Air Quality:

Criteria Pollutant
Lect-6
Detailed of Criteria Pollutant
1.Carbon monoxide, CO
Carbon monoxide, CO, is a colorless odorless
flammable gas, major pollutant of an urban air,
produced from incomplete combustion of fossil fuel and
biomass.
2C + O2 2CO and 2CO +O2 2CO2
Anthropogenic sources: IC engine, cigarette smoke,
biomass burning
Natural sources: biomass burning, atmospheric
oxidation of methane gas and other hydrocarbons.
Concentrations: Background concentration 50 110
ppbv, closely associated with traffic density and
meteorological conditions
Sinks: Atmospheric photochemical processes:
CO +OH CO2 +H; H+O2 +M HO2 +M;
HO2 +NO NO2+OH; NO2 subsequently oxidize to produce
O3; Residence time: 2 months
As a result of these reaction CO is oxidized to CO2
CO +2O2 + h CO2 +O3---- important source of O3 in
atmosphere



2.Sulfur dioxide, SO2
Sulfur dioxide, SO2, is a colorless gas with a sharp odor, primary
pollutant, has anthropogenic (man-made) and natural sources.
Oder detected: 0.38 ppm; At 3 ppm pungent irritating odor
Anthropogenic sources: industries burning sulfur-containing fossil
fuels, ore smelters, oil refineries.
- Sulfur is present in many fuels (e.g., coal, crude oils) over a wide
range of concentrations. Combustion causes its oxidation to sulfur
dioxide.
Natural sources: marine plankton, sea water, bacteria, plants,
volcanic eruption.
SO2 effects:
- At relatively high concentrations SO2 causes severe respiratory
problems.
- Sinks:
- Sulfur dioxide is an acid precursor, which is a source of acid rain
produced when SO2 combines with water droplets to form sulfuric
acid, H2SO4
- Sulfur dioxide is an precursor of sulfate particulates (sulfates) which
affect the radiation balance of the atmosphere and can cause global
cooling
Residence time: 2 to 4 days: Trans- boundary problem
Health effects of Sulphur Dioxide
Concentration of SO2 (ppm) Effects
0.52ppm with particulate (24-hr avg.) Increase death
0.25 ppm with smoke (3-4 days;24-hr
avg.)
Increase death
0.25 ppm with particulates (24-hr
avg. 3-4 days exposure)
Increase illness for elderly
0.11 to 0.19ppm with low particulate
levels(episode of several days
duration)
Increase hospitalization
0.037 to 0.092ppm with smoke
(chronic exposure)
Increase respiratory symptoms and
lung diseases
3. NO2
Nitrogen, N2, is a dominant gas of the
atmosphere about 78% by volume
NOx stands for an indeterminate mixture of nitric
oxide, NO, and nitrogen dioxide, NO2
Nitrogen oxides, NOx, are formed mainly from N2
and O2 during high-temperature combustion of fuel
in cars.
Anthropogenic sources: motor vehicles, biomass
burning
Natural sources: bacteria, lightning, biomass
burning
NOx effects:
causes the reddish-brown haze in city air, which
contributes to heart and lung problems and may be
carcinogenic
NOx is an acid precursor, which is a source of acid
rain produced when nitrogen oxides combines with
water to produce nitric acid, HNO3
Nitrogen oxides are the precursors of nitrate
particulates (nitrates) which affect the radiation
balance of the atmosphere and can contribute to
global cooling
Nitrogen oxides are major contributors to the
formation of ground level bad ozone.


Health Effects of NO2
Concentration of NO2 (ppm) and
exposure period
Effects
150 (5-8 minutes) Potentially fatal
50-100 (<1-hr) May cause bronchopneumonia- but
recovery probable
10 - 40 (intermittent exposure) May cause chronic fibrosis and
Emphysema
0.05 to 0.10 (chronic exposure) Increase chronic bronchitis
<0.05 (long-term average) Increase in heart and lung disease in
general population with increase in
an ambient concentration
4. Ozone
Ozone, O3, is a gas.
At ground level, ozone is a hazard (bad
ozone) - it is a major constituent of
photochemical smog. However, in the
stratosphere, it serves to absorb some of the
potentially harmful UV radiation from the sun,
which is believed to cause skin cancer,
among other things (good ozone).
Sources: ozone is not emitted into the
atmosphere; ozone is formed from the ozone
precursors, VOCs, and nitrogen oxides (will
be discussed in several Lectures).
"Bad" ozone effects:
diverse effects on human health
ecological effects: damage vegetable and
trees,
Criteria Air Pollutants: Ozone
Unpleasant appearance in
urban cities
photochemical smog

