AIR POLLUTION

Definition
Air pollution is defined as the presence of contaminants in air such as dust, fumes, gases, mist, odour, smoke or vapour in

such quantities and characteristics for a particular duration

which may be injurious to human, plant or animal life or to the property or which unreasonably interfere with comfortable environment of life and property

SOURCES OF AIR POLLUTION

Natural sources

Volcano
Accidental forest fire Dust storms Oceans Plants and trees Thunderstorm and lightning Hot springs

SOURCES OF AIR POLLUTION

Anthropogenic sources

Industrial sources
Manufacturing of products from raw materials Industrial sources Utilities Part of our modern life Personal sources Automobile, home furnace, stoves, etc.

CLASSIFICATION OF AIR POLLUTANTS

ORIGIN

Primary pollutant Secondary pollutant

CHEMICAL COMPOSITION Organic compound Inorganic compound

STATE OF MATTER Particulate pollutant Gaseous pollutant

Primary air pollutants

Substances that are emitted directly into the atmosphere from identifiable sources as a result of combustion (automobile exhaust and emissions from thermal power plants), evaporation (volatile substances such as gasoline, paints and cleaning fluids), grinding (vehicle wheel-road surface interaction) and abrasion (ploughing)
Remain in the atmosphere in the form in which they are emitted Example: Particulate matter, CO, NOx, SOx, organic compounds and radioactive compounds

Secondary air pollutants

Produced in the air by the interaction among two or more primary pollutants, or by interaction with normal atmospheric constituents, with or without photo-activation Substances that are created by various physical processes and chemical reactions that take place in the atmosphere (ex: photochemical reaction, oxidation, hydrolysis) Example: ozone (O3), Formaldehyde (HCHO), Peroxyl Acetyl Nitrate (PAN) and photochemical smog

Organic compounds
Primarily contains C & H; may also contain elements such as O2, N2, P, S
Example: aldehydes, ketones, organic sulphur compounds

Inorganic compounds
Example: Minerals, CO, CO2, SOx, NOx, O3

PARTICULATE POLLUTANTS
Settle out of the atmosphere Finely divided solids and liquids including dust, fume, smoke, fly ash, mist

GASEOUS POLLUTANTS
Do not settle out of atmosphere CO, CO2, SOx, NOx, O3 Behave much as air

PRIMARY POLLUTANT GENERATION THROUGH COMBUSTION

Complete combustion of pure hydrocarbon fuel CH4 + 2 O2 CO2 + 2 H2O

Incomplete combustion of fuel (Reasons: temp or oxygen availability not enough, fuel not given enough time to burn completely) Result: Some of the carbon will be released as CO, instead of CO2 Incomplete burning of fuel Result: Emission of partially combusted hydrocarbons CH4 + O2 mostly (CO2 + 2 H2O) + traces of (CO + HC)

PRIMARY POLLUTANT GENERATION THROUGH COMBUSTION

Combustion takes place in air (N2-78% & O2-21%), not in pure oxygen environment

If temperature of combustion is high, some N2 in air reacts with O2 in air and forms various nitrogen oxides:
Air (N2 + O2) + Heat NOx

Most of the fuels are not pure hydrocarbon; they contain other elements such as N, S, Pb (in petrol) and other unburnable materials called ash. Incomplete combustion in air (not in pure O2) of fuels that are not pure hydrocarbons: Fuel (H, C, S, N, Pb, ash) + air (N2 + O2) Emissions (CO2, H2O, CO, NOx, SOx, Pb, particulates) + Ash

GENERATION OF SECONDARY AIR POLLUTANT

HC and other organic compounds that readily vaporize are called Volatile Organic Compounds (VOCs). VOCs react with NOx in the presence of sunlight to produce photochemical smog:

VOCs + NOx + Sunlight

Photochemical smog (O3 + etc.)

The above reactions are greatly simplified; however they do introduce the 6 principal urban air pollutants: CO, NOx, SOx, Pb, O3 and PM (ash and unburnt hydrocarbons) OZONE (O3) Ground level O3 is harmful to our health Stratospheric O3 protects our health by shielding us from ultraviolet radiation from the sun.

