Some Pollutants in the Atmosphere

Combine to Form Other Pollutants

• Primary pollutants

• Secondary pollutants

• Air quality improving in developed countries

• Much more needs to be done in developing countries

– Indoor pollution: big threat to the poor
 Air pollution disasters- shifting bases
London Smog of 1952
Donora, Pennsylvania,
US, 1948
 Primary Pollutants

CO CO2 Secondary Pollutants

SO2 NO NO2
Most hydrocarbons SO3
Most suspended particles HNO3 H2SO4
H2O2 O3 PANs
Most NO3− and SO42− salts
Sources Natural Stationary

Mobile

Fig. 18-4, p. 472

 What Are the Major Outdoor Air Pollutants?
(1)
• Carbon oxides
– Carbon monoxide (CO)
– Carbon dioxide (CO2)
– Sources Automobiles
– Human health and environmental impact
Exposure to CO can reduce the oxygen-carrying
capacity of the blood.
 What Are the Major Outdoor Air Pollutants?
(2)
• Nitrogen oxides (NO) and nitric acid (HNO3)
– Sources Automobiles
– Acid deposition
– Photochemical smog
– Human health and environmental impact
– Nitrogen dioxide can irritate the lungs and lower resistance to respiratory infections such as

.
influenza

• Sulfur dioxide (SO2) and sulfuric acid (H2SO4)

– Sources Coal burning
– Human health and environmental impact
– SOx can react with other compounds in the atmosphere to form small particles.
These particles penetrate deeply into sensitive parts of the lungs and can cause
or worsen respiratory disease, such as emphysema and bronchitis, and can
aggravate existing heart disease, leading to increased hospital admissions and
premature death .
 What Are the Major Outdoor Air Pollutants?
(3)
• Particulates
– Suspended particulate matter (SPM)
• Fine
• Ultrafine (Nano?????)

– Human health and environmental impact

– Exposure to such particles can affect both your lungs and your heart. Small particles of
concern include "inhalable coarse particles" (such as those found near roadways and
dusty industries), which are larger than 2.5 micrometers and smaller than 10 micrometers
in diameter; and "fine particles" (such as those found in smoke and haze), which are 2.5
micrometers in diameter and smaller.
 What Are the Major Outdoor Air Pollutants?
(4)
• Ozone (O3)
– Sources
– Human and environmental impact

• Volatile organic compounds (VOCs)

– Hydrocarbons and terpenes
– Sources
– Human and environmental impact
Eye, nose and throat irritation
headaches, loss of coordination and nausea
damage to liver, kidney and central nervous system
Some organics can cause cancer in animals, some are
suspected or known to cause cancer in humans.
Chemical Reactions That Form Major
Outdoor Air Pollutants
 Greenhouse gases

• Carbon Dioxide - fossil fuel burning, land clearing/burning.

• Methane - Breakdown of organic material by anaerobic bacteria.
• Nitrous Oxide - Biomass burning, automobile exhaust.
• Ozone – automobile exhaust
• Chlorofluorocarbons - Refrigerants, cleaning solventts, propellants.
 Ozone Layer: Function

• Question
– What does the ozone layer do for us?
– Ozone is the only major atmospheric
constituent that absorbs significantly
between 210 and 290 nm.
– The ozone layer is a consequence of
oxygen-only chemistry. It formed once
photosynthetic marine organisms
(cyanobacteria) began “polluting” the
atmosphere with oxygen.
 The Ozone Layer:
Formation and Depletion
Catalytic Cycle
Catalytic Cycles
 Destruction of Ozone Layer by CFCs
• Lecture Question
– How do CFCs destroy ozone? Answer in some detail.

– “Hard” CFCs are unreactive to OH and other reactive radicals in the

troposphere. They are also pretty insoluble in water. That means their
tropospheric lifetimes are easily long enough that the majority of
tropospheric CFCs pass through the tropopause into the stratosphere.
– Once there, they are subject to light of shorter wavelengths (ie, more
energetic photons). In particular, many CFCs absorb in the “uv window”
(centered at 205 nm) between strong O2 and O3 absorption. That
means most can photodissociate in the bottom half of the stratosphere.
– Photodissociation releases chlorine atoms:
• For example: CFCl3 + light  CFCl2 + Cl (l < 225 nm)
– Chlorine atoms deplete odd oxygen (Ox) largely by the following cycle
• Cl + O3  ClO + O2
• ClO + O  Cl + O2
 Destruction of Ozone Layer by CFCs
• Lecture Question
– How do CFCs destroy ozone? Answer in some detail.

