Mekdela Amba university

College of Natural and Computational Sciences

Departments of Chemistry

Environmental chemistry power point

Set by: Mequanintie.G

March ,2023
4/14/2023 Environmental chemistry 1
 CHAPTER -THREE
ATMOSPHERIC CHEMISTRY AND AIR POLLUTION

 Atmospheric chemistry: is a branch of atmospheric science in which the chemistry of the Earth’s
atmosphere and that of other planets is studied.

 Atmospheric science deals with the movement of air masses in the atmosphere, atmospheric heat
balance, and atmospheric chemical composition and reactions.

 The atmosphere is a protective blanket which nurtures life on Earth and protects it from the hostile
environment of outer space.

 Atmosphere is a thin layer of mixed gases covering the earth’s surface.

 The atmosphere is layered in to four distinct zones of contrasting temperature due to differential
absorption of solar energy.
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 Importance and physical characteristics of the atmosphere

 Some importance of the atmosphere are:

 Atmosphere is the source of carbon dioxide for plant photosynthesis and of oxygen for respiration.
 It provides the nitrogen that nitrogen-fixing bacteria and ammonia manufacturing plants use to
produce chemically-bound nitrogen, which is an essential component of life molecules.
 The atmosphere transports water from the oceans to land, thus acting as the condenser in a vast solar-
powered still.
 The atmosphere plays a vital role in the survival of life on earth by absorbing most of the harmful
cosmic rays from outer space and most of the electromagnetic radiation from the sun.
 By reabsorbing much of the infrared radiations re-emitted by the earth to space, the atmosphere
stabilizes the earth’s temperature, preventing temperature extremes.

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 Physical Characteristics of the Atmosphere
 The components of our Earth’s atmosphere may be divided broadly as major, minor and trace
constituents.
 For pollution-free dry air at ground level, the components may be expressed as percent by volume.
 The density of the atmosphere decreases sharply with increasing altitude as a consequence of the gas
laws and gravity.
 The characteristics of the atmosphere vary greatly, with altitude, time (season), location (latitude),
and even solar activity.
 Temperature in the atmosphere may vary from as low as the -92° C to over 1200° C.
 Atmospheric pressure drops from 1 atm. at sea level to 3.0 × 10−7 atm. at 100 km above sea level.
 Dry air within several kilometers of ground level consists of two major components ,Nitrogen(78%)
and oxygen (20.95%) and two minor components, argon (0.934%) and carbon dioxide (0.036%).
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 The four atmospheric layers are: Troposphere, stratosphere, mesosphere, and thermosphere

Troposphere

The lowest region of atmosphere in which the human beings along with other organisms live is called
troposphere.

The lowest layer of the atmosphere extending from sea level to an altitude of 10-16 km is the
troposphere.

Troposphere is a turbulent, dusty zone containing air, much water vapour and clouds.

This is the region of strong air movement and cloud formation.

In this region the composition of the atmosphere is more or less uniform in the absence of air
pollution mainly due to the constant circulation of air masses in this region.

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o However air is far from uniform with respect to density and temperature in this region.

o Density decreases exponentially with increasing altitude.

o Due to the force of gravity and the compressibility of gases, the troposphere contains about 80% of
the total mass of the atmosphere .

o Air temperature drops rapidly with increasing altitude in this layer, reaching about -600 ℃ at the top
of the troposphere .

o A sudden reversal of this temperature gradient creates a sharp boundary, the tropopause, that limits
mixing between the troposphere and the upper zones.

o The very cold layer at the top of troposphere is known as tropopause.

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Other characteristics of troposphere

 All life activities occur in this zone

 Contains water vapor, gases and dust

 The residence time of particle in the troposphere is short due to rain (ppt), gravity, air movement

 Mixing time is rapid due to wind or turbulence

 The water content also varies because of cloud formation, precipitation, and evaporation of water
from terrestrial water bodies.

 Its low temperature and resulting condensation of water to ice particles prevents water from
reaching altitudes at which it would photodissociate through the action of intense UV light.

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 Stratosphere

o The atmospheric layer directly above the troposphere between 10 and 50 km above sea level is
called the stratosphere

o The stratosphere extends from the tropopause up to about 50 km.

o Air temperature in this zone is stable or even increases with higher altitude.

o Although more dilute than the troposphere, the stratosphere has a very similar composition except
two important components: water and ozone.

o The fractional volume of water vapor is about one hundred times lower, and ozone is nearly one
thousand times higher than in the troposphere.

o Ozone is produced by lighting and irradiation of oxygen molecules and would not be present if
photosynthetic organisms were not releasing oxygen.
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o Ozone protects life on the earth surface by absorbing most incoming solar ultra violet radiation

o In this layer the temperature increases with increase in altitude, with a maximum of -2° C at the
upper limit of stratosphere.

o This temperature increase is due to absorption of solar ultraviolet energy by ozone (O3) in
the stratosphere.

o The heating effect is caused by the absorption of ultraviolet radiation energy by ozone.