SOURCE TYPES
Mobile source Modes of transportation highway vehicle, rail, aircraft, boat and ship Stationary source Industry power plants, metal processing plants, petroleum production and refineries, chemical plants (prominent one is electric power plants)

SOURCE TYPES

Point source Line source Area source Volume source

CARBON MONOXIDE (CO)

CO is a colourless, odourless, tasteless, poisonous gas

Source
Produced out of a combustion that involves one or more of the following: insufficient oxygen low combustion temperature fuel not given enough time to burn The parameters do not meet more often in mobile source than in stationary sources: Result: CO emission is high in mobile sources 77% of total CO emission comes from transport sector

Effect
No adverse impact on plants and materials at the level that occur in urban air However, CO is an asphyxiant (gives suffocation due to lack of oxygen) Interferes with the bloods ability to carry O2 from lungs to different organs and tissues CO + Hb (haemoglobin) COHb (Carboxyhaemoglobin)

CARBON MONOXIDE (CO)

Hb has a much greater affinity for CO than it does for O2 Consequence: Even a small amount of CO can seriously reduce the amount of O2 conveyed throughout the body; Brain function affected and heart rate increases in an attempt to offset the O2 deficit.

Typical CO Levels
Place Near busy roadways CO Concentration (ppm) 5 to 50

Congested highways
Cigarette smoke contains Inside bars and restaurants where smoking is permitted

100
400 20 to 30

OXIDES OF NITROGEN (NOx) 7 oxides of nitrogen are known: NO, NO2, NO3, N2O, N2O3, N2O4 and N2O5 Important air pollutants: NO and NO2 (combined referred to as oxides of nitrogen, NOx) N2O: Green house gas (GHG)

Thermal NOx: Formed, when N2 and O2 in the combustion air react in high temperature (about 1000 K) and N2 gets oxidised. Fuel NOx: Results from oxidation of nitrogen compounds bound chemically in fuel molecules (coal has nitrogen compounds about 3% by weight).
Transport sector contributes almost half of the NOx emissions. EFFECTS: NO Has no known adverse health effects at concentrations found in the atmosphere NO oxidises to NO2 and it has many adverse health effects

Adverse effects of NO2 Irritates lungs, causes bronchitis and pneumonia and results in lower resistance to respiratory functions Reacts with hydroxyl radicals (OH) in the atmosphere to form nitric acid (HNO3); HNO3 corrodes metal surface and contributes to the acid rain problem

OXIDES OF SULPHUR (SOx)

SOx emission sources 90% fossil fuel combustion from stationary sources (85% of this is emitted from power plants) 3% from highway vehicles Significant non-combustion sources of sulphur emission: Petroleum refining Copper smelting Cement manufacturing Sulphur in fossil fuels Coal: 1 6 % (About 50 % organic sulphur is chemically bound to coal, other half is physically trapped in the non-carbon portion of coal and gets removed by pulverisation or washing of coal before combustion.)
Petroleum: Trace amount to about 5% All most all sulphur are removed during the process of refining Gasoline has < 1ppm sulphur SO2 emission When S containing fuels are burned, S is released as SO2 and SO3. With moisture, these form H2SO4. SO2 changes to SO4 particles in a few days Principal removal process is wet deposition (with precipitation)

OXIDES OF SULPHUR (SOx) Adverse effects of SO2 Highly water soluble: absorbed in the moist parts of the upper respiratory tracts less harmful

When entrained in aerosols, can penetrate to deeper parts of respiratory system and can damage lungs. Synergy of adverse impacts of particle and SO2 will be more damaging.
(Every major air pollution episode has resulted from the combination of SO2 and PM)

Acidification damages plants by affecting their ability to extract nutrients from the soil because nutrients get leached from the soil. Sulphurous pollutants can discolour paint, corrode metals and cause organic fibers to weaken. Prolonged exposure to sulphates causes damage to building marbles, limestone and mortar as carbonate in these materials are replaced by sulphates.

3 + 2 4 = 4 + 2 + 2
Calcium sulphate (gypsum, CaSO4) is water soluble and easily washes away It leaves a pitted eroded surface Many historic building across world are getting rapidly damaged due to this exposure

VOLATILE ORGANIC COMPOUNDS (VOC)

Atmospheric VOC consists of: Unburnt hydrocarbons emitted form tailpipes and smoke stacks when fossil fuels are not completely combusted Gaseous hydrocarbons that evaporate from solvents, fuels and other organics Natural sources: Isopropene emitted from deciduous trees (minor contribution) Pinene and limonene emitted from conifers

Transport sector responsible for about 1/3 of anthropogenic VOC emissions Industrial sector - responsible for about 2/3 of anthropogenic VOC emissions
ENVIRONMENTAL EFFECT

VOCs react with NOx in the presence of sunlight to produce photochemical smog:
VOCs + NOx + Sunlight Photochemical smog (O3 + etc.)

