AIR POLLUTION

1. Concepts and scales of air pollution

INDEX
2. Atmosphere

3. Air pollutants
Estibaliz Saez de Camara Oleaga
Faculty of Engineering Bilbao (UPV/EHU) 4. Dispersion of air pollutants

Department of Chemical and Environmental Engineering 5. Industrial emissions reduction

2
Contact: estibaliz.saezdecamara@ehu.eus

ESTIBALIZ SÁEZ DE CÁMARA OLEAGA

AIR POLLUTION is “an atmospheric condition in which
substances are present at concentrations higher than their
normal ambient levels to produce measurable adverse
effects on humans, animals, vegetation, or materials”
Seinfeld, 1986

Lesson 1
CONCEPTS AND SCALES OF AIR AIR POLLUTION is “the presence of materials, substances
or energy-sources in the air that can harm public health,
POLLUTION ecosystems, crops, materials or anything that society
values” Spanish Law 34/2007 on Air Quality and Protection of
the Atmosphere
4
 EMISSION is the continuous or discontinuous release of
substances or energy, directly or indirectly, from a source into
the environment
Atmosphere
• Highly mobile fluid
• Unconfined
• Random motion

… Air pollution is
present everywhere
(urban and industrial
areas + remote areas)
IMMISSION or AIR QUALITY relates to the effects of
emissions on the environment. It expresses the concentration
5 of the pollutants in ambient air for a given period of time. 6

1.1. ELEMENTS OF AIR POLLUTION

Anthropogenic sources Natural sources

2. Medium

NATURAL SOURCES mean “emissions of pollutants not

caused directly or indirectly by human activities, including
natural events such as volcanic eruptions, seismic activities,
geothermal activities, wild-land fires, high-wind events, sea
sprays or the atmospheric re-suspension or transport of
natural particles from dry regions” Directive 2008/50/EC of 21 3. Receptors
May 2008 on ambient air quality and cleaner air for Europe 7
1. Sources 8
 The places from which pollutants emanate are called SOURCES.
Pollutants are emitted to the atmosphere by a range of sources.
CLASSIFICATION
1. ORIGIN
• Natural sources: not caused directly or indirectly by human
activities such as volcanoes, dust storms, oceans,…
• Anthropogenic sources: caused by human activities such as
automobiles, heating systems, industrial processes,…
2. MOBILITY
• Fixed or stationary sources: sources that do not move such as
factories, power plants, …
• Mobile sources: sources capable of moving under their own
power such as automobiles, airplanes, trains, ships...
3. GEOMETRY
• Area sources: many small sources of air pollution located together
such as residential wood burners.
• Linear sources: idealized geometric emitters, which can be
represented by a simple line such as a roadway, railway or aircrafts.
• Point sources: single, identifiable sources which are located by the
geographic coordinates such as power stations, oil refineries, paper
mills,…
4. CONTROL/ MANAGEMENT
• Controlled emissions: identified and managed sources
• Fugitive, uncontrolled or diffuse emissions: emissions escaping
from regulated processes.

The atmosphere serves as the MEDIUM through which air

pollutants are transported and transformed, both by physical
and chemical reactions.

Transport is the mechanism that moves the pollution from a source

to a receptor. The wind is the means by which the pollution is
transported from a source to a receptor. However, during this
transit from a source to a receptor, due to diffusion, mixing by
turbulence and some other processes (gravitational settling or wet
removal), tend to make the concentration of the plume as it arrives
at the receptor less than its concentration on release.
In addition to removal by physical processes, pollutants can
undergo chemical transformations. Oxidation is a prime chemical
transformation from organic as well as inorganic gases. 11 12
Sooner or later, the pollutants are removed from the atmosphere.
The places from which pollutants disappear from the air are
called SINKS.
Sinks include soil, vegetation, structures, and water bodies.
A RECEPTOR is something which is adversely affected by
polluted air.
A receptor may be a person or animal that breathes the air. It may
be a tree or a plant that dies. It may also be some material such as
leather, cloth, metal, stone or paint adversely affected.
The location of receptors relative to sources and atmospheric
conditions affect the dose received; the sensitivity of receptors to
these doses determines the effects.
Relationship between the rate constant, half-lives and
lifetimes for first- and second-order reactions
If we could follow all the individual molecules of a substance
emitted into the air…. some might be removed close to their point
of emission… others might get carried high into the atmosphere
and be transported a great distance before they are ultimately
removed. Averaging the life histories of all molecules of a
substance yields an average lifetime or average residence time (tR)
for that substance. 15
Half-life and life-time
The measurements used for the aging of a pollutant are the half-
life and lifetime.
HALF-LIFE (t1/2) is the time it takes for one-half (1/2) of the
quantity of a pollutant emitted from a source to disappear into
its various sinks.
LIFETIME (ζ) is defined as the time it takes for quantity of a
pollutant emitted from a source to fall to 1/e of its initial value.
Both are related to the rate constant and to the concentration of
14
any other reactants involved in the reactions.
If the rate of injection of all the sources of the substance is
balanced by its sinks (S=F), the total mass of the substance (M)
does not change with time.
Under these steady-state conditions, the average lifetime or
average residence time is given by:
Where: M= substance concentration in the atmosphere [M]
F = rate of removal [M·T-1]
S= rate of introduction from sources [M·T-1]
16
Depending on their atmospheric lifetime, pollutants can exhibit an
enormous range of spatial and temporal variability.
Long-lived species
Short lived species
1.2. SCALES OF AIR POLLUTION
Air pollution phenomena are decisively influenced by atmospheric
processes which are commonly classified with regard to their
spatial and temporal scale.