 If the level of stratospheric ozone concentration decreases, we would be exposed to increasing

amount of dangerous UV rays, resulting in:

 Higher rate of skin cancer , Problem with eyes (Cataract, conjunctivitis etc.), Genetic mutations .
Crop failures & Disruption of important living organisms.

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 Other characteristics of stratosphere

 Contain no water vapor and dust

 Amount of ozone vary depending on location and season of the year.

Ozone concentration are lowest above the equator, increasing towards the poles, they also

increased markedly between autumn and spring.

.
 Mixing time is lower.

 Pollution entering in this region tends to remain long time due to low mixing.

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 Mesosphere
 Above the stratosphere, the temperature diminishes again creating the mesosphere, or the middle
layer.

 The mesosphere on the top of the stratosphere extends roughly to50-85 km

 The absence of high levels of radiation absorbing species in the mesosphere immediately above the
stratosphere results in a further temperature decrease to about – 92°C at an altitude around 85 km.

 In this region the temperature falls with increase in altitude, resulting in a temperature decrease to
about -90° C.

 This is due to the absence of high levels of radiation absorbing species, particularly ozone.

 The principal chemical species in this region are O2+ and NO+.
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 The upper atmosphere is characterized by the presence of significant levels of electrons and positive
ions.
 Temperatures decrease as altitude increases.
 This is due to the absence of high levels of radiation absorbing species, particularly ozone.
 Because of the rarefied conditions, these ions may exist in the upper atmosphere for long periods
before recombining to form neutral species.
 At altitudes of approximately 50 km and up, ions are so prevalent that the region is called the
ionosphere.
 Ultraviolet light is the primary producer of ions in the ionosphere.
 In darkness, the positive ions slowly recombine with free electrons.

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 Thermosphere

 Thermosphere is the fourth layer of the Earth's atmosphere and is located above the mesosphere

 The Thermosphere on the top of mesosphere extends roughly to 85km -500km.

 At an altitude of 80 km, another abrupt temperature change occurs.

 This is the beginning of the thermosphere, a region of highly ionized gases.

 Temperatures are very high in the thermosphere because molecules there are constantly bombarded by
high energy solar & cosmic radiation.

 The air is really thin in the thermosphere.

 A small change in energy can cause a large change in temperature. That's why the temperature is very
sensitive to solar activity.
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 When the sun is active, the thermosphere can heat up to 1,500° C or higher
 The lower part of the thermosphere is called the ionosphere; this is where the aurora borealis (northern
lights) appears when showers of solar or cosmic energy causes ionized gases to emit visible light.
 There is no sharp boundary that marks the end of the atmosphere.
 Pressure and density decreases gradually as one travels away from the earth until they become
indistinguishable from the near vacuum of interstellar space.
 The ionosphere is a region of the atmosphere that is filled with charged particles.
 The high temperatures in the thermosphere can cause molecules to ionize.

 This is why an ionosphere and thermosphere can overlap.

 Exosphere is the upper regions of the mesosphere and higher define a region called the exosphere
from which molecules and ions can completely escape the atmosphere.
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 Very high up, the Earth's atmosphere becomes very thin.

 The region where atoms and molecules escape into space is referred to as the exosphere.

 The exosphere is on top of the thermosphere.

 The atmosphere merges into space in the extremely thin exosphere.

 This is the upper limit of our atmosphere and Less dense.

 Incoming solar energy is largely in the visible region of the spectrum.

 The shorter wavelength blue solar light is scattered relatively more strongly by molecules and
particles in the upper atmosphere, which is why the sky is blue as it is viewed by scattered light.

 Temperatures increase as altitude increases.

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 Atmospheric Chemical Reactions

Two constituents of greatest importance in atmospheric chemistry are:

 Radiant energy from the sun, predominantly in the ultraviolet region of the spectrum, and

 The hydroxyl radical, HO•

 Atmospheric chemistry involves the unpolluted atmosphere, highly polluted atmospheres, and a wide
range of gradations in between.

 Many chemical reactions that require a third body to absorb excess energy occur very slowly in the
upper atmosphere.