Deterioration of synthetic
rubber, textiles, paints
Gates Corporation
http://www.gates.com/brochure.cfm?brochure=2833&location_id=3369
US EPA in How Stuff Works Website,
http://science.howstuffworks.com/ozone-pollution.htm
Criteria Air Pollutants: Ozone
Leaf damage
Chlorophyll damage: flecks
Discoloration
Reducing crop yields and forest growth
Tobacco leaf which has sustained ozone damage
http://www.lambtonwildlife.com/nature_notes_98/tobac.fld/tobacp.htm
Ozone damage on white pine (Photograph courtesy of A. Heagle)
NC State, http://www.ces.ncsu.edu/depts/pp/notes/Ornamental/odin19/od19.htm
Ponderosa Pine (left: undamaged;
right: damaged)
Image from Miller et al (1996)
USFS PSW-GTR-155
http://www.cbesurvey.org/aplv/panek/research.htm
5. Lead
Lead alkyls (ethyl and tetra methyl lead)
is the additives in the fuel to boost the
octane rating.
Metals (such as lead, mercury, cadmium,
chromium, nickel) found as impurities in
fuels.
Anthropogenic sources: emitted by metal
mining and processing facilities; motor
vehicle.
Example: lead is a very useful metal, has
been mined for thousand of years
Main effect: They are highly toxic
6.Particulate matters (PM)
Particulate matters (aerosols) are solid or
aqueous particles composed of one or
several chemicals and small enough to
remain suspended in the air
Examples: dust, soot, smoke, sulfates,
nitrates, asbestos, pesticides, bio-aerosols
(e.g., pollen, spores, bacterial cells,
fragments of insects, etc.)
Name:
Aerosol, SPM- Suspended particulate matter;
TSP- Total Suspended particulate matter;
PM
10
are particles with diameter < 10
micrometers (m), PM
2.5
Effects
diverse health effects (e.g., harmful to
human respiratory system)
contribute to urban haze, cause
visibility reduction
play a key role in the Earths radiative
budget and global change
Health Effects of SPM
Concentration of Particulate
(g/m3)
Effects
2000 g/m
3
with 0.4 ppm of SO2 (24-
hr avg) of several days duration.
Increase in death due to bronchitis
1000 g/m
3
with 0.25 ppm of SO2
(24-hr avg) during episodes
Increase mortality from all causes
including respiratory and cardiac
disease
300 g/m3 with 0.21 ppm of SO2 (24-
hr avg)
Significant increase in bronchitis
symptoms
100-200 g/m3 with 0.05 to 0.08 ppm
of SO2 (average seasonal level)
Increase in incidence of bronchitis
reported
Some discussion points
Why particulate pollutants are more
common and their concentration is high in
SA countries?
What are their sources and how we can
control them?
How can we solve transboundary
problem?
How CO affect human health?

Atmospheric Aerosols

Sources
Natural Origin: sea spray, dust from
arid/semiarid areas, volcanic eruption,
forest fire, interplanetary meteors, gas-
phase chemistry
Man-made: combustion, gas-phase
chemistry
Sinks
Coalescence of tiny aerosols due to air
motions
Cloud formation; aerosols as nuclei
Precipitation scavenging
Aerosols - Characteristics
Physical; size,
mode of formation,
settling and optical
properties
Chemical: Organic
or inorganic
Biological: bacteria,
viruses, spores,
pollens
Fig. 17-8 p. 426
Aerosol Composition

Water-soluble: sea salt, sulfate,
nitrate, organic carbon (optical
properties are largely unknown)
Sulfate Particles (natural and
anthropogenic): mainly reflect
sunlight
Soot, carbonaceous materials
(black carbon): mainly absorb
sunlight
Dust-like substance (mineral):
reflect and absorb sunlight
Particulate Matter
Human Hair (70 m diameter)
Hair cross section (70 mm)
PM
2.5
(2.5 m)
PM
10
(10m)

Source: US EPA
Composition of PM
PM
Sulfate:
Ammonium sulfate
((NH
4
)
2
SO
4
), Ammonium
Bisulfate (NH
4
HSO
4
) and
sulfuric acid (H
2
SO
4
)
Water soluble
PM2.5

Geological material:
Oxides of Al, Si, Ca, Ti,
Fe and other metals
Typically about 50% of
PM10 and 5 15% of
PM2.5
Nitrate:
Mostly ammonium
nitrate (NH
4
NO
3
)
Easily evaporates with
changes in temp and RH.