– “Hard” CFCs are unreactive to OH and other reactive radicals in the

troposphere. They are also pretty insoluble in water. That means their
tropospheric lifetimes are easily long enough that the majority of
tropospheric CFCs pass through the tropopause into the stratosphere.
– Once there, they are subject to light of shorter wavelengths (ie, more
energetic photons). In particular, many CFCs absorb in the “uv window”
(centered at 205 nm) between strong O2 and O3 absorption. That
means most can photodissociate in the bottom half of the stratosphere.
– Photodissociation releases chlorine atoms:
• For example: CFCl3 + light  CFCl2 + Cl (l < 225 nm)
– Chlorine atoms deplete odd oxygen (Ox) largely by the following cycle
• Cl + O3  ClO + O2
• ClO + O  Cl + O2
Again!!!!!
 Sources of Catalysts
• Stratospheric NOx
– Source: tropospheric N2O
– Natural sources (mostly)
– 10% increase since 1850 (ie, due to anthropogenic activities...mostly
fertilizer application)
• Stratospheric HOx
– Source: tropospheric CH4, H2, H2O
– Much is natural, however...
– 150% increase in tropospheric CH4 since 1850 (agricultural activities;
landfills; other sources)
• Stratospheric Cl and Br
– Almost entirely due to human activity
– Sources: tropospheric CFCs, HCFCs, halons
 The “Ozone Hole”
Dobson Unit(DU) is defined to be 0.01 mm thickness at STP
(standard temperature and pressure).Ozone layer thickness is
expressed in terms of Dobson units, which measure what its
physical thickness would be if compressed in the Earth's
atmosphere.

The ozone hole is the region

over Antarctica with total
ozone 220 Dobson Units or
lower. (The avg total column
ozone in the atmosphere is
about 300 DU.)

Ozone hole in Sept 2005. Source: NASA

The Ozone Hole – Explained!
 What is Particulate Matter?
Image from http://www.epa.gov/eogapti1/
module3/distribu/distribu.htm
Particulate matter (PM)
describes a wide variety of
airborne material. PM pollution
consists of materials (including
dust, smoke, and soot), that are
directly emitted into the air or
result from the transformation
of gaseous pollutants. Particles
come from natural sources
(e.g., volcanic eruptions) and
human activities such as
burning fossil fuels, incinerating
wastes, and smelting metals.
 Particulate Matter:
Aerodynamic Diameter
Establishing a particle size
definition for irregularly shaped
particles necessitates the use of a
standardized measure referred to
as the aerodynamic diameter,
measured in microns or
micrometers (μm), a unit equal to
one millionth of a meter. The
graph at the right shows the
distribution of the 4 main particle
size categories, with the
categories historically and
currently regulated by EPA
indicated below. By comparison, a
human hair is approximately 70
microns in diameter.
Top: Modified from Online Reference Module by JR
Richards et al. http://registrar.ies. ncsu.edu/ol_2000.
Bottom: U.S. EPA. Office of Research and Development.
 Determinants of PM Concentration

• Weather patterns
• Wind
• Stability (vertical movement of air)
• Turbulence
• Precipitation
• Topography
• Smokestack height and temperature of gases

Nearby natural and built structures may lead to downward moving

currents causing aerodynamic or building downwash of
smokestack emissions.
 How Does PM Cause Health Effects?

Several theories have been advanced as to the mechanism of

action. It is likely that more than one mechanism is involved in
causing PM-related health effects. Theories include the following:

1. PM leads to lung irritation 4. PM causes inflammation

which leads to increase of lung tissue, resulting in
permeability in lung tissue; the release of chemicals
that impact heart function;
2. PM increases susceptibility to
viral and bacterial pathogens 5. PM causes changes in
leading to pneumonia in blood chemistry that
vulnerable persons who are results in clots that can
unable to clear these infections; cause heart attacks.
3. PM aggravates the severity
of chronic lung diseases
causing rapid loss of airway
function;
 Where Does PM Originate?

Sources may emit PM directly into the environment or emit precursors

such as sulfur dioxide (SO2), nitrogen dioxide (NO2), and volatile
organic compounds (VOCs), which are transformed through
atmospheric chemistry to form PM.

