99% of atmospheric gases, including water vapor, extend only 30 kilometers (kms) above earth's

surface.
Most of our weather, however, occurs within the first 10 to 15 kms.
Composition of Atmosphere

Nitrogen - 78%

Oxygen - 21%

Water Vapor 0 to 4%

Carbon Dioxide - .037%

Other gases make up the rest

Temperature Inversion

An increase in air temperature with height often called simply an inversion.

Radiosonde an instrument that measures the vertical profile of air temperature in the atmosphere
(sometimes exceeding 100,000 ft)

Atmospheric Layers

8 layers are defined by constant

trends in average air
temperature (which changes
with pressure and radiation),
where the outer exosphere is
not shown.
1. Troposphere
2. Tropopause
3. Stratosphere
4. Stratopause
5. Mesosphere
6. Mesopause
7. Thermosphere
8. Exosphere

Tropopause

separates

Troposphere from Stratosphere.

Generally

higher

in summer

Lower in winter.

Troposphere

temperature

decreases with height. Most of

our weather occurs in this layer
Varies in height around the
globe, but Averages of about 11
km in height.

The troposphere is the lowest major atmospheric layer, and is located from the Earth's surface up to
the bottom of the stratosphere . It has decreasing temperature with height (at an average rate of
3.5 F per thousand feet (6.5C per kilometer); whereas the stratosphere has either constant or
slowly increasing temperature with height. The troposphere is where all of Earth's weather occurs.
The boundary that divides the troposphere from the stratosphere is called the " tropopause ",
located at an altitude of around 5 miles in the winter, to around 8 miles high in the summer, and as
high as 11 or 12 miles in the deep tropics. When you see the top of a thunderstorm flatten out into
an anvil cloud , like in the illustration above, it is usually because the updrafts in the storm are
"bumping up against" the bottom of the stratosphere

Stratosphere
Temperature

inversion

in

stratosphere Ozone plays a major

part in heating the air at this
altitude

Atmospheric Layers

Mesosphere
Middle atmosphere Air thin,
pressure low, Need oxygen to
live in this region. Air quite Cold
-90C (-130F) near the top of
mesosphere

Thermosphere
Hot layer oxygen molecules
absorb energy from solar Rays
warming

the

air.

Very

few

atoms and molecules in this

Region.

The Stratosphere and Ozone Layer

Above the troposphere is the stratosphere, where air flow is mostly horizontal. The thin ozone layer
in the upper stratosphere has a high concentration of ozone, a particularly reactive form of oxygen.
This layer is primarily responsible for absorbing the ultraviolet radiation from the Sun. The formation
of this layer is a delicate matter, since as only when oxygen is produced in the atmosphere the
ozone layer can form and prevent an intense flux of ultraviolet radiation from reaching the surface,
where it is quite hazardous to the evolution of life. There is considerable recent concern that
manmade flourocarbon compounds may be depleting the ozone layer, with dire future consequences
for life on the Earth.
The Mesosphere and Ionosphere
Above the stratosphere is the mesosphere and above that is the ionosphere (or thermosphere),
where many atoms are ionized (have gained or lost electrons so they have a net electrical charge).
The ionosphere is very thin, but it is where aurora take place, and is also responsible for absorbing
the most energetic photons from the Sun, and for reflecting radio waves, thereby making longdistance radio communication possible.
Atmospheric Mixture & Charge

Additional
layers
include:
a)

The

homospher
e with 78%
nitrogen
and

21%

oxygen
b)

The

poorly
mixed
heterospher
e
c)

The

electrically
charged
ionosphere

Atmospheric Gases

Nitrogen,

oxygen,

argon,

water,

vapor,

carbon

dioxide, and most

other

gases

are

invisible.
Clouds are not gas,
but

condensed

vapor in the form

of liquid droplets.
Ground
smog,
visible,
reactants
Ozone is the primary ingredient of smog!
Variable & Increasing Gases

nitrogen
ozone.

based
which

is

contains
of
and

Nitrogen and oxygen concentrations experience little change, but carbon dioxide, methane, nitrous
oxides, and chlorofluorocarbons are greenhouse gases experiencing discernable increases in
concentration. CO2 has risen more than 18% since 1958. Fossil fuels are the biggest problem!

