ASL385

Fundamentals of Air Pollution Science

Ravi Kumar Kunchala

Centre for Atmospheric Sciences
Indian Institute of Technology, Delhi
Major Sources of Air Pollution Emissions categories

Natural Sources Energy Sector

Anthropogenic Sources Sources Industrial processes
Biogenic Sources Agriculture, Vegetation, Fires and forestry
Waste Sector
Ref: He et al., 2024
In the past decade, multiple articles have summarized the knowledge of air pollution from different
aspects, including air pollution effects on the mean features of climate/weather, climate/weather impacts
on air pollution, health impacts of air pollution, and air pollution-ecosystem interactions.

During recent years, weather and climate extremes (e.g., extreme precipitation, floods, droughts,
wildfires, and heat waves) have received increasing attention due to their significant impacts on socio-
economy, public health, and ecosystems.

For instance, storms in the North Atlantic in 2017 alone led to devastating flooding, which caused more
than $170 billion in damages [28].

Droughts and floods over Asia substantially affect agriculture and food security, leading to ~ $49 billion
loss in the economy during 2008–2018 [29].

Heat waves caused about 70,000 deaths in 2003 in Europe [26] and are projected to increase global
mortality under future climate change [27].

The increasing wildfires in the U.S. alone lead to thousands of deaths due to smoke pollution and
degradation in ecosystem functioning, which requires billions of dollars for suppression expenditures
[30].
 Classifications of air pollutants
Primary Pollutants Secondary Pollutants

Those pollutants which emitted Those pollutants which are

directly into the atmosphere produced by the interaction
and remain in the atmosphere among two or more primary
in its original form are pollutants are called “secondary”
“primary ” pollutants pollutants

CARBON MONOXIDE (CO),

SULFUR OXIDES SUCH AS INCLUDE OZONE (O3),
SULFUR DIOXIDE (SO2), PEROXYACETYL NITRATE
NITROGEN DIOOXIDE (NO2), (PAN), AND SULFURIC ACID
HYDROCARBONS, (H2SO4)
PARTICULATES, AND CARBON
DIOXIDE.

SMOG OR BROWN CLOUD CONTAINS BOTH PRIMARY AND

SECONDARY POLLUTANTS
Ref: Francisc Popescu and Ioana Ionel,2010
Ref:UN Environment Programme
Ref: Rajput et al, Book Chapter
Short-lived climate forcers (SLCFs) are a set of chemically and physically reactive compounds with
atmospheric lifetimes typically shorter than two decades but differing in terms of physiochemical
properties and environmental effects.

SLCFs can be classified as direct or indirect, with direct SLCFs exerting climate effects through their
radiative forcing and indirect SLCFs being precursors of direct climate forcers.

Direct SLCFs include methane (CH4), ozone (O3), shortlived halogenated compounds, such as
hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), and aerosols.

Indirect SLCFs include nitrogen oxides (NOx), carbon monoxide (CO), non-methane volatile organic
compounds (NMVOCs), sulphur dioxide (SO2), and ammonia (NH3).

Aerosols consist of sulphate (SO2–), nitrate (NO–), ammonium (NH+4), carbonaceous aerosols (e.g., black
carbon (BC), organic aerosols (OA)), mineral dust, and sea spray and can be present as internal or
external mixtures and at sizes from nano-meters to tens of micro-meters.

SLCFs can be emitted directly from natural systems and anthropogenic sources (primary) or can be
formed by reactions in the atmosphere
Relative regional and sectoral contributions to the present day (year 2014) anthropogenic emissions of short-
lived climate forcers (SLCFs). Ref: IPCC, Chapter 6
Relative regional and sectoral contributions to the present day (year 2014) anthropogenic emissions of short-
lived climate forcers (SLCFs). Ref: IPCC, Chapter 6
 Spatial scales and relevant pollutants
• Microscale (10 to 100 m) and Middle-scale (100 to
500 m) – dust, traffic, hazardous pollutants.
• Neighborhood scale (500 m to 4 km) – vehicle
exhaust, residential burning, primary industrial
emissions.
• Urban scale (4 to 100 km) – ozone, secondary
sulfates and nitrates, forest fires, regional haze.
• Continental scale (1,000 to 10,000 km) – Asian and
Saharan dust, large scale fires.
• Global scale (> 10,000 km) – greenhouse gases,
halocarbons, black carbon.
Sources of emission data

Pollution levels can be grouped according to their emissions from the various different sources,
collectively call it as emission data, may be used in two ways

1. To identify the main sources of individual pollutants

2. To estimate levels of pollutants where such levels cannot be easily measured on
their own- in which case mathematical models based on emission data are employed

The variety of air pollution sources makes estimating the emissions of specific
atmospheric pollutants a demanding and time-consuming process. The basis of the
process is the systematic compilation of detailed information on pollutant emissions in a given area in the
form of an emission inventory.