Relatively long-lived species are uniformly distributed. As species’

lifetimes become shorter, their spatial and temporal distributions
become more variable.
Most pollutants have a short enough residence time (hours -10
days) to prevent their accumulation in the air. However, several
gases do appear to be accumulating in the air to the extent that
measurements have documented an increase in their concentration
from year to year. The best known example is the CO2.
17 18

Local scale

The characteristic length is < 5 km.

The sources and receptors can be easily identified.
In general, air flow is very complex at this scale, as it depends
strongly on the surface characteristics: topography, buildings,…

CO emitted from motor vehicles lead to 19

Correlation between CO concentration and traffic pattern in 20
high concentrations near roadways New York. Source: Johnson. Science (1968)
 Urban scale
This extends to the order of 50 km (horizontally) and 1-2 km
(vertically). Air pollution problems in urban areas are of two types:
1. Release of primary pollutants such as CO, NOx and/or PM
2. Formation of secondary pollutants such as tropospheric ozone.
In urban areas pollution
events and episodes can
be registered when the
atmospheric conditions
slow down ventilation.
Photochemical smog 21
23
Regional scale. Mesoscale
The characteristic lengths are between 50 km and 1000-2000 km.
At least two types of problems contribute to pollution at this scale:
1. Reactions between urban oxidants in metropolitan areas
2. Relative slow-reacting primary pollutants undergo reactions and
transformations worsening the air quality of background and
remote areas.
For example, the sulfur dioxide (SO2) and nitrogen oxides (NOx)
released through combustion are oxidized during long-distance
transport and then these oxides react with water vapor to form
sulphuric acid (H2SO4) and nitric acid (HNO3) and finally, sulphate
(SO42-) and nitrate (NO3-) particles. They can precipitate and
contribute to acid rain.
22
Global scale
It extends worldwide.
The atmospheric flow is associated with synoptic phenomena.
Several observations demonstrate the effects of the long-range
transport associated to this scale:
• Polychlorinated biphenyls (PCBs) observed in arctic mammals,
thousands of miles from their sources.
•Distribution in the stratosphere of gases and aerosols from
explosive volcanic eruptions
• Chlorofluorocarbons (CFCs) used as propellants in spray cans and
their effect in the ozone layer high in the atmosphere.
• Climate change generated by excessive amounts of greenhouse
gases (GHG), especially methane (CH4) and carbon dioxide (CO2). 24
 SeaWiFS image of ash plume
from eruption Etna, Sicily
on July 22, 2001

Ash plume from Eyjafjallajokull volcano over the

North Atlantic on April 17, 2010; captured by the
26
PCBs in polar bears, from fat samples
25
MODIS instrument on NASA’s Aqua satellite

SeaWIFS images showing a

massive Saharan Dust Storm
blanketing the Canary Islands
off the northwest coast of
Africa on February 26, 2000

Saharan soil dust can be transported across the Atlantic ocean to the The ozone hole is the region over Antarctica on October 4,
Caribbean and North America. 27
2004
28
Is it the A chlorine atom in the stratosphere can destroy up to 100000
ozone ozone molecules.
good or
bad?

good

bad

29 30

Ozone concentration in the atmosphere

The data from Mauna Loa (Hawaii) show that even in the 1950s the
CO2 concentration had increased from the baseline of 280 ppm
(preindustrial value) to 315 ppm and this has continued to climb over31
CO2 seasonal cycle. CO2 level rose from about October to May, and
it fell a little less about every May to October. This fluctuations are
stronger in northern hemisphere.
32

the last 50 years at a nearly constant rate of about 1.6 ppm·year -1

1.3. PRIMARY AND SECONDARY POLLUTANTS Chemical reactions may occur among the primary pollutants and
the constituents of the unpolluted atmosphere.