Aerosols & Pollutants

Human and natural
activities

displace

tiny soil, salt, and

ash

particles

as

suspended
aerosols,
as well as sulfur
and

nitrogen

oxides,
hydrocarbons

and
as

pollutants.

Pressure & Density

Gravity

pulls

gases

toward

earth's surface, and the whole

column of gases weighs 14.7 psi
at sea level,

a pressure of

1013.25 mb or 29.92 in.Hg .

The amount of force exerted
Over an area of surface is called
Air pressure!
Air Density is The number of air
Molecules
(volume)

Vertical Pressure Profile

in

given

Space

Atmospheric pressure decreases

rapidly with height. Climbing to
an altitude of only 5.5 km where
the pressure is 500 mb, would
put you above one-half of the
atmosphere's molecules.

Air Pollution
Air pollutants are usually classified into suspended particulate matter (PM) (dusts, fumes, mists, and
smokes); gaseous pollutants (gases and vapors); and odors .
Suspended PM can be categorized according to total suspended particles:
a) The finer fraction, PM10, which can reach the alveoli, and the most hazardous, b) PM2.5 (median
aerodynamic diameters of less than 10.0 microns and 2.5 microns, respectively). Much of the PM2.5
consists of secondary pollutants created by the condensation of gaseous pollutantsfor example,
sulfur dioxide (SO2) and nitrogen dioxide (NO2).c) Types of suspended PM include diesel exhaust
particles; coal fly ash; wood smoke; mineral dusts, such as coal, asbestos, limestone, and cement;
metal dusts and fumes; acid mists (for example,sulfuric acid); and pesticide mists.
Inventory Source Classification

Selected Industrial Sectors and Their Contribution to Air and Water Pollution and to
Workplace Hazards

Selected Industrial Sectors and Their Contribution to Air and Water Pollution and to
Workplace Hazards (cont)

CLASSIFICATION OF AIR POLLUTANTS

On the basis of origin, air pollutants can be divided into Primary air pollutants and secondary air
pollutants.
a) PRIMARY AIR POLLUTANTS:
There are directly emitted to the atmosphere, and are found there in the form in which they are
emitted.
i.

Carbon Compounds Carbon dioxide, Carbon monoxide

ii.

Sulphur Compounds Carbonyl Sulphide (COS), Carbon disulphide (CS2) Dimethyl sulphide [CH3S),
Hydrogen sulphide (H2S). Sulphur dioxide (SO2), and sulphate (S02-4)

iii.

Hydrocarbons Benzene, Methane (Marsh gas)

iv.

Oxides of Nitrogen (NOx) NO, NO2, N20

v.

Metals Zinc, Cadmium, Lead, Mercury.

vi.

Toxic Substances Arsenic, Asbestos, Carbon tetra chloride, Berylium, Chromium, Copper, Nickel,
Polycyclic aromatic Hydrocarbons(PAH3)

vii.

Organic Compounds Aldehydes, Ketones, Carboxylic acids, Organic sulphur compounds etc. Finer
Particles (Less than 100 in diameter.) Coarse Particles (Greater than 100 in diameter).
Radioactive compounds Radium- 222, Uranium-232, strontium 90, Plutonium -239.

b) SECONDARY AIR POLLUTANTS:

i.

They are produced in air by interaction among two or more primary pollutants or by reaction with
normal atmospheric constituents (Chemical or Photochemical reactions)

ii.

Ozone formaldehyde PAN ( Peroxy Acetyl Nitrate).

iii.

Photochemical smog (coal induced, H2O2 organic peroxides)

iv.