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 Gaseous atmospheric chemical species fall into the following classifications:
 Inorganic oxides (CO, CO2 , NO2 , SO2 ),
 Oxidants (O3 , H2O2 , HO)
 HO• radical, HO2•, ROO• radicals, NO3 ),
 Reductants (CO, SO2 , H2S),
 Organics (also reductants; in the unpolluted atmosphere, CH4 is the predominant organic
species, whereas alkanes, alkenes, and aryl compounds are common around sources of
organic pollution),
 Oxidized organic species (carbonyls, nitrates),
 Photo chemically active species (NO2 , formaldehyde),
 Acids (H2SO4), bases (NH3), salts (NH4HSO4,)
 Unstable reactive species (electronically excited NO2 , HO• radical).
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 Solid and liquid particles in atmospheric aerosols and clouds play a strong role in atmospheric
chemistry as sources and sinks for gas-phase species, as sites for surface reactions (solid particles),
and as bodies for aqueous-phase reactions (liquid droplets).

Photochemical Reactions (Processes)

 The absorption of light (UV) radiation by chemical species from the sun, can bring about reactions,
called photochemical reactions.
 Photochemical reactions can occur, even in the absence of a chemical catalyst.
 Nitrogen dioxide, NO2 , is one of the most photo-chemically active species found in a polluted
atmosphere and is an essential participant in the smog formation process.
 NO2 may absorb light of energy hv, producing an electronically excited molecule.
NO2 + hv →NO2*
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 Electronically excited molecules are one of the three relatively reactive and unstable species that are
encountered in the atmosphere and are strongly involved with atmospheric chemical processes.
 The other two species are atoms or molecular fragments with unshared electrons, called free
radicals, and ions consisting of electrically-charged atoms or molecular fragments.
 Reactions that occur following absorption of a photon of light to produce an electronically excited
species are largely determined by the way in which the excited species loses its excess energy.
 This phytochemical reaction may occur by one of the following processes:
1-Physical quenching - loss of energy to another molecule or atom (M) followed by dissipation of the
energy as heat: O2* + M → O2 + M(higher translational energy).
2- Dissociation of the excited molecule (the process responsible for the predominance of atomic oxygen
in the upper atmosphere): O2* → O + O•.
3- Direct reaction with another species: O2* + O3 → 2O2 + O•
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 Luminescence consisting of loss of energy by the emission of electromagnetic radiation
NO2* → NO2 + hv
 If the re-emission of light is almost instantaneous (immediate, rapid, sudden) luminescence is called
fluorescence, and if it is significantly delayed, the phenomenon is phosphorescence.
4- Chemiluminescence is said to occur when the excited species (such as NO2* below) is formed by a
chemical process:
O3 + NO →NO2* + O2(higher energy).
5- Intermolecular energy transfer in which an excited species transfers energy to another species
which then becomes excited:
O2* + Na → O2 + Na*.
 A subsequent reaction by the second species is called a photosensitized reaction.
6. Intramolecular transfer in which energy is transferred within a molecule
7. Photoionization through loss of an electron
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 Reactions in Troposphere

 The main reactions in troposphere takes place are:`

 Acid–base reactions, photochemical smog formation, acid rain formation, redox reaction,
complexation reaction, precipitation and others.

a) Acid–base reactions

 Acid-base reactions occur between acidic and basic species in the atmosphere.
 The atmosphere is normally at least slightly acidic because of the presence of a low level of
carbon dioxide, which dissolves in atmospheric water droplets and dissociates slightly:

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 Atmospheric sulfur dioxide forms a somewhat stronger acid when it dissolves in water:

SO2(aq)+ H2O → H + + HSO−

3

 In terms of pollution, however, strongly acidic HNO3 and H2SO4 formed by the atmospheric
oxidation of N oxides, SO2, and H2S are much more important because they lead to the formation of
damaging acid rain.

 Basic species are relatively less common in the atmosphere. Particulate calcium oxide, hydroxide,
and carbonate can get into the atmosphere from ash and ground rock, and can react with acids such as
in the following reaction.

 The most important basic species in the atmosphere is gas-phase ammonia, NH3.

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 The major source of atmospheric ammonia is from biodegradation of nitrogen containing biological

matter and from bacterial reduction of nitrate.

 Ammonia is particularly important as a base in the air because it is the only water-soluble base

present at significant levels in the atmosphere.

 Dissolved in atmospheric water droplets, it plays a strong role in neutralizing atmospheric acids:

NH3 (aq) + HNO3 (aq) → NH4NO3 (aq)

NH3 (aq) + H2SO4 (aq) → NH4HSO4 (aq)

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 Reactions in Stratosphere
Ozone layer formation and depletion
i) Ozone formation and depletion in Stratosphere

 Stratospheric ozone, O3, serves as a shield to absorb harmful ultraviolet radiation in the stratosphere,
protecting living beings on the earth from the effects of excessive amounts of such radiation.