The pollutants manufactured in the air are called SECONDARY

PRIMARY AIR POLLUTANTS are emitted directly into the POLLUTANTS.
atmosphere from sources.
They are not directly emitted but they form when primary pollutants
A substantial portion of the gas and vapors emitted to the react in the atmosphere.
atmosphere tends to be relatively simple in chemical structure. Example Ozone (O3)
Examples Carbon dioxide (CO2) It is the result of the reactions between the nitrogen
Carbon monoxide (CO) oxides (NOx) and Volatile Organic Compounds (VOC) in
Sulphur dioxide (SO2) the presence of solar radiation.
Nitrogen monoxide (NO) The primary pollutants that react are termed the PRECURSORS
Hydrogen sulphide (H2S) of secondary pollutants.
Ammonia (NH3) 33 34

Chlorhidric acid (HCl)

Ambient air quality

The concentration of criteria pollutants in the ambient air is

referred to as ambient air quality.

AMBIENT AIR QUALITY STANDARDS prescribe pollutant levels

that cannot legally be exceeded during a specific time period in
a specific geographic area.

Europe:
http://ec.europa.eu/environment/air/quality/standards.htm
USA:
https://www.epa.gov/criteria-air-pollutants/naaqs-table
WHO guidelines:
35 36
http://www.who.int/mediacentre/factsheets/fs313/en/
 The most recent report of the European Environmental Agency
ESTIBALIZ SÁEZ DE CÁMARA OLEAGA
(EEA) about 'Air quality in Europe' affirms that “Despite falling
emission levels and reductions of some air pollutant concentrations
in recent decades, air pollution problem is far from solved. Two
specific pollutants, particulate matter and ground-level ozone,
continue to be a source breathing problems, cardiovascular disease
and shortened lives”
“Estimates of the health impacts attributable to exposure to air
pollution indicate that PM2.5 concentrations in 2015 were
responsible for about 422.000 premature deaths originating from Lesson 2
long-term exposure in Europe. The estimated impacts on the
population in European countries of exposure to NO2 and O3 ATMOSPHERE
concentrations in 2015 were around 79.000 and 17.700 premature
deaths per year, respectively.”
37

The ATMOSPHERE composes the layer of mixed gases covering 2.1. STRUCTURE
the Earth’s surface.

More than the 99% of the total mass of the atmosphere is

found within approximately 20 km of the Earth’s surface The Earth’s atmospheric
pressure (density) varies
with altitude, as does the
temperature.

Compared with the average radius of the 39 40

Earth, it is an incredibly thin layer.

 According to the homogeneity of atmospheric composition, two
More than the 99% of the total mass of the atmosphere is found layers can be defined:
approximately within 20 km of the earth's atmosphere.
• Homosphere
The lower layer, up to an
altitude of 80-100 km
Due to continuous turbulent
mixing the composition is

Altitude (km)
relatively constant.
• Heterosphere
Above 80-100 km
Chemical composition becomes
stratified and varies according to
the molecular mass of chemical
% of total mass of air below 41 species (N2, O2 → H2, He, …) 42

Atmospheric Boundary Layer

Using temperature as the basis, the atmosphere is divided into 4
layers:
The lowest layer of the troposphere is called the Atmospheric
•Thermosphere > 85 km Boundary Layer.
T increases with altitude because O2 and N2 absorb UV radiation
Atmospheric Boundary Layer (ABL) is the part of the
• Mesosphere 50-85 km
troposphere that is directly influenced by the presence of the
T decreases with altitude.
Earth’s surface, and responds to surface forcing with a time
Absorption and scattering of solar radiation.
scale of about an hour or less
• Stratosphere 12-50 km
T increases with altitude as O3 absorbs UV radiation. O3 layer 25-32 km.
Global transport of air pollution Characteristics ≈ 1000-1500 m deep.
Temperature profile varies. Diurnal cycle.
• Troposphere
Ii is influenced by surface friction & heat fluxes.
It extends from the surface to 12 km (tropopause)
There is turbulence.
T decreases with altitude 43 44

It is the primary focus of air pollution

 2.2. COMPOSITION

The average gaseous composition of unpolluted tropospheric air is

Diurnal cycle of Atmospheric Boundary Layer
given in next table.
Exclusively of water, atmospheric air is 78% nitrogen, 21% oxygen,
0.9% argon and 0.03% carbon dioxide.
Unpolluted air or clean air is a theoretical concept; what the
composition of the air would be if humans and their influences
were not on Earth. We will never know the precise composition of
unpolluted air because by the time we had the means and the
desire to determine its composition, humans had been polluting
the air for thousands of years. Now, even at the most remote
locations at sea, at the poles, and in the deserts and mountains, the
45 air may be best described as dilute polluted air. 46

The gaseous composition of unpolluted or clean air (dry base)

(T=293.15 K, P=101325Pa)
UNIT CONVERSION
ppm (mL/m3) μg/m3
N2 780840 9.085·108
O2 209460 2.78·108 It is common practice to express the concentration of gaseous
H2O - - pollutants present in the air as parts per million, parts per billion
Ar 9340 1.55·107 and parts per trillion in volumetric basis. The concentration of
CO2 379 6.93·105 pollutants as a mass basis is commonly expressed as milligrams,
Ne 18.18 15245 micrograms or nanograms per cubic meter of air.
He 5.24 872
CH4 1.7 1130
Kr 1.0 3482
N2O 0.3 549
H2 0.5 42
Xe 0.08 436
47 48
Org. vapours 0.02 -
 UNIT CONVERSION UNIT CONVERSION

