mNO X   0.260   5.68 × 10
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  
 MJ   year   1000 g   1000 kJ 
 1.48 × 10 3 kg NO 2 / year
Note: Although NOX consists of a mixture of NO and NO2, the total mass is expressed as
equivalent NO2 because NO2 is the criteria air pollutant.

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Example 4.4: Particulate emissions from a coal-fired power plant

If the ash content of the coal in Example 4.2 is 9.8% by weight, calculate the annual
atmospheric emissions of particulate matter (PM) from the power plant assuming
that 80% of the ash in the coal is entrained in the combustion exhaust gas, while the
remaining 20% (called bottom ash) is collected as a solid waste at the combustor.

Solution:

Because the power plant burns 2  108 kg coal per year, the total mass of ash
entering the plant is

mash = (0.098)  2 × 108 kg / year  = 1.96 × 10 7 kg ash / year

Thus, the annual atmospheric emissions of PM

mPM = (0.80) 1.96 × 10 7 kg / year  = 1.57 × 10 7 kg PM / year

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Clean Air Act

 The Environmental Protection Agency (EPA) was created in December 1970 in the United
States to address the Nation’s environmental problems. In the same year the Clean Air
Act (CAA) was passed to safeguard public health.

 The CAA is the comprehensive federal law that regulates air emissions from stationary
and mobile sources.

 It authorizes the EPA to set standards to protect public health and public welfare and to
regulate emissions of hazardous air pollutants.

 The CAA is one of the United States’ first and most influential modern environmental laws,
and one of the most comprehensive air quality laws in the world.

 Numerous countries around the globe have enacted similar legislation to achieve healthy
air quality.

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Criteria pollutants
 A group of six common air pollutants that are the most prevalent and the most
harmful to human health and the environment.

 Harmful to humans if concentration in ambient air is above certain levels.

 In the United States, the National Ambient Air Quality Standards (NAAQS) sets
limits for each pollutant based on health and welfare standards.

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Criteria pollutants
 NAAQS have been established for the following six ‘criteria pollutants’.

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Criteria pollutants
 Primary standards provide public health protection, including protecting the health of
"sensitive" populations such as asthmatics, children, and the elderly.

 Secondary standards provide public welfare protection, including protection against

decreased visibility and damage to animals, crops, vegetation, and buildings.

 As long as the concentration of the pollutants remain below the secondary standards,
crops, buildings, etc. will not likely be damaged.

 Primary and secondary emission standards have been established for each criteria
pollutant, except carbon monoxide.

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Carbon monoxide (CO)

 Description: Colorless, odorless gas; forms during incomplete combustion of carbon-containing
fuels.

 Major human sources: Cigarette smoking, incomplete burning of fossil fuels. About 77% (95% in
cities) comes from motor vehicle exhaust.

 Health effects: Reacts with hemoglobin in red blood cells and reduced the ability of blood to
bring oxygen to body cells and tissues. This impairs perception and thinking; slows reflexes;
causes headaches, drowsiness, dizziness, and nausea; can trigger heart attacks and angina;
damages the development of fetuses and young children; and aggravates chronic bronchitis,
emphysema, and anemia. At high levels, it causes collapse, coma, irreversible brain cell damage,
and death.

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Nitrogen dioxide (NO2)

 Description: Reddish brown irritating gas; can be converted to nitric acid (HNO3), a major
component of acid deposition.

 Major human sources: Fossil fuel burning in motor vehicles (49%), and power plants and
industries (46%).

 Health effects: Lung irritation and damage; aggravates asthma and chronic bronchitis;
increases susceptibility to respiratory infections such as the flu and common colds
(especially in young children and older adults).

 Environmental effects: Reduces visibility; acid deposition of HNO3 can damage trees,
soils, and aquatic life in lakes.

 Property damage: HNO3 can corrode metals and eat away stone on buildings; statues,
and monuments; NO2 can damage fabrics.

