Characterizing

Air Pollution
CEV 301 Air Quality Management
Fate and transport of
pollutants in the
envionment • Advection
Physica • Dispersion

l •
• Complexation
• Biodegradation
• Activation
• Metal catalysis
•
Difusion
Liquid stratifcation
• Volatilization
• Density stratifcation
• Sedimentation
• Filtration
• Oxidation/reduction
• photolysis

Biologi Chemic • Adsorptio

n
cal al • Dissolutio
n
• İonization
Basic Chemical Concept
Environmental chemistry is the discipline that concerns
itself with how chemicals are formed, how they are
introduced into the environment, how they change after
being introduced, where they end up in organisms and
other receptors, and the efects they have (usually the
damage they do) once they get there.
Element is a material substance that has decomposed
chemically to its simplest form. These are what appear
on the periodic table of elements.
Elements may be further broken down only by nuclear
reactions, where they are released as subatomic
particles. Such particles are important sources of
pollution and often are environmental contaminants.
Elements in the horizontal rows,
known as periods, grow increasingly
diferent
with the distance moved to the left or
right. So, O difers physically and
chemically more from boron (B) than
O does from F, and O is a very
diferent
from lithium (e.g. O is a nonmetal and
Li is a light metal).
Lanthanides
Actinides
An element shares many
physicochemical properties with its
vertical
neighbors, but difers markedly from
its horizontal neighbors. For example,
oxygen (O) will chemically bind and
react similarly to sulfur (S) and
selenium
(Se), but behaves very diferently
from nitrogen (N) and fuorine (F).
• Metals: Every element except the nonmetals
• Heavy metals: Metals near the center of the table
• Light metals: Groups I and II
• Alkaline earth metals: Group IIA
• Alkali metals: Group IA
• Transition metals: All Group VIII and B families
• Actinons: Elements 90–102
• Rare earths: Lanthanons (Lanthanides), Elements
58–71
• Metalloids: Elements separating metals and
nonmetals, Elements 5, 14,32, 33, 51, 52, and 84
• Nonmetals: Elements 2, 5–10, 14–18, 33–36, 52–
54, 85, and 86
• Halogens: Group VIIA
• Noble gases: Inert elements, Group 0
An atom is the smallest part of an
element that can enter into a chemical
reaction.
Most atoms combine by chemical bonding
to other atoms, creating molecules.
The molecule, which may also be an
atom, is the smallest subdivision of an
element that is able to exist as a natural
state of matter.
The nucleus of an atom, consisting of
protons and neutrons (hydrogen has only
one proton in its nucleus), account for
virtually all of the atomic mass, or the
atomic mass unit (amu).
 Physicochemical
Processes in the
Formation of Air Toxics
The important processes under which toxic compounds are formed;
• Combustion reactions
Hydrocarbon + oxygen → CO2 + H20 + CO + SO2 + NOx + VOCs
(e.g. Benzene, toluene ..) + POPs (e.g. PAHs + PCBs + dioxins +
heavy metals +..) ?
• Ionization reactions
An atom or a molecule acquires a negative or positive charge by
gaining or losing electrons to form ions. Ionization can result from
the loss of an electron after collisions with subatomic particles,
collisions with other atoms, molecules and ions, or through the
interaction with light. 
• Solubility and electrolytes
• Dissociation of ionic compounds (anions and cations) in water,
the rxn’s of nonelectrolytes, strong electrolytes, and/or weak
electrolytes in water difers. Nonelectrolytes do not ionize.
 Combustion Rxn’s
• Complete combustion

Hydrocarbon + oxygen → carbondioxide +

water + energy

• Incomplete combustion

Hydrocarbon + oxygen → CO2 + H20 + CO +

SO2 + NOx + VOCs (e.g. Benzene, toluene ..) +
POPs (e.g. PAHs + PCBs + dioxins + heavy
Environmental Acid and
Base Chemistry
• For many air pollution situations, an acid is
considered to be any substance that causes
hydrogen ions to be produced when dissolved in
water.
• Conversely, a base is any substance that
produces hydroxide ions when dissolved in
water.