Assuming that the pollutant gas behaves as an ideal gas, at given If P is taken as 101.3 kPa (1 atm) and T as 25ºC (298.15 K),
pressure and temperature the relationship between ppm and reducing the equation, for 1 mol, V is 24.5 L; then, the basic
milligrams per cubic meter is found from: relation between the concentration (C) in mg·m-3 and a ppm is:

Where: P= pressure (atm)

T= temperature (K)
V= volume (L) The concentration C at other conditions can be determined by
n= moles multiplying the constant by the appropriate ratio of temperatures
MW= molecular weight (g·mol-1) and pressures according to the Ideal Gas Law.
R= 0.082 atm·L·mol-1·K-1 49 50

Conversion factors between volume and mass units

UNIT CONVERSION of concentration (T=293 K, P =101325 Pa)

According to Annex VI (Reference methods for assessment of

concentrations…) of Directive 2008/50/EC on ambient air quality
and cleaner air for Europe:

C. STANDARIZATION

For convenience, the molecular mass and conversion units for

common pollutants are shown in next table. 51 52
 2.3. ENERGY BALANCE
UNIT CONVERSION

The Earth receives most of its energy from the sun.

A common standardized volume in air
pollution is the normal cubic meter The total solar flux is 3.9·1026 W.
(Nm3). A normal cubic meter of gas The sun radiates as a blackbody with an effective T of 6000 K. Using
corresponds to 1 cubic meter at Wien’s Law, it has been found that the maximum intensity occurs at

Nm3 standard conditions.

It is important to list the temperature
and pressure being used as standard,
0.5 μm (VIS).

since many standards are used

worldwide.
Where λ =wavelength
Internationally, Nm3 typically refers to T= temperature of the body
0°C (273.15 K) and 101.325 kPa. 53 54

0.5 µm
The intensity of this energy flux at the distance of the Earth is about
2 cal·cm-2min-1 on an area normal to a beam of solar radiation,
approximately, ≈ 1370 W·m-2. This value is the solar constant.

10-11 µm

This incoming solar radiation (1370 W·m-2) is spread over surface of

Spectrum of the incoming solar radiation (short wavelength) and 55 rotating Earth: 56

the outgoing terrestrial radiation (long wavelength)

 24 h This average radiant energy reaching the outer limits of the
atmosphere is depleted as it attempts to reach the Earth’s surface,
by absorption by molecular oxygen (O), ozone (O3) and water vapor,
scattering and reflection to space by clouds. With average
cloudiness, about the 50% of the incoming radiation (168 W·m-2)
beam of
solar reaches the Earth’s surface.
radiation Because most UV radiation is absorbed, the peak of solar radiation
which reaches the Earth’s surface is in the visible part of the
spectrum. The Earth re-radiates as a blackbody at a mean T of 290 K.
The maximum intensity occurs at 10-11 μm (IR).
Disc of radius R Sphere of radius R
Area π R2 Area 4 π R2 As this radiation tries to reach outer space, primarily water vapor
1370 W·m-2 1370 W·m-2 /4= 342 W·m-2 and several gases in the atmosphere (GHG) absorb and reemit it.
This natural effect is referred as the greenhouse effect. Without this
The average energy reaching the top of the atmosphere is 342 W·m57 -2. greenhouse effect, the Earth would be quite different (T=-18ºC). 58

2.3.1. Greenhouse effect

The gases with absorptive wavelengths in the spectrum of the

terrestrial radiation, but transparent to most of the solar
radiation, are called GREENHOUSE GASES (GHG)

Energy fluxes in the atmosphere
The molecules which absorb both solar radiation (O3 and water
vapor) and terrestrial radiation (water vapor, CO2 and O3) more
intensely, are the less abundant ones. See next slide.
Thus, a slight increase in the concentration of any of these GHG
greatly limits the amount of heat transmitting into space, thus
promoting the warming of the atmosphere and climate change.
59 60
 61 62

Radiation transmitted by the atmosphere

Concentrations of CO2 and CH4, insolation and air temperature at

Global average atmospheric concentrations of some of the 63
Vostok station (Antarctica) during the last four glacial-interglacial 64
major greenhouse gases from 1978 to 2017
cycles
According to Intergovernmental Panel on Climate Change (IPCC)
“Global atmospheric concentrations of CO2, CH4 and N2O have
increased markedly as a result of human activities since 1750 and
now far exceed pre-industrial values”.
“Most of the observed increase in global average temperatures
since the mid-20th century is very likely due to the observed
increase in anthropogenic GHG concentrations; mainly, CO2, CH4,
N2O and fluorinated gases”.
The panel stated that “warming of the climate system is
unequivocal, as is mow the evident from observations of increases
in global average air and ocean temperatures, widespread
melting of snow and ice and rising global average sea level.”
65 66