Formation of Acid mist (H2SO4)due to reaction of sulphur dioxide and dissolved oxygen, when water
droplets are present in the atmosphere.

Earth's

atmosphere

is

slightly warmer than what it

should be due to direct solar
heating because of a mild
case of greenhouse effect

The ground is heated by

visible and (some) infrared
light from the Sun.

The heated surface emits

infrared light.

The

majority

of

Earth's

atmosphere (N2 and O2) are

not good greenhouse gas.

The

small

greenhouse

amount
gases

of
(H2O,

CO2) traps (absorb and reemit) the infrared radiation,

increasing the temperature
of the atmosphere

Greenhouse Gases

The primary components of Earth's atmosphere, N2 and O2 do not have absorption in the IR
wavelength range, therefore, do not have a significant role in setting the surface temperature of the
planet

Greenhouse gas are efficient in absorbing IR light The most important greenhouse gases are:
H2O Water vapor.
CO2 Carbon dioxide
CH4 methane
The most abundant greenhouse gas in Earth's atmosphere is water vapor. Most of the greenhouse
heating of Earth's atmosphere is due to Water vapor absorption of IR radiation emitted by Earth,
and then transferring the energy to the surrounding air molecule
The Atmosphere of Earth

The atmosphere of Earth contains primarily N2 (77%) and O2 (21%).

What happened to all the CO2 ?

Where did all the O2 come from?

Atmospheres of the Terrestrial Worlds

CO2
CO2 is a colorless gas

condenses into solid form (dry ice) at -78C in atmospheric pressure.

condenses into liquid at -57C at pressure above 5.1 atmospheric pressure.

Atmospheric CO2 is derived from (The sources )

Volcanic outgassing

burning of organic matter

Respiration of living organisms

CO2 can be stored in (The Sinks )

Highly soluble in water: forms H2CO3

Dissolved CO2 in water can interact with silicate minerals to form carbonated minerals

Carbon Dioxide Cycle

The mechanism by which Earth self-regulates its temperature is called the carbon dioxide cycle , or
the CO2 cycle for short.
Starting with the carbon dioxide in the atmosphere:

Volcanoes outgas CO2 into the atmosphere.

Atmospheric carbon dioxide dissolves in the oceans.

At the same time, rainfall erodes rocks on Earth's continents and rivers carry the eroded minerals to
the oceans.

In the oceans, the eroded minerals combine with dissolved carbon dioxide and fall to the ocean
floor, making carbonate rocks such as limestone.

Over millions of years, the conveyor belt of plate tectonics carries the carbonate rocks to subduction
zones, and subduction carries them down into the mantle.

As they are pushed deeper into the mantle, some of the subducted carbonate rock melts and
releases its carbon dioxide, which then outgasses back into the atmosphere through volcanoes.
The CO2 Cycle

The CO2 cycle acts as a thermostat that regulates the temperature of the Earth

If Earth warms up a bit, then

carbonate minerals form in the oceans at a

higher rate.

The rate at which the oceans dissolve

CO2 gas increases, pulling CO2 out of the
atmosphere.

The reduced atmospheric CO2concentration

leads to a weakened greenhouse effect that
counteracts the initial warming and cools the
planet back down.
If Earth cools a bit,

carbonate minerals form more slowly in the

oceans.

The rate at which the oceans dissolve

CO2 gas decreases, allowing the CO2released
by volcanism to build back up in the
atmosphere.

The increased CO2 concentration strengthens

the greenhouse effect and warms the planet
back up

Feedback Loop
Positive Feedback
Mechanisms that make things worse
e.g., Increasing CO2 in the atmosphere leads to the release of more CO2
Negative Feedback
Mechanisms that are self-correcting
e.g., Increasing CO2 in the atmosphere leads to higher rate of CO2 removal, such as our CO2 cycle.

Plate Tectonics
Plate tectonics plays an important role in the CO2 cycle in that it helps to carry the carbonate rocks
into the mantle, which are then released again by volcanic activities.
Earth's lithosphere is broken into pieces (the plates).
These plates float on top of the mantle, interacting with each other to produce the geological
features we see and feel today.