PHOTOCHEMICAL SMOG AND OZONE

NOx, VOC and sunlight, when come together, initiate a complex set of reactions produce Secondary pollutants, known as photochemical oxidants O3 is the most abundant photochemical oxidant NO NO2 O3 photochemical reaction sequence (without added hydrocarbons) N2 + O2 2NO + O2 NO2 + h O + O2 + M O3 + NO
sunlight

2NO 2NO2

(Formation of NO during combustion) (Nitric oxide getting oxidized to NO2)

NO + O (Photolysis: a photon with right amount energy decomposes NO2

and produces a free atomic oxygen, h represents a photon)

O3 + M

(Free atomic oxygen combines with diatomic oxygen (O2) to form ozone (O3)

NO2 + O2 (Ozone convert NO back to NO2)

NO2 tends to create O3, whereas, NO tends to destroy O3

EFFECT OF PHOTOCHEMICAL OXIDANTS

Respiratory effects: coughing, shortness of breath, headache, chest tightness and eye, nose and throat irritation Symptoms can be severe for asthmatics Long term exposure can lead to permanent scarring of lung tissues, loss of lung function Damage to tree foliage and growth rate Reduced yield of major agricultural crops such as wheat, soybeans and peanuts

Ozone
Upper ozone: Increased UV radiation Skin cancer Cataract Crop Tree

Lower ozone

Generated ground level ozone respiratory system vegetation and ecosystem

PARTICULATE POLLUTANTS

Definition
A particle consists of a single continuous unit of solids or liquid containing many molecules held together by intermolecular forces and primarily larger than molecular dimensions (< 0.001m). Atmospheric particulate matter (PM) consists of any dispersed matter, solid or liquid, in which the individual aggregates range from molecular clusters of 0.005 m diameter to coarse particles up to about 100 m.

A particle may also be considered to consist of two or more such unit structure held together by inter-particle adhesive forces such that it behaves as a single unit in suspension or upon deposit.

PARTICULATE POLLUTANTS
Source
Particulate matter results from the disintegration of solids. Transport, construction and industrial activities, volcanic eruption, desert storms, sea salts, secondary aerosols and resuspension of crustal matter are some of the major sources of air pollution. The finer the particles the more is its retention time in atmosphere.

PARTICULATE MATTER
Several terms for PM Aerosol: Dust: Any tiny particles, liquid or solid, dispersed in the atmosphere Solid particle caused by grinding or crushing operations

Fume:
Mist/Fog:

Solid particle formed when vapour condenses; size: 0.3 m to 3 m

Liquid particles suspended in air; particles or droplets formed by condensation of vapour; mist particles may coalesce; normally <

10 m in size.
Smoke/Soot: Particles composed primarily of carbon that result from incomplete combustion; normally < 1 m in size. Smog: Fly ash: A combination of smoke and fog. Noncombustible parts of coal that comes out with flue gas: size: 1 m to 100 m

PARTICULATE MATTER
PHYSICAL CHARACTERISTICS Size Measured in m (10-6 m in diameter) Particles > 500 m can be seen in naked eye Particles < 0.005 m can only be observed through microscope Particle size of air pollution interest: 0.01 to 100 m

Particles < 1 m do not tend to settle out rapidly

Mode of formations Solid particle: dust, smoke, fume, fly ash

Liquid particle: mist, spray

Settling properties Major natural process of removal of particulate matter from the atmosphere

PARTICULATE MATTER
PHYSICAL CHARACTERISTICS Optical qualities Reduction of visibility due to dust cloud Visibility reduction is primarily due to scattering of lights by particle Particle size range most effective in visibility reduction: 0.38 to 0.76 m Depends of particle shape and surface characteristics

PARTICULATE MATTER
CHEMICAL CHARACTERISTICS PM contains both organic and inorganic components

Common organic compounds found in PM:

Phenols, organic acids and alcohols

Common inorganic compounds found in PM: Nitrate, sulphate, metals

PARTICULATE MATTER
BIOLOGICAL CHARACTERISTICS PM contains micro organisms like protozoa, bacteria, virus, fungi, spore, pollen, algae