ESTIBALIZ SÁEZ DE CÁMARA OLEAGA

POLLUTANT is “any substance present in the air and likely
to have harmful effects on human health and/or the
environment as a whole” European Directive 2008/50/EC on
ambient air quality and cleaner air for Europe

The most common gaseous air pollutants are inorganic, mainly

oxides of nitrogen (N2O, NO and NO2), oxides of sulphur (SO2) and
oxides of carbon (CO).
Lesson 3
Some other air pollutants of concern are hydrocarbons such as
AIR POLLUTANTS methane (CH4), Volatile Organic Compounds (VOCs) and
Particulate Matter (PM).

68
 3.1. CARBON MONOXIDE (CO) Lifetime ≈ 30 - 90 days
Background concentration ≈ 0.2 - 50 ppm (hourly average)
As it is stable, CO is one of the most abundant and widely
Characteristics
distributed air pollutants.
CO is a colorless, odorless, inflammable and toxic gas.
Sources and sinks
Global CO sources: oxidation of CH4 by ·OH radicals, biomass
burning, wildfires and the oxidation of non-methanic
hydrocarbons (NMHC).
CO sinks: Oxidation by ·OH radicals to CO2. It is also lost by
deposition to soils.

69 70

Sources and sinks of CO in Tg CO·year-1

sources
Vegetation 60-160
Oceans 20-200
Oxidation of CH4 400-1000
Oxidation of NMHC 200-600
Biomass burning 300-700
Fossil and domestic fuel 300-550
sinks
Surface deposition 250-640
OH reaction 1500-2700

It is produced by both natural and anthropogenic sources. The

major source of anthropogenic CO is the incomplete combustion of
fuels containing carbon. CO emissions in the EU-28: (a) trend in CO emissions from the five
71
most important key categories, 1990–2014; (b) share of emissions by
sector group, 2014
In urban areas one of the main source of CO is incomplete
Modern automobiles use catalytic exhaust reactors to cut down on
combustion of fossil fuels in vehicles with internal combustion
CO emissions by pumping excess O2 into the exhaust gas, resulting
engines. Thus, the highest levels of this toxic gas tend to occur in
in oxidation of CO to CO2. They also convert nitrogen oxides (NOx)
congested urban areas in rush hours, when the ↑ number of people
and hydrocarbons (HC) to less harmful nitrogen (N2), carbon di-
are exposed.
oxide (CO2) and water (H2O).

73 74

Catalytic converter

The introduction of catalytic converters has reduced CO emissions

significantly.

European emission standards for vehicles, from Euro-1 to Euro-6 75

Development in EU-28 emissions, 2000-2016 (% of 2000 levels)

 3.2. SULPHUR DIOXIDE (SO2) The source of anthropogenic SO2 is the combustion of sulphur-
carrying coal-fired power plants.
Characteristics
SO2 is a colorless, non-flammable and non-explosive gas.
Lifetime ≈ 3 days
Ambient concentration 1 ppb - 2 ppm (24-hour average)
[SO2] > 0.3-1 ppm → taste SO2 > 3 ppm → pungent odor
Its main air pollution effects: formation of PM and acid rain
Sources and sinks
SO2 is produced chemically from carbonile sulphide (COS),
hydrogen sulphide (H2S) and dimethyl sulphide (DMS). DMS is In recent decades the amount of SO2 being released into the
emitted by phytoplankton and other marine organisms. atmosphere has been reduced due to the decreasing use of coal
for power generation and its replacement by natural gas and
SO2 sink: Homogeneous and heterogeneous oxidation
77 cleaner fuels. 78

The largest reduction of emissions from 2000-2016 of main

primary pollutants and precursors corresponds to SO2 (>72%).

SOX emissions in the EU-28: (a) trend in SOX emissions from

the five most important key categories, 1990–2014; (b) share 79 Development in EU-28 emissions, 2000-2016 (% of 2000 levels) 80

of emissions by sector group, 2014

Gas phase oxidation of S (VI) Aqueous phase oxidation of S (VI)

The free radicals produced from the degradation of hydrocarbons
(hydroxyl radical ·OH) oxidize SO2 to reactive intermediates such as
bisulfite ion (HSO3-) and sulphur trioxide (SO3).
These intermediates combine rapidly with water vapor to form
sulphuric acid (H2SO4), which can fall to Earth as acid rain or form
fine sulphate particles: SO4-2 (s).
Whereas the homogeneous oxidation by free radicals is the
dominant mechanism when the relative humidity is < 70 % (dry
atmospheres), the heterogeneous mechanism produces more
rapidly S(VI) from S(IV) in cloud and rain droplets.
This involves the transport and dissolving of SO2 in water droplets,
with the subsequent chemical reactions in the water phase.