Where Did O2 Come From?

The most important source of O2 on

Earth is

Life and Photosynthesis.

Photosynthesis converts CO2 to O2 , and

incorporates carbon into amino acids,
proteins, and other components of living
organisms.
O2 will be depleted from the atmosphere
very rapidly without a source.
O2 is a very reactive chemical that likes to
be combined with other elements
through oxidation. For example, CO2 ,
H2O, FeO (rust) That's how we make
fire!
O2 Absorbs UV, which also transform
some of the O2 into O3, which absorbs
even more UV
O2 not only supports life, it also
protect life!
UV light can break the water molecules
to release oxygen, but the contribution is
small.

The Role of the Magnetic Field of Earth

Another important characteristics of the Earth is its magnetic fields, which shield us from the
bombardment of the high-energy charged particles, mostly from the Sun.

Without magnetic field, the high energy particles of solar wind can strip much of the Earth's
atmosphere by breaking the bonds between the atoms in the air molecules
N2 N + N
O2 O + O
H2O H + H + O

The lighter gases then higher probability of acquiring velocity higher than escape velocity and
escape from Earth!

Runaway Greenhouse Effect

If we were to move the Earth closer to the Sun, like where Venus is now, then we would suffer
runaway greenhouse effect, lose all the water and will become hot like Venus.

Global Warming

There is a gradual increase in

the average temperature of the
Earth's atmosphere in the last
100 yearsIt has risen about
1C since 1900

Are human activities causing

global warming?

What

other

factors

can

(non-human)
cause

global

warming?

How does global warming affect

our life?

Earth's Temperature Variation in the past 1,100 years

Surface Temperatures over the last 1,100 Years

Reconstructions of (Northern Hemisphere average or global average) surface temperature variations

from six research teams (in different color shades) along with the instrumental record of global
average surface temperature (in black). Each curve illustrates a somewhat different history of
temperature changes, with a range of uncertainties that tend to increase backward in time (as
indicated by the shading). Reference: NRC, 2006. (Figure reprinted with permission from Surface
Temperature Reconstructions (2006) by the National Academy of Sciences, Courtesy of the
National Academies Press 22 18, Washington, D.C.).
Reproduced from EPA Climate Change Website.
The Long-Term Stability of Earth's Climate 400,000 years
The atmospheric Changes in Carbon Dioxide and Temperature in the last 400,000 years
concentration

of

CO2 measured from

Antarctic
data

ice

core

implies

that

Earth's climate has

been pretty stable
over

the

400,000 years

past

 It also shows a

rapid

increase

of

about 30% in the

past few centuries
270 ppm (parts
per million) to 370
ppm

Fluctuations in temperature (blue) and in the atmospheric concentration of

carbon dioxide (red) over the past 400,000 years as inferred from Antarctic icecore records . The vertical red bar is the increase in atmospheric carbon dioxide
levels over the past two centuries and before 2006. From A. V. Fedorov et al.
Science 312, 14s85 (2006) 17. 18.
Reproduced from EPA Climate Change Website.
How do we measure atmospheric CO2 concentration in the past?

Precise measurements of atmospheric CO2 concentration is available only in the last few decades

Information about atmospheric CO2 concentration and temperatures in the past can be inferred by
several different methods, such as
Tree-ring
Deep ocean sediment
Ice core records Coral
s
Link to NOAA Paleoclimatology Website
Paleoclimatology is the study of climate prior to the widespread availability of records of
temperature, precipitation and other instrumental data.

Antarctic Ice Core

Located high in mountains

and in polar ice caps, ice
has

accumulated

snowfall

over

from
many

millenia . Scientists drill

through the deep ice to
collect ice cores. These
cores contains dust, air
bubbles,

or

isotopes of

oxygen, that can be used

to

interpret

the

past

climate of that area.