 The two reactions by which stratospheric ozone is produced (formed) are,

O2 + hv → O + O (λ < 242.4 nm)

O + O2 + M → O3 + M (energy-absorbing N2 or O2)

And it is depleted (destroyed) by photodissociation,

O3 + hv →O2 + O (λ < 325 nm) and a series of reactions from which the net result is the
following:

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O + O3 →2O2 Environmental chemistry 24
 The concentration of ozone in the stratosphere is a steady-state concentration resulting from the
balance of ozone production and destruction by the above processes.

 A total of about 350,000 metric tons of ozone are formed and destroyed daily.

 Ozone never makes up more than a small fraction of the gases in the ozone layer.

 Absorption of electromagnetic radiation by ozone converts the radiation‘s energy to heat.

 The reason that the temperature maximum occurs at a higher altitude than that of the maximum ozone
concentration arises from the fact that ozone is such an effective absorber of ultraviolet light.

 The major cause in ozone depletion consists of chlorofluorocarbon (CFC) compounds, commonly
known as “Freons”.

 In the stratosphere, the photochemical dissociation of CFCs by intense ultraviolet radiation yields
chlorine atoms.
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 CF2Cl2 + hv→ Cl• + CClF2•
Cl• + O3 →ClO• + O2
ClO• + O →Cl• + O2
 The net effect of these reactions is catalysis of the destruction of several thousand molecules of O3
for each Cl atom produced.
 Because of their widespread use and persistency, the two CFCs of most concern in ozone destruction
are CFC-11 and CFC-12, CFCl3, and CF2Cl2, respectively.
 There must be other O3 destruction pathways which is Catalytic ozone destruction.
X + O3 → XO + O2
XO + O → X + O2
Net reaction: O + O3 → 2O2
Where X, is a third component, acts as a catalyst
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 The important catalysts for stratospheric O3 destruction

Chlorine and bromine (Cl and Br)  Hydroxyl radical (OH)

•OH + O3 → HO2• + O2
Cl• + O3 → ClO• + O2
HO2• + O → •OH + O2 HOx cycle
ClO• + O → Cl• + O2 ClOx cycle
Net: O + O3 → 2O2
Net: O + O3 → 2O2

 Nitric oxide (NO)

NO + O3 → NO2 + O2

NO2 + O → NO + O2 NOx cycle

Net: O + O3 → 2O2

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 ii) Formation of Free Radicals

 Free radicals are atoms or groups of atoms with unpaired electrons.

 The strong pairing tendencies of the unpaired electrons make free radicals highly reactive and are
involved with most significant atmospheric chemical phenomena.
 The hydroxyl radical, HO•, is the single most important reactive intermediate species in
atmospheric chemical processes.
 It is formed by several mechanisms.
 At higher altitudes it is produced by photolysis of water:
H2O + hν → HO• + H
 Hydroxyl radical is removed from the troposphere by reaction with methane or carbon monoxide:
CH4 + HO• → H3C• + H2O
CO + HO• → CO2 + H
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 iii) Reactions of Atmospheric Oxygen
 In addition to O2, the upper atmosphere contains oxygen atoms, O; excited oxygen molecules, O2*;
and ozone, O3.
 Atomic oxygen, O, is stable primarily in the thermosphere, where the atmosphere is so rarefied that
the three-body collisions necessary for the chemical reaction of atomic oxygen seldom occur.
 Atomic oxygen is produced by a photochemical reaction:
O2 + hν → O + O
 Molecular oxygen and excited oxygen atoms (O*) are produced due to the photolysis of atmospheric
ozone O3 + hν (λ < 308 nm) → O* + O2

iv) Reactions of Atmospheric Nitrogen

 Unlike oxygen, molecular nitrogen is not readily dissociated by ultraviolet radiation.

 However, at altitudes exceeding approximately 100 km, atomic nitrogen is produced by

photochemical reactions:
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 N2 + hν → N + N

v) Atmospheric Carbon Dioxide

 The one significant photochemical reaction that it undergoes, and a major source of CO at higher
altitudes, is the photodissociation of CO2 by energetic solar UV radiation in the stratosphere:
CO2 + hν → CO + O
vi) Atmospheric Water
 The water vapor content of the troposphere is normally within a range of 1–3% by volume with a
global average of about 1%.
 The percentage of water in the atmosphere decreases rapidly with increasing altitude.
 The cold tropopause serves as a barrier to the movement of water into the stratosphere.
 Thus, little water is transferred from the troposphere to the stratosphere, and the main source of water
in the stratosphere is the photochemical oxidation of methane:
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 The water thus produced serves as a source of stratospheric hydroxyl radical as shown by the
following reaction:
H2O + hν → HO• + H

Reactions in Thermosphere
 Thermosphere is one of the stratification of atmosphere.
 It is rich in Oxygen atom; hence two types of reactions are common in Thermosphere; these are:
 Photo-dissociation
 Photo-ionization