SO2(g) + ·OH + M → HSO3- (g) • Dissolution of SO2 (g) into liquid-water drops to produce
dissolved sulphur dioxide: SO2 (aq).
HSO3(g) + O2(g) → SO3 (g) + ·HO2 (g) • In-drop conversion of dissolved sulphur dioxide SO2 (aq) to
sulfurous acid H2SO3 (aq) and dissociation of H2SO3 (aq) to
SO3(g) + H2O(g) → H2SO4 (g) bisulfite ion (HSO3-) and sulfite ion (SO32- )
This oxidation mechanism is dominant in urban polluted areas
81 • In-drop oxidation of HSO3- and SO32- to sulphates (SO42-). 82

during daytime.

Thus, SO2 contributes notably to acid deposition (dry or wet).

Oxidants
Oxygen (O2)
Ozone (O3)
Hydrogen peroxide (H2O2)

Heterogeneous oxidation of the SO2 83 84

 3.3. OXIDES OF NITROGEN
The oxides of nitrogen most commonly found in the atmosphere are
the nitrous oxide (N2O), nitric oxide (NO) and nitrogen dioxide (NO2).
N2O, a commonly used anesthetic known as “laughing gas”, is
produced mainly by natural processes. It is relatively unreactive
(lifetime≈120 years) and does not significantly influence important
chemical reactions in the lower atmosphere. However, it is one of
the main contributors of the Greenhouse effect and the depletion of
the ozone layer.
NO and NO2 are referred together as NOx due to their inter-
convertibility in photochemical reactions. NO is a colorless, odorless,
non flammable and toxic gas. NO2 is a reddish-brown gas with a
pungent odor. The average concentrations are 0.02-1000 ppb and85 1
ppb-0.5 ppm (hourly average), respectively.
PHOTOLYSIS or PHOTOCHEMICAL DISSOCIATION is a process
in which the sunlight causes transformations of compounds
Photolysis can be considered a two-step process. The absorption of a
photon of energy by species A leads to an excited state A*.
A + hv →A*
This is followed by the dissociation of A* into two products such as
A* → B + C
Either B or C may be really reactive. e.g. Free radicals Hence they
bring about a chain of reactions which culminate in the undesirable
air pollutants.
87
Sources and sinks of NOx
NO is emitted naturally by microorganisms in soils, by natural
combustion processes and storms with lightning strikes. Nevertheless,
the major NO sources are anthropogenic. Well over 90% of all the
man-made nitrogen oxides are formed when oxygen (O) in the air and
nitrogen (N) in the fuel react at high temperatures during combustion:
N2 + O2 → 2NO
NO tends to oxidize to NO2 in a few seconds via the following
homogeneous reaction:
2NO + O2 → 2NO2
Their main air pollution effects: smog and acid rain
During the day, the NO2 undergoes photolysis. This reaction is one of
the most important photochemical reactions in the lower
atmosphere, since it produces highly active O, which regenerates
86
tropospheric ozone (O3) and nitric oxide (NO).
NO2 photolytic cycle
NO + O3 → NO2 + O2 ka
NO2 + hν → NO + O(3P) kb
O2 + O + M → O3 + M kc
All three reactions noted above are very fast, and the
combination would tend to maintain at steady-state a constant
and low level of ozone. The photostationary state expression for
ozone is:
During the daytime, NO2 can be removed slowly from the
photostationary state cycle, as it reacts with hydroxyl radicals
(·OH), producing nitric acid (HNO3) and then, nitrates: NO3- (s). 88
 Like sulphuric acid, nitric acid (HNO3) contributes to aerosol
formation -nitrates: NO3- (s)- and acid deposition.

NOX emissions in the EU-28: (a) trend in NOX emissions from

the five most important key categories, 1990–2014; (b) share 89 90

of emissions by sector group, 2014

3.4. HYDROCARBONS Methane is a colorless gas,

odorless at low concentrations
but with a sweetish
On a global scale most hydrocarbons (HC) are emitted from natural chloroform-like odor at high
sources, principally vegetation and the decomposition of organic concentration. It is the most
matter by bacteria. Anthropogenic sources contribute to a long-lived (≈ 9-10 years),
considerably less significant fraction of total ambient HC. simple and abundant HC in the
atmosphere (≈ 1.7 ppm)