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Sulfur dioxide (SO2)

 Description: Colorless, irritating; forms mostly from the combustion of sulfur containing
fossil fuels such as coal and oil; in the atmosphere can be converted to sulfuric acid
(H2SO4), a major component of acid deposition.

 Major human sources: Coal burning in power plants (88%) and industrial processes
(10%).

 Health effects: Breathing problems for healthy people; restriction of airways in people with
asthma; chronic exposure can cause a permanent condition similar to bronchitis.

 Environmental effects: Reduces visibility; acid deposition of H2SO4 can damage trees,
soils, and aquatic life in lakes.

 Property damage: SO2 and H2SO4 can corrode metals and eat away stone on buildings;
statues, and monuments; SO2 can damage paint, paper and leather.

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Particulate matter (PM)

 Description: Variety of particles and droplets (aerosols) small and light enough to remain
suspended in the atmosphere for short periods (large particles) to long periods (small
particles); cause smoke, dust and haze.

 Major human sources: Burning coal in power and industrial plants (40%), burning diesel
and other fuels in vehicles (17%), agriculture (plowing, burning off fields), unpaved roads,
construction.

 Health effects: Nose and throat irritation, lung damage, and bronchitis; aggravates
bronchitis and asthma; shortens life; toxic particulates (such as lead, cadmium and dioxins)
can cause mutations, reproductive problems, cancer.

 Environmental effects: Reduces visibility; acid deposition of H2SO4 droplets can damage
trees, soils, and aquatic life in water bodies.

 Property damage: Corrodes metal; soils and discolors buildings, clothes, fabrics and
paints.

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 The degree of damage of PM depends on the size of PM, number of

particles inhaled, and the general health of the person who inhaled.

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 Larger particles may be trapped in the nose or eliminated through

coughing and sneezing. Fine particles can penetrate deep into the
lungs, and ultrafine particles may even enter the blood stream. These
particles can carry toxic chemicals which are linked to cancer.

Phagocytosis by alveolar macrophages

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Ground level ozone

 Description: Highly reactive, irritating gas with an unpleasant odor that forms in the
troposphere as a major component of photochemical smog.

 Major human sources: Chemical reaction with volatile organic compounds (VOCs, emitted
mostly by cars and industries) and nitrogen oxides to form photochemical smog.

 Health effects: Breathing problems; coughing; eye, nose, and throat irritation; aggravates
chronic diseases such as asthma, bronchitis, emphysema, and heart disease; reduces
resistance to colds and pneumonia; may speed up lung tissue aging.

 Environmental effects: Ozone can cause more damage to plants than any other
pollutants; smog can reduce visibility.

 Property damage: Damages rubber, fabrics, and paints.

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Lead (Pb)
 Description: Solid toxic metal and its compounds, emitted into the atmosphere to
particulate matter.

 Major human sources: Paint (old houses), smelters (metal refineries), lead manufacture,
storage batteries, leaded gasoline (being phased out in developed countries).

 Health effects: Accumulates in the body; brain and other nervous system damage and
mental retardation (especially in children); digestive and other health problems; some lead-
containing chemicals can cause cancer.

 Environmental effects: Can harm wildlife.

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Air quality index

 The air quality index (AQI) is an index for reporting air quality on a daily basis.

 It is a measure of how air pollution affects one's health within a short time period.

 The AQI is based on measurement of PM2.5 and PM10, O3, NO2, SO2 and CO emissions.

 Every day, monitors record concentrations of the major pollutants. These raw
measurements are converted into a separate AQI value for each pollutant PM2.5 and PM10,
O3, NO2, SO2 and CO) using standard formulae developed by the US EPA.

 The purpose of the AQI is to help people know how the local air quality impacts their health.
It quickly disseminates air quality information in real-time.

 The higher the AQI value, the greater the level of air pollution and the greater the health
concerns.