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 Photo-dissociation
 This reaction involves the rapture of chemical bonds from the absorption of photons to form atoms or
molecules:
O2 + hv → 2O + 120 kcal/mol
 This reaction absorbs most of the high energy radiation.
 It releases considerable amount of heat that is responsible for the increase in temperature in the
thermosphere.
Photo-ionization
 This reaction generates ions by absorption of photons and ejection of single electrons from molecules.
N2 , O2 , & O absorb radiations of λ < 240 nm

O2 + hv → O2+ + e-

O + hv → O+ + e-
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 AIR POLLUTION

 Air pollution may be defined as any atmospheric condition in which certain substances are present in
such concentrations that they can produce undesirable effects on man and his environment.

These substances include gases (SOx, NOx, CO, HCs, etc) particulate matter (smoke, dust, fumes,
aerosols) radioactive materials and many others.

 Air pollution is a problem of obvious importance in most of the world that affects human, plant and
animal health.

 Air pollution is one of the most serious environmental problems in societies at all level of economic
development.

 It is also defined as concentration of foreign matter in air in excessive quantity which is harmful to
the health
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of man. Environmental chemistry 33
 Atmospheric (air) pollution occurs when the concentration of certain substances become high enough
to toxify the atmospheric environment.

Types of Air Pollution

 Indoor and Outdoor

 Pollutions from the housing made materials and living and working activities of the house, such as:
natural radiation-radon, domestic combustion-coal gas, and human habits tobacco smoking.

Out door air pollution

 Pollutions from out door services and environmental mixings, such as: transportation-automobiles,
industries-refineries, atomic energy plant-nuclear, and community activities-cleaning of streets.

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 Air Quality

 Air quality is defined as a measure of the condition of air relative to the requirements of one or more
biotic species and/or to any human need or purpose.

 Air Quality is a dynamic and complex environmental phenomenon exhibiting large temporal
and spatial variation.

 The temporal and spatial variations in atmospheric levels of pollution, which is the essence of
air quality, are caused by

(a) changes in the pollutant source(s) emission rates, and

(b) changes in meteorology and topography

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 Ambient air quality monitoring can be defined as a systematic, long-term assessment of air pollutant

levels in our communities.

 In general, ambient air monitoring networks are typically used to:

Characterize local, regional, and national air quality conditions

 Assess health impacts

Assess effectiveness of control programs

Help form the basis for new control programs

Assess source impacts

Provide information to the public

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 Environmental Protection Agency (EPA) has set primary and secondary standards that would provide
an ample margin of safety and established acceptable levels of concentration or criteria in the ambient
air for six pollutants.

 Those six pollutants were: sulfur dioxide (SO2), particulate matter having diameters of 10 m or less
(PM10 and PM2.5), carbon monoxide (CO), ozone (O3), nitrogen dioxide (NO2) and lead (Pb).

 There are two types of ambient air standards, primary standards and secondary standards.

 Primary standards are those in which the attainment and maintenance is requisite to protect the public
against adverse health effects.

 Secondary ambient air quality is defined as a level of air quality which is required to protect the
public welfare from any known or anticipated adverse effects associated with the presence of such air
pollutants in the ambient air.
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 The purpose of the secondary standard is to provide broader protection to the public and protect the
environment from long-term damage.

 With sulfur dioxide (SO2) as the only exception, EPA has established only one level for both the
primary and secondary standard.

 Collectively, these standards form the National Ambient Air Quality Standards (NAAQS).

 Air quality monitoring can also be used to determine the following information:

(1) document a facility’s progress toward compliance,

(2) establish baseline pollutant levels for controlled substances,

(3) control policy development,

(4) provide short-term data requirements for episode control plans

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(5) provide valuable data to epidemiological studies designed to establish the relationship between
pollutant levels and the human health and welfare effects of exposed populations,

(6) determine the Air Quality Index

(7) confirm air pollution modeling validation, and

(8) assess trends in the atmospheric levels of regulated and unregulated pollutants.

Nature and Classification of Air Pollutants

Classification of Air Pollutants

 Air Pollution can be defined as the addition of harmful substances (pollutants) to the atmosphere
resulting in damage to the environment, human health, and quality of life.

 There are a number of ways of classifying air pollutants.

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 Most commonly they are classified on the basis of

A) differences in their physical or chemical characteristics,

B) their origin,

C) the way pollutants reach the atmosphere, and

D) their legal status

A) Based on Differences in Their Physical or Chemical Characteristics

 Aerosols: Are tiny particles dispersed in gases and include both liquid and solid particles.
 Air pollution terminology relating to atmospheric aerosols includes dusts, fog, fumes, hazes,
mists, particulate matter, smog, smoke, and soot.