VOCs
NO2 Ammonia (NH3)
SO2
PM
Ammonia (NH3)
Sources of PM and PM Precursors

Mobile Sources Stationary Sources

(vehicles) (power plants, factories)
VOCs, NO2, PM NO2, SO2, PM

Area Sources Natural Sources

(drycleaners, gas stations) (forest fires, volcanoes)
VOCs PM
DMS originates primarily from DMSP, a
major secondary metabolite in
some marine algae.[2] DMS is the most
abundant biological sulfur compound
emitted to the atmosphere.[3][4] Emission
occurs over the oceans by phytoplankton
DMS is also produced naturally by
bacterial transformation of dimethyl
sulfoxide (DMSO) waste that is disposed of
into sewers, where it can cause
environmental odor problems.[
 1. Smog
• Orginally phrased by Dr.Henry Antoine Des Voeux
• Mixture of Smoke and Fog
• Famous Smogs
-London or The Classical Smog
-Los Angeles or The Photochemical Smog

31
 Major Episodes of Severe Air Pollution
due to Inversions
1930: Meuse River Valley, Belgium
• An inversion led to a high concentration of
pollutants during a period of cold, damp
weather
• Main sources: zinc smelter, sulfuric acid
factory, glass manufacturers
• 60 deaths recorded
1948: Donora, Pennsylvania
• Similar inversion to Meuse River Valley
• Main sources: iron and steel factories, zinc
smelting, and an acid plant
• 20 deaths observed
1952: London
• Killer fog (right)
• Primary source: domestic coal burning
• 4,500 excess deaths recorded during week- The Great London Smog
long period in December (1952)
 1.1 London Smog
• December 1952
• Huge amounts of coal
burning
• 4000 people died of
respiratory problems
• Followed by additional
8000 deaths in the
following months

www.martinfrost.ws/htmlfiles/smog4.gif

33
 From: http://www.portfolio.mvm.ed.ac.uk/studentwebs/session4/27/greatsmog52.htm
The London Smog Disaster of 1952.
Days of toxic darkness.

Early on 5th of December 1952 the London sky was clear, the weather was considerably colder than usual, as it
had been for some weeks. As a result the people of London were burning large amounts of coal and smoke
bellowed from the chimneys. The winds were light and the air near the ground was moist, conditions ideal for
formation of radiation fog.

During the day of 5th December the fog was not particularly dense, it possessed a dry smoky character,
however when nightfall came the fog thickened and visibility dropped to a few metres.
In central London the visibility remained below 500 meters continuously for 114 hours and below 50 meters
continuously for 48 hours.
At Heathrow airport visibility remained below 10 for almost 48 hours from the morning of 6 December.
Road, rail and air transport were brought to a standstill. Theatres had to be suspended when fog in the
auditorium made conditions intolerable. But, most importantly the smoke laden fog that shrouded the capital
brought the premature death of an estimated 12,000 people and illness to many others.
This "pea soup" smog stayed stewing away for five days from the 5 to the 10 December as more and more
pollution entered it before winds from the west blew it down the Thames Estuary and out into the North sea.
 Some SO2 Chemistry in the atmosphere

X In the gas phase (clear sky, no clouds):

•
SO2 + •OH +NM  HSO3
•
HSO3 + O2 + NM  HOO• + SO3

SO3 + H2O  H2SO4

In mist:

H2SO4(g) + H2O  H2SO4(aq)

SO2(g) + H2O(l)  H2SO3(aq)

 The Role of Inversions

An inversion is an extremely
stable layer of the atmosphere
that forms over areas.
Temperature inversions trap
pollutants close to the ground.
These inversions involve
layers of hot air sitting above
cooler air near ground level.
When particles accumulate in
the air layer, they are unable to
rise into the atmosphere where
winds will disperse them.