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Environmental impacts

Local Impact

Regional Impact

+
Global Impact

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Photochemical Smog
(Local Impact)

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Ozone in the atmosphere

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Bad ozone
 Ground level or “bad” ozone is not emitted directly into the atmosphere but is
created by chemical reactions of oxides of nitrogen (NOX) and volatile organic
compounds (VOCs) in the presence of sunlight.

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Bad ozone makes photochemical smog

 Noxious mixture of pollutants (mostly ozone, aldehydes, and peroxyacetyl nitrate) formed
when NOX, VOCs, and hydrocarbons, mainly from motor vehicle and industrial emissions,
react in presence of sunlight, creating a reddish brown haze above cities.

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Bad ozone makes photochemical smog

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Effect of photochemical smog on plants

 Ground level ozone causes more damage to plants than all other air pollutants combined.

 Ozone enters leaves through stomata during normal gas exchange. As a strong oxidant,
ozone causes several types of symptoms including chlorosis and necrosis.

 High concentrations of ozone cause plants to close their stomata, slowing down
photosynthesis.

 Prolonged ozone exposure reduces health and productivity of crops.

 High ozone concentrations can also affect soil fertility. Plants that are exposed to high
ozone concentrations metabolize less carbon dioxide, so less carbon is available in the
soil, and fewer soil microbes grow and thrive.

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Effect of photochemical smog on humans

 Ozone air pollution causes over 150 thousand premature deaths every year, and millions
more chronic diseases, particularly in children and the elderly.

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Preventing photochemical smog

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NOX control: Selective catalytic reduction

 Selective catalytic reduction (SCR) is an advanced NOX emissions control technology that
injects a liquid-reductant agent through a special catalyst into the exhaust stream of a diesel
engine. The reductant source is usually automotive-grade urea, otherwise known as diesel
exhaust fluid (DEF). The DEF sets off a chemical reaction that converts NOX into nitrogen
and water, which is then expelled through the vehicle tailpipe.

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If you own a car or plan to have one, what incentives, if any,

would encourage you to rely less on the automobile and to
travel to school or work by bicycle, on foot, by mass transit,
or by electric scooter?

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Acid Deposition
(Regional Impact)

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Acid deposition (acid rain)

 The accumulation of acids or acidic compounds on land, in water, or in the tissues of
vegetation, as a result of acid precipitation or of the settling or absorption of such
compounds directly from the atmosphere.

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Acid deposition is a regional problem

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Chemistry of acid deposition

 Both sulfur dioxide and nitrogen dioxide are acidic oxides and react with water to form
acids.

 Sulfur dioxide reacts with water to form sulfurous acid.

SO2 (g) + H2O (l) → H2SO3 (aq)

 Substances in the upper atmosphere then catalyse the reaction between sulfurous acid
and oxygen to form sulfuric acid.

2H2SO3 (aq) + O2 (g) → 2H2SO4 (aq)

 Similarly, nitrogen dioxide reacts with moisture to form a mixture of nitric acid and nitrous
acid.

2NO2 (g) + H2O (g) → HNO3 (aq) + HNO2 (aq)

 Substances in the atmosphere then catalyse the reaction between nitrous acid and oxygen
causing the formation of more nitric acid.

2HNO2 (aq) + O2 (g) → 2HNO3 (aq)

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Effect of acid rain on terrestrial ecosystems

 Acid rain causes demineralization of soil. Base cations like Ca2+, Mg2+, Na+, and K+ are
leached away and replaced by acid cations such as H+, Al3+ ions.

 Nitrogen fixation ability of nitrifying bacteria diminishes rapidly below pH 6.

 Acidification of soil adversely affects soil fauna and lead to reduced forest productivity.

 Acid rain also retards the growth of vegetables, such as pea, beans, raddish, spinach, etc.

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Effect of acid rain on aquatic ecosystems

 Many bacteria and blue green algae are killed due to acidification, disrupting the whole
ecological balance.

 Acidic water can also leach aluminium from the soil. This runoff carry dissolved aluminium to
lakes, rivers and streams causing massive fish death by clogging their gills and thus them
depriving of oxygen.