CH4
Effects
CH4 has a negligible photochemical activity. As it is orders of
HC magnitude less reactive than other HC it is usually excluded from
the reports, which refer to non-methane hydrocarbons (NMHC).
The main environmental concern with CH4 is the role it plays as a
VOC greenhouse gas.
91 92
Sources
Methane is emitted by natural sources such as decomposition of
plant and animal matter by methane producing bacteria, cud-
chewing animals, rice paddies and wetlands. The anthropogenic
sources are farming, production of fossil fuels, wet rice cultivation,
biomass burning and landfills.
Volatile Organic Compounds (VOC) shall mean “organic
compounds from anthropogenic and biogenic sources,
other than methane, that are capable of producing
photochemical oxidation by reactions with nitrogen oxides
in the presence of sunlight” Directive 2008/50/EC on ambient
air quality and cleaner air for Europe

On a global scale natural VOC emissions are predominant, mainly

vegetation.
However, on a local scale, anthropogenic emissions can be ≥ than
the natural ones. VOC come from a variety of sources including
solvent usage, combustion (motor vehicles) and fuel storage and
transport, among others.
Sink 93 94

Oxidation by hydroxyl radical

The relative abundance and frequency of the VOCs depends on

their reactivity. Their reactivity differs because of their chemical
structure and molecular weight. VOCs have been ranked according
to their rate of reaction with various types of oxidizing species.

Short-lived VOCs interact

with NOx to produce
photochemical smog

NMVOC emissions in the EU-28: (a) trend in NMVOC emissions from the
five most important key categories, 1990–2014; (b) share of emissions by
sector group, 2014 95 Rate constants and approximate lifetimes of the less 96

reactive VOCs. CO is included for comparisons.

 3.4.1. Photochemical smog NO net formation Net formation of
of ozone ozone

The term smog is a shorthand combination of “smoke-fog”. It is code

word for photochemical oxidant smog.
Smog is characterized by a relatively high level of oxidants, which
irritate the eyes and throat and damage plants.
Photochemical smog forms when NOx and VOCs react in the
presence of solar radiation. It initiates when VOCs photolyze or they
are oxidized by different compounds to produce radicals. These
radicals convert NO to NO2, which photolyzes to O, which reacts
with O2 to form ozone (O3) and other oxidation products.
Of all these oxidation products O3 is the most notorious one due to
Schematics of the reactions involved in NO-to-NO2 conversion
the high levels and its effects on human health, plants and materials.
and ozone formation. a) in the absence of VOCs and b) in the
97
presence of VOCs 98

The atmosphere can be considered a huge photochemical reactor

in which the main inputs are the atmospheric pollutants (both from
natural and anthropogenic origin); the energy-source is the solar
radiation; and the main outputs are the oxidants.

99 100
Generalized scheme for the photochemical smog Time concentrations of the precursors and components of photochemical smog
Emissions of the main ground-level ozone precursor pollutants have 3.5. AEROSOLS
decreased over the last decades. However, no (or little) ozone
decrease has occurred generally over Mediterranean Europe.
In addition to gases, the atmosphere contains a mixture of small
(0.001-100 μm) liquid and solid particles that are suspended in the
air. These particles are referred to as aerosols or Particulate Matter.
Particles can be grouped into two broad classifications:
• Primary aerosols (emitted directly from sources)
• Secondary aerosols (formed in the atmosphere).
Particle emission sources may be natural or anthropogenic.
• Natural sources include volcanic eruptions, soil-dust uplift, sea-
spray uplift, natural biomass burning fires,…
• Anthropogenic sources include fugitive dust emissions such as
dust from road paving and building construction and demolition,
Ozone trends in Europe
101
fossil-fuel combustion, industrial emissions,… 102

Contribution of different natural and anthropogenic sources to

the global amount of Particulate Matter (PM)
Chemical composition of PM
Annual production or emission
It is highly variable and directly
(Tg·y-1)
Range Probable
associated with the characteristics
estimation of the surrounding gas.
Natural It includes:
Wind erosion 1000 – 3000 1500
• inorganic ions and elements
Marine aerosol 1000 - 10000 1300
Volcanoes 4 – 10000 30 • elemental carbon
Primary biological particles 26 – 80 50 • organic compounds
Forest fires 3 – 150 20 • crustal substances
Secondary inorganic particles 100 – 260 180
The organic fraction is difficult to
Secondary organic particles 40 – 200 160
characterize, since it often Composition of PM2.5 when
Anthropogenic
contains thousands of organic concentrations rise above
Direct emissions 50 – 160 120
air quality standards in USA
Secondary inorganic particles 260 – 460 330 compounds.
Secondary organic particles 5 – 25 10 103 104
Size
Processes
PM is frequently divided into two subclasses which include
Small colloidal particles are subject to diffusion processes.
• Fine particles: d < 2.5 μm
Some particles serve as nuclei upon which vapors condense.
• Large or coarse particles: d > 2.5 μm
Some particles react chemically with atmospheric gases or vapors
Next figures illustrates the distribution of the PM, the sources, the to form different compounds.
primary processes involved in introducing mass into each size range When two particles collide in the air, they tend to adhere to each
and the removal mechanisms. other, thereby forming progressively larger and larger particles by
Particles can be divided into three modes: coagulation. The larger a particle becomes, the greater its weight
and the greater its likelihood of falling to the ground:
1. Nucleation mode: d < 0.1 μm
sedimentation (dry deposition).
2. Accumulation mode: 0.1-2.5 μm
Particles in the nucleation and accumulation modes together are Washout of particles by rain or other forms of precipitation
fine particles (snowflakes, hail, mist, fog…) is a common form of agglomeration
and sedimentation (wet deposition).
3. Large mode: d > 2.5 μm 105 106