From

NOAA

Paleoclimatology Website.

This figures shows estimates of the changes in

carbon dioxide concentrations during the
Phanerozoic . Three estimates are based on
geochemical modeling: GEOCARB III (Berner
and Kothavala 2001), COPSE (Bergmann et al.
2004)

and

Rothman

(2001).

These

are

compared to the carbon dioxide measurement

database of Royer et al. (2004) and a 30 Myr

CO2 over 500 million years

filtered average of those data. Error envelopes

are shown when they were available. The
right hand scale shows the ratio of these
measurements to the estimated average for
the last several million years (the Quaternary).
Customary labels for the periods of geologic
time appear at the bottom.

Direct determination of past carbon dioxide

levels relies primarily on the interpretation of
carbon

isotopic

ratios

in

fossilized

soils

(paleosols) or the shells of phytoplankton and

through interpretation of stomatal density in
fossil plants. Each of these is subject to
substantial systematic uncertainty.

Estimates of carbon dioxide changes through

geochemical

modeling

instead

rely

on

quantifying the geological sources and sinks

for carbon dioxide over long time scales
particularly:

volcanic

inputs,

erosion

and

carbonate deposition. As such, these models

are

largely

independent

of

direct

measurements of carbon dioxide.

Both

measurements

considerable

and

uncertainty

models
and

show

variation;

however, all points to carbon dioxide levels in

the past that have been significantly higher
than they are at present.

Which gas is keeping the Earth warm?

The major natural greenhouse gases are

water vapor, which causes about 36-70% of the greenhouse effect on Earth ( not
including clouds );

carbon dioxide, which causes 9-26%;

methane, which causes 4-9%, and

ozone, which causes 3-7%.

Note that it is not really possible to assert that a certain gas causes a certain
percentage of the greenhouse effect , because the influences of the various gases
are not additive. (The higher ends of the ranges quoted are for the gas alone; the
lower ends, for the gas counting overlaps.) [3] [4]
rom http://en.wikipedia.org/wiki/Greenhouse_gas

So, what's the big deal if human CO2 causes 1C temperature increase?

An increase in atmospheric temperature

(human or natural origin) will lead to the
increase in the water vapor content of the
troposphere.

Because

water

vapor

is

strong

greenhouse gas, the increase in H2O vapor

in turn causes enhanced greenhouse effect,
raising the temperature more.

Higher atmospheric temperature will cause

more evaporation of water

Which leads to even higher temperature

Runaway Green House Effect!

How about Clouds and Ice?

Water vapor (water in gaseous phase) is one of the most potent and abundant
greenhouse gasbut

Clouds (water in liquid form) reflect sunlight, decreasing the solar energy input into Earth's
atmosphere during the day, but they trap IR radiation from the Earth during the night. It's net effect
is not well know so far
Albedo of clouds range from close to 0 to 70%.
Testing climate impact of clouds after Sept. 11, 2001

Ice has a very high albedo , ~ 80 to 90%.

Thus, reduction of the polar ice cap can cause more heating

Contrails and Climate

Contrails are artificial clouds made by
the exhaust of the aircraft engines, or
the

wingtip

vortices

(http://en.wikipedia.org/wiki/Contrail).
Contrails produced by the heavy air
traffic

over

the

US

may

have

noticeable influences on the weather

Commercial air traffic were suspended

for three days after the Sept. 11, 2001
attack. This provided a rare chance for
the climate scientist to test their
theory

Measurements

show

that

without

contrails the local difference of day and

night-time temperatures was about 1
degree Celsius higher than immediately
before the attack

How About The CO2 Cycle?

The CO2 cycle acts as a thermostat that regulates the temperature of the Earth
If Earth warms up a bit, then

carbonate minerals form in the oceans at a

higher rate.

The rate at which the oceans dissolve

CO2 gas increases, pulling CO2 out of the
atmosphere.