Micro organisms survive for short time because of:

Lack of nutrients Effect of ultraviolet radiation from sun

Certain bacteria and fungi can survive for longer periods

SIZE OF PARTICULATE MATTER

Sea salt nuclei: between 0.05 to 0.5 m Smoke and fly ash particles: covers a wide size range (0.05 to 200 m) Particles in urban atmosphere: Particle mass distribution in urban atmosphere exhibits two maxima: Between 0.1 and 1.0 m (produced as a result of condensation) Between 1.0 and 30.0 m (fly ash and dust generated by mechanical disintegration) Particles formed as a result of photochemical reaction: Usually very small (< 0.04 m)

SCALE OF AIR POLLUTION

Air pollution problem may occur on three scales: Micro-scale: Covers less than a centimeter to the size of a house or slightly larger Ex: Indoor air pollution Meso-scale: Covers a few hectares up to size of a city or country Macro-scale:

Extends across provinces, nations and up to global scale

Ex: Transboundary pollution, acid rain, ozone layer depletion, global warming

EFFECT OF AIR POLLUTANTS ON HUMAN

PARTICULATE POLLUTANTS Depends on the aerodynamic characteristics of particles in the flow stream Aerodynamic propertied depend on size, shape and density of particle Fibre type particle behaviour depends on its orientation to the direction of flow

EFFECT OF AIR POLLUTANTS ON HUMAN

GASEOUS POLLUTANTS Impact is mostly influenced by solubility of gaseous molecules in the lining of the different regions of the respiratory system SO2 Highly soluble; absorbed in the upper airways NO2 and O3 Less soluble; may penetrate to the pulmonary regions

FACTORS AFFECTING DEGREE OF HEALTH RISK

Composition
Size Concentration Time of exposure

PARTICULATE MATTER SIZE

Equivalent aerodynamic diameter: Aerodynamic diameter is an expression of a particle's aerodynamic behavior as if it were a perfect sphere with unit-density and diameter equal to the aerodynamic diameter.

For a particle having irregular shape, the aerodynamic diameter of the particle is the diameter of a spherical particle of unit density (1g/cc) having the same gravitational settling velocity as that of the irregular shaped particle in question.
da = (s.g./X)1/2 * dp

Where, s.g. = specific gravity X = shape factor (= 1 for spherical particles) da = aerodynamic diameter dp = actual particle diameter da = dp (s.g.)1/2

PARTICULATE MATTER SIZE

Airborne dust Suspended particulate matter (SPM or TSPM): > 10 m (up to 100 m) Respirable particulate matter (RSPM, RPM or PM10): < 10 m PM10 = PMcoarse + PMfine = PM2.5-10 + PM2.5

PARTICULATE MATTER SIZE

PICK UP VELOCITY
The minimum velocity required to raise the dust from ground surface and make it air borne
Pick up velocity of dry dust

STUDY OF HEALTH EFFECTS

Epidemiological study

Clinical study
Toxicological study

PARTICULATE MATTER
Settling velocity of the spherical particle When particle reaches terminal velocity, the gravitational force pulling it down is balanced by the force due to buoyancy and frictional drag force. For particles < 30 m and density much greater than air, simplified stokes law can be applied for drag force. Drag force Gravitational force = Drag force

3 mg = d g = 3vd 6

d2 g v= 18

Gravitational force

m = mass of particle (g) g = gravitational acceleration (9.8 m/s2) d = particle diameter (m) = particle density (g/m3) = viscosity of air (0.0172 g/m.s) v = settling velocity (m/s)

SETTLING VELOCITIES OF PARTICULATE MATTER

Particle size 0.1 m

1 m 10 m 100 m

Approximate settling velocity (cm/s) 4 x 10-5

4 x 10-3 0.3 30

Numerical: Settling velocity of a spherical particle

Find the settling velocity of a spherical droplet of water with diameter 2m, and estimate the residence time of such particles if they are uniformly distributed in the lower 1000m of atmosphere. Solution: With density of water equal to 106 g/m3
d2 g (2 106 m)2 106 /3 (9.8 / 2 ) v= = 18 18 0.0172 g/

v = 1.27 104 /

Using simple box model to estimate the residence time of particles uniformly distributed in a box of atmosphere with height h (m), Residence time = h/v = 1000/(1.27 x 10-4 m/s) = 7.9 x 106 s = 91 days