Source: http://www.epa.gov/apti/
course422/ ce1.html
 The science.
The fog was triggered by the formation of a static layer of cooler air close to the ground as the night time
temperature dropped. This is known as temperature inversion.
Normally, air closer to the ground is warmer than the air above it, and therefore rises. Inversions are frequent
on winter nights after the ground has cooled down so much that it begins to chill the air closest to it often
causing mist to form as water vapour precipitates on dust particles. Normally the morning sun swiftly breaks
through the mist and heats the ground, which warms the air above it, breaking the inversion. But in
December 1952 the accumulation of smoke close to the ground was so great that the sun never broke
through, and the air stayed cool and static.
The term smog simply describes fog that has soot in it. Winter smog in which smoke, sulphur dioxide from
the city’s chimneys, accumulated in the foggy air had been a feature of London life since at least the 17th
century. However the industrial revolution of the 19th century in Britain’s major cities gave a dramatic increase
in air pollution.
On 5th December 1952 hanging in the air were thousands of tonnes of black soot, sticky particles of tar and
gaseous sulphur dioxide, which had mostly come from coal burnt in domestic hearths. Smoke particles
trapped in the fog gave it a yellow-black colour.
The water from the fog condensed around the soot and tar particles. The sulphur dioxide reacted inside these
foggy, sooty droplets to form a solute sulphuric acid creating in effect a very intense form of acid rain.
During the four days between the 4 and 8 December 1952 smoke measurements taken at the National
Gallery in London suggest that the PM 10 concentration reached 14mg/m3 which was 56 times the
level normally experienced at the time and the levels of sulphur dioxide in the air increased by 7 fold
peaking at around 700ppb.
Smoke and Sulphur dioxide pollution was monitored at various sites in London at the time of the December
Smog. The daily average measurements for 10 of these sites are given.
 Death rates
During the smog the death rate rose dramatically. The previous week the death rate had been 2062, which
was close to normal for that time of year. In the following week 4703 people died. The death rate peaked on
the 8th and 9th, at 900 per day. In parts of the East End, death rates during the period of the London smog
were nine times the normal. The death rate remained above normal through the winter and was still 2 per cent
up the following summer. There were almost a thousand more deaths per week than expected according to
the normal winter rates until the spring of that year.
How many people actually died?
The accepted figure is that the London smog killed around 4000 people. The official reports published at the
time used these figures. However they count only the deaths during and for two weeks after the smog. The
reason this was done was that death rate returned to normal at this time for a short while. However, there was
a second peak in deaths and people have since realised that the rates returning to normal was due to
registrations being delayed because of Christmas holidays. Deaths remained higher than normal for a long
time after this point. These delayed deaths add an extra 8000, bringing the total number of people the smog
killed up to 1, 2000. Many people nowadays accept this as the real figure for deaths due to the London smog.
Exactly how many people died as a result of the Great London Smog can never be known.
Who died?
The majority of the people who died were old and many already suffered from chronic respiratory and
cardiovascular complaints. Mortality from bronchitis and pneumonia increased more than sevenfold.
However, Officials at the time stated that the smog’s victims had been only the old and the sick. One medical
officer wrote in his official account of the smog published in 1954:
‘The fog was in fact a precipitating agent, operating on a susceptible group of patients whose life expectation,
judging from their pre-existing diseases, must even in the absence of fog, have been short.’
However in private many doctors disagreed with this. In fact only two thirds of the 4000 victims were over 65.
The death rate actually rose most in the 45 to 64 year olds. In fact it rose to three times the normal value. Had it
been true that only a ‘susceptible group of patients’ had been affected, then the number of deaths occurring for
some time after the incident would have fallen below normal. However as we know, this did not happen.
In the official reports infant mortality was played down and often did not mention it at all. However in fact twice
 1.2 Los Angeles Smog
• New kind of smog
• Primary source-
Vehicle emissions
• First observed
in Los Angeles

http://www.physics.ohio-state.edu 40
 2. Physical Significance
• Amount of pollutants released into the atmosphere
• Big problem in developing countries and in many major cities
• Effects
Plants - reducing or stopping the growth
Humans - affects heart and lungs and even genetic
diseases
Affects materials also

41
 3. Photochemical Smog
• Action of sunlight upon the exhaust gases to form pollutants harmful
at low altitudes
• Mixture of air pollutants
– Nitrogen oxides (NOX)
– Ozone
– Volatile organic compounds (VOCs)
– Peroxyacyl Nitrates (PAN)

• A major concern in urban cities-capable of travelling with wind

affecting huge population

42
Global Outlook: Photochemical Smog
in Santiago, Chile
 3.1 Pollutants in Photochemical Smog
3.1.1 Ozone
• Production at low altitudes
• NOx from exhaust gases
• Ozone production is dominant
when NO2/NO is greater than 3

Effects of Ground Level Ozone

• Damage to crops
• Irritates the respiratory tract and eyes
• High levels of O3 results in chest tightness, coughing and wheezing
• Increased hospital admissions and premature death

44
3.1.2 Volatile Organic Compounds (VOCs)
• Carbon based molecules (aldehydes, ketones,
hydrocarbons)
• Short- and long-term adverse health effects
• Sources
– Paints; wood preservatives; aerosol sprays; cleansers
and disinfectants; moth repellents and air fresheners
etc.
• Health Effects
– Eye, nose, and throat irritation; headaches; damage
to liver, kidney, and central nervous system. Some
organics can cause cancer in animals; some are
suspected or known to cause cancer in humans.