The reduced atmospheric CO2concentration

leads to a weakened greenhouse effect that
counteracts the initial warming and cools the
planet back down.
If Earth cools a bit,

carbonate minerals form more slowly in the

oceans.

The rate at which the oceans dissolve

CO2 gas decreases, allowing the CO2released
by volcanism to build back up in the
atmosphere.

The increased CO2 concentration strengthens

the greenhouse effect and warms the planet
back up

Feedback Loop

Positive Feedback
Mechanisms that make things worse
e.g., Increasing CO2 in the atmosphere leading to the release of more CO2

Negative Feedback
Mechanisms that are self-correcting
e.g., Increasing CO2 in the atmosphere leading to higher rate of CO2 removal, such as our
CO2cycle.

History

First studies on rain chemistry were conducted in late 1800s, but modern investigations date back to
1960s.

Nowadays the chemistry of atmospheric precipitation is fairly well known.

The phenomenon of acid rain has been known and studied from 1950s.

1960 lowered fish production in Scandinavian lakes

In 1972 it became an international public policy issue at the first United Nations Conference on the
Environment held in Stockholm.

The transboundary effect of atmospheric pollution has been officially accepted, based on the fact
that sulphur and nitrogen oxides are commonly emitted in one location while the acid deposition
occurs in distant area.

In Sweden and Norway around 90% of the acid deposition comes from other countries, primarily
UK, Germany, Poland and other Central Europe countriess. Canada receives major acid contribution
from the US.

Rain that is more acidic than normal because it contains sulfuric acid or nitric acid

result of SOx, NOx, acidic particulates in air

involves all forms of acid deposition, even if rain is not involved

Utility plants contribute to 70% SO2 production and 30% NOx production in USA Coal contains as
high as 5% sulfur
Mechanism of acid rain

Acid Deposition Formation

Acid deposition can form as a result of two processes. In some cases, hydrochloric acid can be
expelled directly into the atmosphere. More commonly it is due to secondary pollutants that form
from the oxidation of nitrogen oxides (NOx) or sulfur dioxide (SO2) gases that are released into the
atmosphere. Reactions at the Earth's surface or within the atmosphere can convert these pollutants
into nitric acid or sulfuric acid. The process of altering these gases into their acid counterparts can
take several days, and during this time these pollutants can be transported hundreds of kilometers
from their original source. Acid precipitation formation can also take place at the Earth's surface
when nitrogen oxides and sulfur dioxide settle on the landscape and interact with dew or frost.
Emissions of sulfur dioxide are responsible for 60-70% of the acid deposition that occurs globally.
More than 90% of the sulfur in the atmosphere is of human origin. The main sources of sulfur
include:
1. Coal burning - coal typically contains 2-3% sulfur so when it is burned sulfur dioxide is liberated.
2. The smelting of metal sulfide ores to obtain the pure metals. Metals such as zinc, nickel, and copper
are all commonly obtained in this manner.
3. Volcanic eruptions - although this is not a widespread problem, a volcanic eruption can add a lot of
sulfur to the atmosphere in a regional area.
4. Organic decay.
5. Ocean spray.
After being released into the atmosphere, sulfur dioxide can either be deposited on the Earth's
surface in the form of dry deposition or it can undergo the following reactions to produce acids that
are incorporated into the products of wet deposition.
SO2 + H2O H2SO3
H2SO3 + 1/2O2 H2SO4

Some 95% of the elevated levels of nitrogen oxides in the atmosphere are the result of human
activities. The remaining 5% comes from several natural processes. The major sources of nitrogen
oxides include:
1. Combustion of oil, coal, and gas.
2. Bacterial action in soil.
3. Forest fires.
4. Volcanic action.
5. Lightning.
Acids of
NO