 Fresh water lakes are fairly alkaline with Ca2+ and Mg2+ and HCO3– as the dominant ions.
Phytoplankton and zooplankton are affected by acidity of water.

 Snails, clams, oysters etc. having their shells of calcium carbonate are among the first animals
to die in acidic lakes.

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 Acid rain is responsible for the destruction of thousands of lakes

and streams in the United States, Canada and parts of Europe.

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Effect of acid rain on vegetation

 Acid rain does not kill trees directly. Instead, it weaken trees by damaging their leaves,
limiting the nutrients available to them, or exposing them to toxic substances slowly
released from the soil. Quite often, injury or death of trees is a result of these effects of
acid rain in combination with one or more additional threats.

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 Acid rain increases the concentration of Al3+ in groundwater, thereby

adversely affecting plant growth. Large sections of established
forests have been severely damaged in many areas of the eastern
United States.

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Effect of acid rain on architecture

 Acid rain causes extensive damage to monuments and stone sculptures of marble,
limestone, slate etc. The damage caused to rocks and marble by acid rain is called as
marble-leprosy or stone-leprosy.

CaCO3 + H2SO4 → CaSO4 + H2O + CO2

 Acid rain corrodes houses, buildings, bridges, fences and railing that require huge cost for
maintenance every year.

Cu + H2SO4 → CuSO4 + H2

Zn + H2SO4 → ZnSO4 + H2

 Acid precipitation causes damage to steel, oil based paints and automobile coatings. It
also disintegrates textile, paper etc.

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 The shiny white marble facade of the Taj Mahal, one of the seven
wonders of the modern world, is turning yellow due to acid rain.

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Effect of acid rain on humans

 Acid rain does not directly affect human health.

 The acid in the rainwater is too dilute to have direct adverse effects.

 The particulates responsible for acid rain (sulfur dioxide and nitrogen oxides), however,
effect the human nervous system, respiratory system and digestive system.

 Acidification of drinking water reservoirs and concurrent increase in heavy metal

concentration can have serious health effects.

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Preventing acid deposition

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SO2 control: Flue gas desulfurization

 Flue gas desulfurization (FGD) technology employs a slurry of pulverized limestone
mixed with water to remove SO2 from the combustion exhaust gas of power plants via
chemical reactions that take place in a vessel commonly known as scrubber.

CaCO3 + H2O SO2 + (CaCO3 +

2H2O) + 1/2O2 →
CaCO3 + H2O
CO2 + (CaSO4.2H2O)

CaSO4.2H2O

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Example 4.5: SO2 removal with an FGD system

The power plant described in Example 4.2 decides to install a wet limestone FGD
system to reduce its current SO2 emissions by 95%. The FGD system requires a
reagent stoichiometry of 1.03 (i.e., 3% more limestone than theoretically needed to
remove a mole of SO2). Calculate (a) the new annual SO2 emissions and (b) the
annual quantity of limestone required by this power plant.

Solution:

(a) From Example 4.2, the current SO2 emissions are 5.82  106 kg/year. The FGD
system will reduce SO2 emissions by 95%. Thus, the new emissions will be 5%
of the current value.

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SO 2 removed = (0.95)  5.82 × 10 6 kg / year 

= 5.53 × 106 kg / year

SO 2 emissions with FGD = (0.05)  5.82 × 10 6 kg / year 

 2.91 × 105 kg / year

(b) SO2 is removed according to the following reaction:

1
SO 2  (CaCO 3 + 2H 2 O)  O 2  CO 2  (CaSO 4 .2H 2 O)
2
The theoretical reagent requirement is 1.00 mol Ca/mol SO2 removed.
However, the actual requirement is 1.03 mol Ca/mol SO2 removed.