An air pollutant emissions inventory is a schedule of the sources of an air pollutant or pollutants within
particular geographical area.

The inventory usually includes information on the amount of the pollutant released from major industrial
sources, as well as average figures for the emission from smaller sources and from transport throughout
the area.
Sources emission data

In an emission inventory, data are collected for the three types of sources (line, area and
point) within the selected geographical area.
Clearly, it is difficult/impractical to measure at each and every emission source
In a large area. The majority of the emissions are therefore estimated from other local
information such as fuel consumption figures, vehicle kilometers travelled or some other
activity relating to pollutant emissions.

Emission factors are then applied to the activity data in order to estimate the likely emissions.
It is a number that represents the relationship between the mass of a given pollutant emitted
from a particular sources and given amounts of raw material processed

This is given as

Activity rate X Emission factor= Emission rate

AIR POLLUTANTS

The substances which are responsible for causing air pollution are called air
pollutants.
Air pollutants can be categorized by various means:

A. Based on source of origin

B. Based on method of origin
C. Based on chemical composition
D. Based on state of matter

1. Natural air pollutants: Natural air pollutants are emitted from natural sources such as
volcanic activity, dust, sea-salt, forest fires, lightening, soil outgassing etc.

2. Anthropogenic air pollutants: These pollutants include the emissions from stationary
point sources (e.g. emission from industries), mobile sources (e.g. vehicular emission, marine
vessels, airplanes etc.), waste disposal landfills, controlled burning etc. 0
 B. Based on method of origin

1. Primary air pollutants: Those pollutants which are emitted directly from any
emission source in the atmosphere are termed as Primary air pollutants. E.g. Sulphur
dioxide (SO2), Carbon monoxide (CO), Lead (Pb), Ammonia (NH3) etc.

2. Secondary air pollutants: Secondary pollutants are formed by the reactions between
primary air pollutants and normal atmospheric constituents. In some of the cases, these
pollutants are formed by utilizing the solar energy. E.g. Ozone, Peroxyacetyl nitrate
(PAN), Nitrogen dioxide (NO2), Smog etc.

C. Based on chemical composition

1. Organic air pollutants: Examples are hydrocarbons, aldehydes, ketones,

amines, and alcohols etc.

2. Inorganic air pollutants: Examples are carbon compounds (CO and

carbonates), nitrogen compounds (NOX and NH3), sulphur compounds (H2S,
SO2, SO3, H2SO4), halogen compounds (HF, HCl etc.), flyash, silica etc.
D. Based on state of matter

1. Gaseous air pollutants: Pollutants which are in the form of gas are termed as
gaseous air pollutants. E.g. SO2, NOX, O3, CO etc.

2. Particulate air pollutants: Particulate air pollutants or particulate matter

(PM) can be defined as the microscopic solid or liquid matter suspended in the
earth’s atmosphere.

There are various subtypes of particulate matter:

a. Total suspended particulate matter (TSPM): The concentration of particulate

matter which is obtained when a high volume bulk sampling is done on a filter
substrate. It includes particles of all sizes.
b. PM10: These are the particles less than 10 µm in diameter.
c. PM2.5: These are the particles less than 2.5 µm in diameter.
d. PM1.0: These are the particles less than 1 µm in diameter.

Particles which lie between 10 µm to 2.5 µm are termed as Coarse

particles whereas particles with diameter less than 2.5 µm are called Fine
particles. Fine particles also include ultra-fine particles of size less than 0.1 µm
(PM0.1).
Some important pollutants related to air pollution and air quality
Major Classes of Air Pollutants
• Particulate Matter and other aerosol particles
• Nitrogen Oxides
• Sulfur Oxides
• Carbon Oxides
• Volatile Organic Compounds
• Ozone
• Carbon monoxide
• Other gases such as CO2 and methane (in direct role, but involves in
the chemistry)
Particulate Matter Composition
PM is composed of a mixture of primary and secondary compounds.