45
3.1.3 PAN
• Important contributor to photochemical smog

• Secondary pollutant-formed from other pollutants by

chemical reaction
• Contributor to production of groundlevel ozone, by
transporting NOx
• Powerful respiratory and eye irritants and toxic
• Higher concentrations lead to damage of vegetation

46
 4. Topography and Meterology
• Two factors influencing the formation of photochemical smog
4.1 Topography

• Very important for

formation of photochemical
smog
• Restriction of air movement,
city in valley experience more
smog problem, than plains

http://www.uwsp.edu/geo/faculty/ritter/imag
es/atmosphere/misc/smog.jpg 47
4.2 Temperature Inversion

• Increase of air temperature

with height for some distance
above ground causing the
smog trapped close to ground
• Consequences
– Air becomes still and dust
and pollutants are no
longer lifted from surface
• Serious problem in many cities

http://www.ec.gc.ca/cleanair-airpur

48
 CATALYTIC CONVERTERS – Invention of
Nanotechnology
• A catalytic converter is an
after-treatment device used
to reduce exhaust
emissions outside of the
engine.

FIGURE 24-1 Typical catalytic converter.

The small tube into the side of the
converter comes from the air pump. The
additional air from the air pump helps
oxidize the exhaust into harmless H2O and
CO2.
 CERAMIC MONOLITH CATALYTIC
CONVERTER
Catalytic Converter Operation
• The converter contains small amounts of rhodium, palladium, and
platinum.
• These elements act as catalysts.
– A catalyst is an element that starts a chemical
reaction without becoming a part of, or being
consumed in, the process.
– In a three-way catalytic converter (TWC),
three exhaust emissions (NOX, HC, and CO)
are converted to carbon dioxide (CO2) and
water (H2O).
 Ozone Layer: Function

• Question
– What does the ozone layer do for us?
– Ozone is the only major atmospheric
constituent that absorbs significantly
between 210 and 290 nm.
– The ozone layer is a consequence of
oxygen-only chemistry. It formed once
photosynthetic marine organisms
(cyanobacteria) began “polluting” the
atmosphere with oxygen.
 Missing Element –
Catalytic Destruction of Ozone

• Four main “families” of chemicals responsible for catalyzing ozone

destruction:
1. Nitrogen oxides: NOx
• NO + NO2
2. Hydrogen oxides: HOx
• OH + HO2 A common type of catalytic
3. Chlorine: ClOx destruction cycle (there are others)
• Cl + ClO
4. Bromine: BrOx Y+O3  YO+O2
• Br + BrO
YO+O  Y+O2
where Y = NO, OH, Cl or Br
 CFCs
• Lecture Question
– What are CFCs? What are they used for?

– CFCs are chlorofluorocarbons; they are small molecules that contain

chlorine, fluorine and carbon atoms. Usually there are only 1-2 carbon
atoms.
– CFCs are sometimes called Freons (that was their trade name for
DuPont)
– CFCs are referred to by a number. The most common CFCs are: CFC-
11, CFC-12, CFC-113 (formulas on the next page)
– HCFCs are CFCs that contain hydrogen. This makes them more
reactive to the OH radical, decreasing their tropospheric lifetime. That
means that, on a pound-per-pound basis, HCFCs (“soft CFCs”) destroy
less stratospheric ozone than CFCs (“hard CFCs”) because a smaller
fraction of HCFCs “survive” to reach the stratosphere

Molina and Rowland

 Most Stratospheric Chlorine is Anthropogenic

Despite the fact that

CFC-11: CFCl3 tropospheric concentration
CFC-12: CF2Cl2 of HCl is far greater than
CFC-113: CF3CCl3 of CFCs, it is not a great
HCFC-22: CHF2Cl contributor of
stratospheric chlorine.
 Destruction of Ozone Layer by CFCs
• Lecture Question
– How do CFCs destroy ozone? Answer in some detail.

– “Hard” CFCs are unreactive to OH and other reactive radicals in the

troposphere. They are also pretty insoluble in water. That means their
tropospheric lifetimes are easily long enough that the majority of
tropospheric CFCs pass through the tropopause into the stratosphere.
– Once there, they are subject to light of shorter wavelengths (ie, more
energetic photons). In particular, many CFCs absorb in the “uv window”
(centered at 205 nm) between strong O2 and O3 absorption. That
means most can photodissociate in the bottom half of the stratosphere.
– Photodissociation releases chlorine atoms:
• For example: CFCl3 + light  CFCl2 + Cl (l < 225 nm)
– Chlorine atoms deplete odd oxygen (Ox) largely by the following cycle
• Cl + O3  ClO + O2
• ClO + O  Cl + O2