6 2

Processes aerosols undergo in the atmosphere

107
Prototypical trimodal distribution of atmospheric aerosol with 108
several sources and pathways of how the particles are formed
Nucleation mode
1
They are also known as Aitken
nuclei and Cloud Condensation
Nuclei (CCN) as they can become
activated to form to cloud droplets
in the presence of supersaturation
of water vapor.
They are mainly produced when hot
supersaturated, condensate and coagulate.
Chemical composition: variable
Lifetime: short, of the order of minutes, as they increase in size by
coagulation.
Accumulation mode
2
These particles have significant but
small settling velocities; therefore,
they can be suspended in the air
for long periods of time.
They tend to form from the condensation of low volatility gases
gases become and coagulation of Aitken nuclei.
Chemical composition: variable. It is determined by their origin
and the characteristics of the surrounding area.
Lifetime: long; thus, they travel long distances
109 110

Large mode
3
Originate from windblown dust,
sea salt and other debris in the
atmosphere as well as from
mechanical processes, grinding,
pulverization, and so on.

Lifetime: hours, as they are heavy enough to sediment out rapidly.

However, this mode predominate near its sources: urban
atmospheres, industrial areas, roadways, ….

Nucleation mode has the highest number concentration, the

accumulation mode has the highest surface area concentration and
111 112

coarse mode has the highest volume (mass) concentration of PM

Number, surface and volume distributions of PM
 For these reasons, air quality standards which regulate the total
Effects
suspended particulates classify the particles according to their size
Fine particles are challenging because based on the 50% cut-off point. The measurements are taken by
• They can travel long distances and specific sampling instruments with inlets using size exclusion
serve as vehicles on which mechanisms to segregate the mass of each size fraction.
contaminants (sulphur, nitrate, heavy
metals, and persistent organic
compounds) are able to reach water
bodies and soils.
• They are hazardous for human
health, as they are small enough to be
absorbed deeply into lungs and cause
health problems .
• They are also a major contributor to
reduced visibility. 113 114

Filter, before and after sampling

Theoretical and real efficiencies for a sampling device

calibrated for PM10 PM10 refers to “particulate matter which passes through a
η size-selective inlet as defined in the reference method for
100 % retained the sampling and measurement of PM10, EN 12341, with a
50 % efficiency cut-off at 10 µm aerodynamic diameter”
100 % Directive 2008/50/EC on ambient air quality and cleaner air for
Europe
50 % Greater particles, NOT COLLECTED

Exclusion diameter
PM2.5 refers to “particulate matter which passes through a
10 μm size-selective inlet as defined in the reference method for
d
Smaller particles, COLLECTED
the sampling and measurement of PM2.5, EN 14907, with
0 % retained a 50 % efficiency cut-off at 2.5 µm aerodynamic
diameter” Directive 2008/50/EC on ambient air quality and
50% mass collection efficiency cleaner air for Europe
115 116
 Atmospheric aerosols

Since most particles are not spherical, the particle size is often
described using an equivalent diameter. The equivalent
diameter is the diameter of a sphere that has the same fluid
properties as the particle under consideration.
Assuming spherical particles with a diameter ≈ 1 µm Stokes’ Law
can be applied:

Where: νt = terminal or settling velocity [L·T-1]

d= diameter of the particles [L]
g = acceleration of gravity [L·T-2]
ρp = density of the particles [M·L-3]
ρg = air density [M·L-3]
118

Most particles are not spherical µ = air viscosity [M·L-1·T-1]

From previous equation, the effective diameter for an irregular

particle is derived: Stokes’ diameter.

Stokes’ diameter is the diameter of a sphere with the same

density and settling velocity as the particle

Deviations
• PM < 1 μm as settling particles “slip between” air molecules
• PM >10 μm because they settle rapidly and generate
turbulence as they fall
Thus, Stokes’ Law is only applicable between 1-10 μm.
Since the density of a particle is often not known an arbitrary
density of 1 g·cm-3 is conventionally assigned to ρp; when this is
done, the diameter calculated from the equation is called the PM2.5 emissions in the EU-28: (a) trend in PM2.5 emissions from
aerodynamic diameter.
119
the five most important key categories, 2000–2014; (b) share of
emissions by sector group, 2014
PM10 emissions in the EU-28: (a) trend in PM10 emissions from the
five most important key categories, 2000–2014; (b) share of
emissions by sector group, 2014