Organic carbon:
Includes hundreds of
compounds containing
more than 20 Carbon
molecules (> C
20
)
Semi-volatile
Elemental carbon:
Pure carbon
Also known as soot
Liquid Water:
Soluble compounds
absorb water when RH is
> 70%.
Composition and
shape of soot

Different forms

Dusts:
Solid aerosols generated by the handling, grinding,
abrasion, or cutting of a bulk material
Dust particle size is related to the amount of energy
involved in creation; the higher the energythe smaller
the particle created; the lower the energythe larger
the particle created
Examples: Saw dust, coal dust
Smoke:
Fine, solid particles resulting from incomplete combustion
of organic particle such as coal, wood or tobacco,
consists mainly of carbon and other combust able
material. Size -0.1 to 1 micron
Fumes: are fine solid particles formed by condensation of
vapors of solid material.



Other form
Fly ash:
It consists of finely divided non combust able particles contained in
flue gases arising from combustion of coal. Fly ash shows
properties of dust, smoke, and fumes.
Like dust it has particle range 1-100 micron
Like smoke: it results from burning
Like fumes: It consists of inorganic metallic or mineral substance

Mists:
Liquid aerosols generated by condensation from a
gaseous state or by the breaking up of a bulk liquid into
a dispersed state
Droplet size related to energy input as in dusts and
fibers
Examples: Metal working fluid from lathe, paint spray,
liquid mixing operations
Spray: consists of liquid particles formed by atomization
of parent liquids such as pesticides and herbicides.




Effects
diverse health effects (e.g., harmful to
human respiratory system)
contribute to urban haze, cause
visibility reduction
play a key role in the Earths radiative
budget and global change

Climate Effects of Black Carbon
Aerosols in China and India


Surabi Menon, James Hansen, Larissa Nazarenko,
Yunfeng Luo

In recent decades, there has been a tendency toward
increased summer floods in south China, increased
drought in north China, and moderate cooling in China
and India while most of the world has been warming.
We used a global climate model to investigate possible
aerosol contributions to these trends. We found
precipitation and temperature changes in the model that
were comparable to those observed if the aerosols
included a large proportion of absorbing black carbon
("soot"), similar to observed amounts. Absorbing
aerosols heat the air, alter regional atmospheric stability
and vertical motions, and affect the large scale
circulation and hydrologic cycle with significant regional
climate effects (Science, 27 September 2002).
Particle removal Process
Most important process
1. Coagulation
2. Sedimentation
3. Washout
Less important process
1. Diffusion (through air to ground or to
upper atmosphere)
2. Impaction (Attachment to obstacle)
1. Coagulation
Coagulation occurs when two particles
collide and then coalesce resulting in
fewer but larger particles i.e smaller
particles tend to disappear.
Consider aerosols consisting of
identical particles at a number density
N. The rate at which each particle
strike other is proportional to the
number density of target N
The rate of coagulation N
2

Non uniform size
If N consists of two size groups r
1
and r
2
Then
rate of coagulation can be shown to
be

dN/dT = c (2 + r
1
/r
2
+r
2
/r
1
)N
2
Monodisperse aerosol :
r
1
/r
2
=
1

Rate =
4 c N
2
Polydisperse aerosol :
Rate = c(2 + r
1
/r
2
)

N
2
If
r
1
/r
2
=
100 Rate = 102 c N
2
2. Sedimentation
Settling is the major natural self cleansing
process for removal of particles from the
atmosphere.
Particle classified as:
Suspended particles: 1m to 20 m
Settle-able or dust fall > 10m
Airborne behavior, such as settling
velocity, is a function of Size, Specific
gravity, Shape Surface properties: Using
Stokes law
V
t
= g D
2
(
p
-
air
)/18

Holds for 1m to 100 m

Assumptions
1. The fluid is continuous
2. The flow is laminar, Cd = 24/ Re
3. Newton,s law of viscosity holds
4. In the resulting equation the term that
involves square of velocity is negligible
Particle too large for stokes law:
Flow becomes turbulent i.e. Cd> 0.4 and
assumption 4 does not hold good.
Particles too small for Stokes law: Fluid
will not be continuous; Cunnigham
correction is required.

Scavenging
Wash out by precipitation
q = q
o
exp (-w
p
t)
w
p
: washout coefficient depends on
rainfall rate and size of the droplet.

Size distribution
Coagulation
determines lower
end of the size
distribution
And Sedimentation
determine the upper
end of the size
spectrum

Size distribution of
natural aerosols
measured at a
number of locations
in Germany (data
taken from Junge,
1963).

Junge size distribution
N(r) = dn/dlogr = cr
-

and dN/dr = c r
-( +1)

Where
n(r)= no of particles per unit volume
per log size interval

N= No of particles per unit volume

dN = No of particle per increment

in log r

C=
is a constant whose value depends on
concentration
= the slope of the distribution curve

Problem
If a continental aerosol contains 10
4

particles of radii 0.1 m per cm
3
, how
many particles would you expect to
have with radii 0 .5 m and 1m