 Gases and Vapors: Are composed of widely separated freely moving molecules which will expand to
fill a larger container and exert a pressure in all directions
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B) Based on Their Origin
 Air pollutants are classified in different ways based on their origin. These are:
 Mobile and Stationary Sources:
Mobile sources of emissions include automobiles, trains, and airplanes while stationary sources
include Electric power plants, chemical manufacturing industries, air strippers, and soil vapor
extraction operations.
 Direct and Indirect Sources:
A direct source emits pollutants directly while indirect sources do not themselves emit pollutants
but attract mobile sources (e.g. a shopping mall, athletic stadium).
 Point Source and Area Sources:
 A point source is defined as a stationary source whose emissions significantly impact air quality.
Area sources are those that, individually do not have significant impact on air quality but, are
significant when viewed together (e.g. dry cleaners, open burning).
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 C) Based on the Way Pollutants Reach the Atmosphere

 Air pollutants are classified as primary and secondary pollutants based on the way they reach the
atmosphere.

 Primary pollutants are those that are emitted directly into the atmosphere from an identifiable
source. Examples include carbon monoxide and sulfur dioxide.

 Secondary pollutants, on the other hand, are those that are produced as a result of chemical
reactions in the atmosphere. example, ozone, which is a major component of urban smog, formed as
a result photochemical reactions.

D) Based on Their Legal Status

 Based on the way in which they are regulated, or their legal status, six pollutants have been
identified
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by the Environmental Protection Agency (EPA) as criteria pollutants because they are both common and
detrimental to human health.
Gaseous Inorganic Air Pollutants
 A number of gaseous inorganic pollutants enter the atmosphere as the result of human activities.
 Those added in the greatest quantities are SO2, NO, NO2 and CO. Other inorganic pollutant gases
include NH3, N2O, N2O5, H2S, Cl2, HCl, and HF.
Sulfur Dioxide
 Sulfur dioxide forms as coal and petroleum products burn; it enters the air as a primary air pollutant.
 While sulfur oxidizes readily to sulfur dioxide during the combustion.

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  Sulfur trioxide dissolves in water droplets of the atmosphere to produce sulfuric acid, a major
component of acid rain and a secondary air pollutant.

Nitrogen Oxides

 Nitrogen oxides, NOx, form another group of air pollutants.

 Unlike the sulfur of SOx, the nitrogen of these pollutants comes principally from the air itself rather
than from impurities in fuels.
 Molecules of the nitrogen and oxygen of the air combine at very high temperatures to form nitric
oxide, NO, a colorless gas.

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 Once in the atmosphere, nitric oxide reacts with additional oxygen to form nitrogen dioxide, NO2, a
red-brown, toxic gas that causes irritation to the eyes and the respiratory system.

Carbon Monoxide
 Carbon Monoxide (CO) is a colorless, odorless poisonous gas produced by incomplete, or inefficient,
combustion of fuel.
 It is predominantly produced by road transport, in particular petrol-engine vehicles.
 CO prevents the normal transport of oxygen by the blood which results in a significant reduction in
the supply of oxygen to the heart, particularly in people suffering from heart disease.
 The major process responsible for the removal of CO from the atmosphere is its conversion to CO2
by reaction with hydroxyl radical.
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 CO + HO• → CO2 + H

Acid-Rain

 With or without air pollution, simply the natural presence of carbon dioxide in the earth’s atmosphere
makes rain acidic.

 The carbon dioxide of the atmosphere dissolves in raindrops as they form and fall to the ground, and
it reacts with the rainwater to form carbonic acid.

CO2 + H2O → H2CO3

 Carbon dioxide can dissolve in water until the solution is saturated, which results in an acidic
solution of pH 5.6. Because of this the purest rain, falling through an unpolluted sky, can reach earth
as an acidic solution of pH 5.6.

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 Since the pH of pure rainwater can be as low as 5.6, we might consider rain whose pH is lower than 5.6 to be
acid rain.

Organic Air Pollutants

 Organic pollutants may have a strong effect upon atmospheric quality.

 The effects of organic pollutants in the atmosphere can be divided into two major categories.

 The first consists of direct effects, such as cancer caused by exposure to vinyl chloride.

 The second is the formation of secondary pollutants, especially photochemical smog.

 Some of the most common organic air pollutants are:

Organic Compounds from Natural Sources

 Methane is one of the organic compounds since it is the most important greenhouse gas after carbon
dioxide
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 Methane is produced by the bacterial action, when dead organic matter is subjected to an oxygen-
depleted highly reducing aqueous or terrestrial environment as per the following equation:

 Methane undergoes photochemical dissociation in the stratosphere to give water vapour

 But in the troposphere it undergoes photochemical reaction to give CO and O3.