1. Hydrolysis
2. Photolysis
3. Precipitation reactions
Strong acids, that are important in air pollution:
• hydrochloric acid (HCl)
• nitric acid (HNO3)
• sulfuric acid (H2SO4)
• Perchloric acid (HClO4)
Many weak acids: carbonic acid (formed by CO2),
acetic acid, and phosphoric acid.
Strong bases :
• sodium hydroxide (NaOH)
• potassium hydroxide (KOH)
Weak bases :
• ammonia (NH3),
• ammonium hydroxide (NH4OH)
• organic amines (i.e. compounds with the radical:
NH).
Why is rain naturally
acidic?
Dissolved CO2 causes most rainfall to be
slightly acidic:
CO2(aq) + H2O(l) ⇔ H(aq) + HCO3(aq) Ka :
4.3 107-
Acidic precipitation, popularly known as
“acid rain” contains the strong acids H2SO4
and HNO3, mainly from the combustion of
fossil fuels that contain sulfur.
Exercise:
1. What is [OH-] concentration in
unpolluted rainwater?
2. How many times more acidic, [H+], is
acid rain than unpolluted rain?
3. What are the molar concentrations of
[H] and [OH] of rainwater at pH 3.7 at
25°C?
Atmospheric Chemistry
Atmospheric chemistry encompasses all of the
chemical transformations occurring in the various
atmospheric layers from the troposphere to beyond
the stratosphere.
Atmospheric chemical transformations are classifed
in terms of whether they occur as a
• Gas phase rxn’s (homogeneous) (e.g. O3, NO2
formation),
• Gas to solid rxn’s, rxn’s on a surface
(heterogeneous) (e.g. Formation of aerosols), or
• Gas to liquid rxn’s, rxn’s in a liquid droplet
(heterogeneous) (e.g. Formation of acid rain).
Types of Atmospheric
Chemical
Transformations
• Oxidation / Reduction Rxn’s
The chemical transformations occurring in
the atmosphere are best characterized as
oxidation processes. Photochemical rxn’s;
free radical (O, H, OH,
HO2) involved rxns
Thermal rxn’s

• Endothermic Reactions – A chemical change

that absorbs heat
• exm. ice melting or water evaporation
CO2 (s) → CO2 (g)
• Exothermic Reactions – A chemical change
that gives of heat
• Exm. Digesting food, fre burning or condensation

CH4 + 2O2 → CO2 + H2O

Gas phase reactions:
 GOOD AND BAD
OZONE

Good
(UV shield)

Bad
(greenhouse gas)

Good
(OH source)

Bad
(smog)

NOx = NO + NO2: nitrogen oxide radicals

VOC (volatile organic compounds) = light hydrocarbons
and substituted organic compounds
Daily urban pollutant conc.
profles
As the morning rush
hour begins, the NO
levels increase,
followed quickly by
NO2. As the latter
reacts with sunlight,
O3 and other oxidants
O3 are produced. The
hydrocarbon level
similarly increases at
the beginning of the
day and then drops of
in the evening.
This is a cyclic process that
needs light and nitrogen oxides
to generate oxygen atoms. Once
formed, the oxygen atoms react
with water to form hydroxyl
radicals. The hydroxyl radicals
then react with hydrocarbons
according to equations 5 through
8 to form peroxyacyl nitrates (or
PAN).
Free Radicals
Monthly ozone profle
Ozone trends in remote air at northern mid-latitudes
RISING OZONE BACKGROUND
IN EUROPE
Hohenpeissenberg/
Payerne 3-5 km
polluted
Naja et al. [2003]

background

Changes in anthrop. NOx emissions

Mace Head, 1987-2004

[Simmonds et al., 2004]
Heterogenous rxn’s
• gas–liquid or gas–solid phases reactions
• involve the dissolving of NO2 and SO2 in
water droplets, with subsequent chemical
reactions occurring to form HNO3 and
H2SO4 in the liquid phase.
• The heterogeneous oxidation of SO2 in
liquid droplets and water flms is also a
major pathway for conversion to sulfate
in wet plumes and during humid or foggy
conditions.
Scavenging and removal
from the atmosphere
The removal of material from the atmosphere involves two
processes:
• Wet deposition
• Dry deposition

The water solubility of gases ( SO2 and NO2) infuences

the extent of removal by wet versus dry deposition.
• Soluble gases may be removed by wet deposition of
liquid droplets in the form of rain or fog.
• Less soluble gases such as O3 and hydrocarbon vapors
are removed by transport to the surface of the earth,
where they difuse to vegetation, materials, or water
bodies.