● Primary PM (directly ● Secondary PM (precursor gases that

emitted) form PM in the atmosphere)
• Suspended dust • Sulfur dioxide (SO2): forms sulfates
• Sea salt • Nitrogen oxides (NOx): forms nitrates
• Organic carbon • Ammonia (NH3): forms ammonium
compounds
• Elemental carbon
• Volatile organic compounds (VOCs):
• Metals from combustion form organic carbon compounds
• Small amounts of sulfate
and nitrate

29
AREP GAW, WMO Report
Particulate Matter Composition
Most PM mass in urban and nonurban areas is composed of a
combination of the following chemical components
• Geological Material – suspended dust • NaCl – salt is found in PM near sea
consists mainly of oxides of Al, Si, Ca, coasts and after de-icing materials are
Ti, Fe, and other metal oxides applied
• Ammonium – ammonium bisulfate, • Organic Carbon (OC) – consists of
sulfate, and nitrate are most common hundreds of separate compounds
containing mainly carbon, hydrogen, and
• Sulfate – results from conversion of SO2 oxygen
gas to sulfate-containing particles
• Elemental Carbon (EC) – composed of
• Nitrate – results from a reversible carbon without much hydrocarbon or
gas/particle equilibrium between oxygen. EC is black, often called soot.
ammonia (NH3), nitric acid (HNO3), and
particulate ammonium nitrate • Liquid Water – soluble nitrates,
sulfates, ammonium, sodium, other
inorganic ions, and some organic
material absorb water vapor from the
atmosphere

Chow and Watson (1997)

30
Major Classes of Air Pollutants
• Particulate Matter and other aerosol particles
• Nitrogen Oxides
• Sulfur Oxides
• Carbon Oxides
• Volatile Organic Compounds
• Ozone
• Carbon monoxide
• Other gases such as CO2 and methane (in direct role, but involves in
the chemistry)
Particulate Matter (PM) pollution consists of tiny particles or droplets in the air that can be harmful to
human health and the environment.

Some particles, such as dust, dirt, soot, or smoke, are large or dark enough to be seen with the naked eye.
Others are so small they can only be detected using an electron microscope.

These particles vary in size and composition, but they are commonly classified into two categories based
on their diameter:

1.PM10: Particles with a diameter of 10 micrometers or smaller. These can be inhaled and cause
respiratory issues but are generally filtered by the nose and throat.

2.PM2.5: Finer particles with a diameter of 2.5 micrometers or smaller. These can penetrate deep into the
lungs and even enter the bloodstream, causing more severe health problems.

Sources of Particulate Matter:

Particulate matter pollution originates from various sources, both natural and human-made:

•Natural Sources: These include dust storms, wildfires, volcanic eruptions, and sea spray.

•Human-Made Sources: These are mainly due to industrial activities, vehicle emissions, construction,
agricultural practices, and the burning of fossil fuels like coal and oil.
Primary is a direct emission source and forms a significant portion of the PM pollution.
This comprises of metals, elemental carbon (also known as black carbon), and organic
carbon.

Other primary pollutants include sulfur dioxide, nitrogen oxides, volatile hydrocarbons,
methane, carbon monoxide, and carbon dioxide — all which are in the gaseous form.

Secondary is due to chemical transformation of primary gaseous emissions.

In PM, the secondary aerosol components include sulfates from sulfur dioxide emissions,
nitrates from nitrogen oxide emissions, organic aerosols from hydrocarbon emissions, and
ammonium from ammonia emissions.
The path and the quantity of chemical transformation depends on the strength of the
pollutant emissions and the mix of the emissions. In an atmospheric chemical mechanism,
these interlinkages can run into 300+ equations.
Other secondary pollutants include ozone (in the gaseous form) – a result of a mix of
reactions between NOx and VOC emissions in the presence of sunlight.
Particulate Matter is a mixture of solid, liquid or solid and liquid
particles suspended in the air.

These suspended particles vary in size, composition and origin.

It is convenient to classify particles by their aerodynamic

properties (size, shape, and density) because:

Ø they govern the transport and removal of particles from the air;
Ø they also govern their deposition within the respiratory system;
and
Ø they are associated with the chemical composition and sources
of particles.

Particles are sampled and described on the basis of their

aerodynamic diameter, usually called simply the particle size.
Effects of Particulate Matter Pollution:

Health Effects:

•Respiratory and Cardiovascular Problems: PM pollution can cause or exacerbate conditions

like asthma, bronchitis, heart attacks, and strokes. Fine particles (PM2.5) are particularly
harmful as they can penetrate deep into the lungs and even enter the bloodstream, leading to
severe health issues.

•Premature Death: Long-term exposure to high levels of PM2.5 is associated with an increased
risk of premature death due to cardiovascular and respiratory diseases.