Volatile Organic Compounds (VOCs)

 VOCs originate from a number of sources: furnishings, furniture and carpet adhesives, glues,
building materials, cosmetics, cleaning agents, fungi, tobacco smoke and fuel combustion.

 By far, the greatest peak exposure to VOCs occurs during home decorating using solvent-based
paints.
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 Some of the compounds are aliphatic and aromatic hydrocarbons, halogenated compounds and
aldehydes.

 Hydrocarbons

 The gaseous and volatile liquid hydrocarbons are of particular interest as air pollutants.

 Hydrocarbons can be saturated or unsaturated, branched or straight-chain, or can have a ring structure
as in the case of aromatics or other cyclic compounds.

 Hydrocarbons predominate among the atmospheric pollutants because of their widespread use in
fuels.

 They enter the atmosphere either directly from the fuel or as by-products of partial combustion of
other hydrocarbons.

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 The hydrocarbons in air by themselves alone cause no harmful effects.

 They are of concern because the hydrocarbons undergo chemical reactions in the presence of
sunlight and nitrogen oxides forming photochemical oxidants of which the predominant one is ozone.

 Oxygen-Containing Organic Compounds: Aldehydes and ketones

 The aldehydes and ketones enter the atmosphere from a large number of sources and processes.

 These include direct emission from internal combustion engine exhausts, incinerator emission, spray
painting, polymer manufacture, printing, and lacquer manufacture.

 They are also produced from hydrocarbons by the photochemical oxidation in the atmosphere

 Aldehydes are capable of absorbing UV radiation longer than 290 nm and this leads to photochemical
degradation.

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  Organohalide Compounds

 Organohalide compounds contain at least one atom of F, Cl, Br or I.

 They may be saturated or unsaturated and exhibit different physical and chemical properties.

 Chlorofluro carbons (CFCs) are used in wide variety of industrial applications including aerosol
propellents, refrigerants, and foam blowing.

 The CFC's which have attracted most attention in ozone depletion are CFCl3, CF2Cl2

 The predominant anthropogenic source is CH3Br and CF3Br. Sometimes sources such as CF2BrCl
and C2H4Br2 are entirely man made.

 The three major oxidants involved are ozone, PAN, and nitrogen oxides. Of these, PAN has the
highest toxicity to plants, attacking younger leaves and causing bronzing‖ and glazing of their
surfaces.
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 Photochemical Smog
 Smog = fog + smoke
 Smoke: Particles formed by incomplete combustion of fuel
 Fog: Term denoting high level of water droplets
 The conditions for the formation of photochemical smog are air stagnation, abundant sunlight, and
high concentrations of hydrocarbon and nitrogen oxides in the atmosphere.
 Smog arises from the photochemical reactions in the lower atmosphere by the interaction of
hydrocarbons and nitrogen oxide released by exhausts of automobiles and some stationary sources.
 This interaction results in a series of complex reactions producing secondary pollutants such as ozone,
aldehydes, ketones, and peroxyacyl nitrates.
 The typical smog episode occurs in hot, sunny weather under low humidity conditions.
 The characteristic symptoms are the brown haze in the atmosphere, reduced visibility, eye irritation,
respiratory
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 Chemical Reactions Involved in Smog Formation in the Atmosphere

 Smog is a secondary air pollutant that forms sometime after and some distance from the injection into
the atmosphere of the primary pollutant nitrogen oxides and reactive hydrocarbons required for its
formation.

 Photochemical smog, also known as summer smog, is a type of smog that is produced when UV light
originating from the sun interacts with the oxides of nitrogen present in the atmosphere.

 Photochemical form is formed by a complex series of chemical reactions involving sunlight, oxides
of nitrogen, and volatile organic compounds that are present in the atmosphere as a result of air
pollution.

 These reactions often result in the formation of ground level ozone and certain airborne particles.

 The formation of photochemical smog is closely related to the concentration of primary pollutants in
the atmosphere.
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 Common examples of primary pollutants that contribute towards photochemical smog includes oxides
of nitrogen such as nitric oxide, nitrogen dioxide, and nitrous oxide and most VOCs (volatile organic
compounds).

 Common examples of secondary pollutants that contribute towards the formation of photochemical
smog include aldehydes, tropospheric ozone, and peroxyacyl nitrates (often abbreviated to PAN).

 It is called a mixture of primary and secondary air pollutants.

 When it is exposed to ultraviolet radiation, the NO2 molecule is known to undergo a complex series of
hydrocarbon reactions to produce the photochemical smog components.

 These components include a mixture of ozone, aldehydes, nitric acid, peroxyacyl nitrates
(abbreviation: PANs) and many other secondary pollutants.