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Thus a stoichiometric ratio of 1.03 corresponds to a mass ratio of

m CaCO 3  mol Ca   100 g CaCO 3 / mol Ca 

=  1.03  
mSO 2  mol SO 2   64 g SO 2 / mol SO 2 

g CaCO 3 kg CaCO 3
= 1.6094  1.6094
g SO 2 removed kg SO 2 removed

The annual mass of limestone required is thus

m CaCO 3 = (1.6094) (5.82  10 6 )  9.37 × 10 6 kg CaCO 3 / year

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Preventing outdoor air pollution

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Ozone Depletion
(Global Impact)

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Ozone depletion
 Gradual thinning of Earth’s ozone layer caused by the release of certain chemical
compounds from industry and other human activity that contain gaseous chlorine.

 Chlorofluorocarbons (CFCs) and other halogenated ozone depleting substances (ODS)

such as hydrochlorofluorcarbons (HCFCs), halons, methyl chloroform and carbon
tetrachloride are mainly responsible for man-made chemical ozone depletion.

 Dramatic loss of ozone in the lower stratosphere was first noticed in the early 1970s. The
thinning was most pronounced in the polar regions, especially over Antarctica and has
been called ozone hole.

 Ozone depletion is a major environmental problem because it increases the amount of

ultraviolet (UV) radiation that reaches Earth’s surface, increasing the rate of skin cancer,
eye cataracts, and genetic and immune system damage.

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Ozone depletion
 Satellites observed the largest ozone hole over Antarctica in September, 2006. The center
of this image shows a large area where the concentration of ozone decreased by 50% or
more.

24 September 2006

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Stratospheric ozone depletion

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Ozone hole is a springtime phenomenon

 The ozone hole is not technically a “hole” where no ozone is present, but is actually a
region of exceptionally depleted ozone in the stratosphere over the Antarctic that happens
at the beginning of Southern Hemisphere spring (August–October).

 The hole forms in the Antarctic because cold air is trapped as a result of the polar vortex
― strong, circulating winds.

 The cold temperatures allow the formation of polar stratospheric clouds (PSCs), or ice
clouds.

 These PSCs are conducive to the breakdown of chlorine-containing compounds, which

are there because of our production of CFCs. This makes the area especially susceptible
to ozone depletion.

 When the sun hits the PSCs in early spring, large amounts of chlorine are formed from
CFCs and ODS.

 Fortunately, by early summer, ozone from other areas comes in to help fill this hole.
However, due to continued CFC production, the hole returns next year.

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Environmental effects of ozone depletion

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Reversing ozone depletion

 The Montreal Protocol on ‘Substances that deplete the ozone layer’ is a landmark
international agreement designed to protect the stratospheric ozone layer.

 The treaty was originally signed in 1987 and substantially amended in 1990 and 1992.

 The Montreal Protocol stipulates that the production and consumption of compounds that
deplete ozone in the stratosphere are to be phased out by 2000.

 The Montreal Protocol has, contributed to a significant drop in total global production and
consumption of ozone depleting substances used in agricultural, consumer and industrial
sectors around the world.

 It has also generated climate benefits as some of these substances are greenhouse
gases, too.

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Reversing ozone depletion

 The Montreal Protocol has been keeping our planet cool for years by phasing out ozone-
depleting substances that are also potent global-warming gases.

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Recovery stages of global ozone

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If you were a sustainability expert representing the needs of

your community to local government, what changes would
you propose to reduce air pollution?

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Indoor Air Pollution

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Indoor air pollution

 Indoor air contains higher concentrations of pollutants than outdoor air.

 Indoor air pollution usually is a greater threat to human health than outdoor air pollution.

 Developed countries – chemicals used in building materials and products.

 According to the US Environmental Protection Agency (EPA), four most dangerous indoor air
pollutants in developed countries include tobacco smoke, formaldehyde, radioactive radon-222
gas and very small (ultrafine) particles.

 Less-developed countries – indoor burning of wood, charcoal, dung, crop residues, coal, and
other fuels in open fires.

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Important indoor air pollutants

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Preventing indoor air pollution

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Preventing air pollution

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Why our exposure to indoor air pollutants has increased

over the past several decades?

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