•Cancer: Some components of particulate matter, such as polycyclic aromatic hydrocarbons

(PAHs), are carcinogenic and can increase the risk of developing cancer.
Environmental Effects:

•Air Quality Degradation: PM pollution reduces visibility, leading to haze and smog in urban and rural
areas.

•Soil and Water Contamination: When particulate matter settles, it can contaminate soil and water
bodies, affecting ecosystems and agricultural productivity.

•Climate Change: Particles like black carbon absorb sunlight and contribute to global warming by
increasing the temperature of the atmosphere. They can also alter weather patterns and affect cloud
formation.

Economic Effects:

•Healthcare Costs: The health impacts of PM pollution lead to increased healthcare costs due to the
treatment of diseases and lost productivity.

•Agricultural Losses: Crop yields can be affected by particulate matter deposition, reducing
agricultural output and impacting food security.
Particulate matter pollution results primarily from combustion, including industrial activities, vehicles, and
wildfires.

It is classified according to the size of its particles, the smaller categorization of which — PM2.5 — accounts
for much of the pollutant’s detrimental effect on human and environmental health.

Although the effects of PM are well studied, it remains in excess of benchmark levels for a large majority of
the world’s population, prompting the need to take action in order to achieve cleaner air.

Particulate matter is not composed of a single substance, but rather a combination of solid and liquid particles
such as dust, pollen, ash, soot, dirt, and smoke. Some of these particles may be visible, such as by the
appearance of haze, and others are too small to see with the naked eye.

Particulate matter is commonly divided into four categories based on the size of its particles: Coarse, PM10,
PM2.5, and PM1. Coarse PM particles are 10 micrometers (μm) or bigger, while PM 10 and PM2.5 consists
of particles that are 10 or 2.5 μm or smaller in diameter, respectively. Both PM10 and PM2.5 are
considered inhalable particles, meaning that they are small enough to be inhaled deep into the lungs.
Particulate Matter Size
• PM is classified by size and composition
• Diameter < 2.5 µm: fine PM
• Formation
• Coagulation of smaller particles
• Condensation of gases on smaller particles
• Much fine PM is a secondary pollutant
• Removal
• Sedimentation (removal by gravity) is slow
• Main removal mechanisms: scavenging, coagulation
• Effects
• More important in atmospheric chemistry
• More important in terms of health effects
• Diameter > 2.5 µm : coarse PM
• Formation
• Mechanical breaking up of larger particles
• Both natural and direct anthropogenic sources
• Removal by sedimentation is rapid
 Particulate Matter Composition
PM is composed of a mixture of primary and secondary compounds.

● Primary PM (directly ● Secondary PM (precursor gases

emitted) that form PM in the atmosphere)
• Suspended dust • Sulfur dioxide (SO2): forms
• Sea salt sulfates
• Organic carbon • Nitrogen oxides (NOx):
forms nitrates
• Elemental carbon
• Ammonia (NH3): forms
• Metals from ammonium compounds
combustion
• Volatile organic compounds
• Small amounts of (VOCs): form organic
sulfate and nitrate carbon compounds
40
AREP GAW, WMO Report
 Particulate Matter Composition
Most PM mass in urban and nonurban areas is composed of a
combination of the following chemical components
• Geological Material – suspended • NaCl – salt is found in PM near sea
dust consists mainly of oxides of Al, coasts and after de-icing materials
Si, Ca, Ti, Fe, and other metal are applied
oxides
• Organic Carbon (OC) – consists of
• Ammonium – ammonium bisulfate, hundreds of separate compounds
sulfate, and nitrate are most common containing mainly carbon, hydrogen,
and oxygen
• Sulfate – results from conversion of
SO2 gas to sulfate-containing • Elemental Carbon (EC) –
particles composed of carbon without much
hydrocarbon or oxygen. EC is
• Nitrate – results from a reversible
black, often called soot.
gas/particle equilibrium between
ammonia (NH3), nitric acid (HNO3), • Liquid Water – soluble nitrates,
and particulate ammonium nitrate sulfates, ammonium, sodium, other
inorganic ions, and some organic
Chow and Watson (1997)
material absorb water vapor from the
atmosphere
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Classification system used to assess spatiotemporal PM2.5 risk across the globe during 1998–2016. Ref: Lim et al, 2020
Map showing regional or country average source apportionments for PM2.5. Ref: Hopke et al., 2020
Map showing regional or country average source apportionments for PM10. Ref: Hopke et al., 2020