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 Photochemical Smog formation

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 Smog-forming automotive emissions
 Internal combustion engines used in automobiles and trucks produce reactive hydrocarbons and
nitrogen oxides, two of the three key ingredients required for smog to form.

 Photochemical production of ozone in the troposphere occurs from the photolysis of nitrogen dioxide
(NO2), producing oxygen atoms (O):

a) NO2 + hv → NO + O
In the troposphere, the oxygen atoms react quickly with oxygen molecules (O2), producing ozone
(O3):
b) O + O2 → O3
Ozone can also react with nitric oxide, producing NO2:
c) O3 + NO → NO2 + O2
 These three reactions result in a fast cycle where ozone is produced through reactions (b), but
destroyed
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through reaction (c). Environmental chemistry 56
 Under normal conditions, the ozone formed, by the reaction of O and O2, will be quickly removed by
reaction with NO to provide NO2 and O2
 Hydrocarbons, indicated by symbol RH compete for free oxygen released by NO2 decomposition to
form oxygen bearing free radicals such as acyl radical

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 This radical takes part in a series of reactions involving the formation of still more reactive species, which in
turn react with O2, hydrocarbons and nitric oxide.

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 Further the acylate radical (RCO2•) can react with NO to generate even more NO2.

 The NO level in the atmosphere eventually drops off with the accumulation of NO2 and O3.

 When the reactions such as these increase the NO2 level sufficiently, another reaction begins to
compete for the peroxyacyl radical.

 The end products are known as peroxyacyl nitrates or PANS. Numerous PANS could be formed,
corresponding to different possible R groups. Three of the common members of PAN family are:

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 In addition to ozone, oxidant peroxyacyl nitrates and aldehydes found in smog are eye irritants.

 Ozone is the most abundant of the photochemical oxidants.

 Eye irritation is caused by other components of photochemical smog, principally formaldehyde,

peroxybenzoyl nitrate (PBzN), peroxyacetyl nitrate (PAN) and acrolein.

 In the very simplest terms, we can express the formation of photochemical smog as:

 HC + NOx + Sunlight → Photochemical smog.

 Ozone absorbs ultraviolet radiation very strongly in the region 220-330 nm.

 The reactions by which stratospheric ozone is produced are:

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 Chlorofluoro Compounds and Ozone Layer Depletion

 Chlorofluoro compounds (chlorofluorocarbons, CFCs), such as dichlorodifluoromethane (CCl2F2),

commonly called Freons are volatile 1- and 2-carbon compounds that contain Cl and F bonded to
carbon. These compounds are notably stable and nontoxic.

 One of the important properties of CFCs is that they are almost completely inert both biologically and
chemically in the earth's environment, in the troposphere.

 Because they do not react, they circulate through the troposphere until they escape into the
stratosphere.

 While unreactive in the troposphere, CFCs undergo photodecomposition by the action of high-energy
ultraviolet radiation in the stratosphere, which is energetic enough to break their very strong C-Cl
bonds thereby releasing Cl atoms:
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 CCl2F2 + hv → Cl• + •CClF2

 The Cl atoms are very reactive species.

 Under the rarefied conditions of the stratosphere, one of the most abundant reactive species available
for them to react with is ozone, which they destroy through a process that generates ClO:

Cl + O3 → ClO + O2

 Ozone depletion has a number of consequences for human health and agriculture.

 These include increased rate of skin cancer and eye cataracts, weakening of immune systems, damage
to crops, reductions in primary producers (plankton) in the ocean and increasing air pollution.

 Ozone “hole:” a depletion or thinning of ozone concentration in stratosphere.

 Depletion caused by chlorine-based aerosols, such as chlorofluorocarbons (CFCs).

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 Greenhouse Gases and Global Warming
 A rapid increase in the average temperature of the atmosphere, oceans, and landmasses of Earth in
general is known as global warming.
 By absorbing and reflecting infrared waves radiated by Earth, these gases conserve heat as the glass
in a greenhouse does and are thus known as greenhouse gases.
 As the atmosphere becomes richer in these gases, it becomes a better insulator, retaining more of the
heat provided to the planet by the Sun.
 The net result is that more heat is received from the sun than is lost back to space, a phenomenon
known as greenhouse effect.
 Global warming is caused by the presence in the atmosphere of greenhouse gases (CO2, H2O vapor,
CH4 etc.), which by absorbing the radiation emitted from the surface of the earth and preventing its loss
to space results in the conservation of heat.
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 Effects of global warming

o The world is expected to have a more extreme weather, with more rain during wet periods,
longer droughts, and more powerful storms.

o Melting of the polar ice caps, leading to a rise in sea level.

o Diseases like malaria may become more common in the regions of the globe between the
tropics and the polar regions.

o Climate change may bring extinction for many of the world’s plant species, and for animal
species.

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