nitrogen form

as a result of
+

the following atmospheric chemical reactions

1/2O2
NO2

2NO2 +
NO2 + OH HNO3

H2O

HNO2 +

HNO3

Finally, the concentrations of both nitrogen oxides and sulfur dioxides are much lower than
atmospheric carbon dioxide which is mainly responsible for making natural rainwater slightly acidic.
However, these gases are much more soluble than carbon dioxide and therefore have a much
greater effect on the pH of the precipitation.
Effects of Acid Deposition
Acid deposition influences the environment in several different ways. In aquatic systems, acid
deposition can effect these ecosystems by lowering their pH. However, not all aquatic systems are
effected equally. Streams, ponds, or lakes that exist on bedrock or sediments rich in calcium and/or
magnesium are naturally buffered from the effects of acid deposition. Aquatic systems on neutral or
acidic bedrock are normally very sensitive to acid deposition because they lack basic compounds
that buffer acidification.
One of the most obvious effects of aquatic acidification is the decline in fish numbers. Originally, it
was believed that the fish died because of the increasing acidity of the water. However, in the 1970s
scientists discovered that acidified lakes also contained high concentrations of toxic heavy metals
like mercury, aluminum, and cadmium. The source of these heavy metals was the soil and bedrock
surrounding the water body. Normally, these chemicals are found locked in clay particles, minerals,
and rocks. However, the acidification of terrestrial soils and bedrock can cause these metals to
become soluble. Once soluble, these toxic metals are easily leached by infiltrating water into aquatic
systems where they accumulate to toxic levels.
Lake acidification

The severity of the impact of acid deposition on vegetation is greatly dependent on the type of soil
the plants grow in. Similar to surface water acidification, many soils have a natural buffering
capacity and are able to neutralize acid inputs. In general, soils that have a lot of lime are better at
neutralizing acids than those that are made up of siliceous sand or weathered acidic bedrock. In less
buffered soils, vegetation is effected by acid deposition because:
1. Increasing acidity results in the leaching of several important plant nutrients, including calcium,
potassium, and magnesium. Reductions in the availability of these nutrients cause a decline in plant
growth rates.
2. The heavy metal aluminum becomes more mobile in acidified soils. Aluminum can damage roots and
interfere with plant uptake of other nutrients such as magnesium and potassium.
3. Reductions in soil pH can cause germination of seeds and the growth of young seedlings to be
inhibited.
4. Many important soil organisms cannot survive is soils below a pH of about 6.0. The death of these
organisms can inhibit decomposition and nutrient cycling.
5. High concentrations of nitric acid can increase the availability of nitrogen and reduce the availability
of other nutrients necessary for plant growth. As a result, the plants become over-fertilized by
nitrogen (a condition known as nitrogen saturation).
6. Acid precipitation can cause direct damage to the foliage on plants especially when the precipitation
is in the form of fog or cloud water which is up to ten times more acidic than rainfall.
7. Dry deposition of SO2 and NOx has been found to affect the ability of leaves to retain water when
they are under water stress.
8. Acidic deposition can leach nutrients from the plant tissues weakening their structure.
How Acid Rain Affects The Environment

Acid rain is an extremely destructive form of pollution, and the

environment suffers from its effects. Forests, trees, lakes, animals,
and

plants

suffer

from

acid

rain.

Trees
The needles and leaves of the trees turn brown and fall off.
Trees can also suffer from stunted growth; and have damaged bark
and leaves, which makes them vulnerable to weather, disease, and
insects.

Lakes are also damaged by acid rain. Fish die off, and that removes the main source of food for
birds. Acid rain can even kill fish before they are born when the eggs are laid and come into contact
with the acid.
Fish usually die only when the acid level of a lake is high; when the acid level is lower, they can
become sick, suffer stunted growth, or lose their ability to reproduce.
Also, birds can die from eating "toxic" fish and insects.

The combination of these effects can lead to plants that have reduced growth rates, flowering ability
and yields. It also makes plants more vulnerable to diseases, insects, droughts and frosts.
The effects of acidic deposition on humans can be divided into three main categories. Acid
deposition can influence human health through the following methods:
1. Toxic metals, such as mercury and aluminum, can be released into the environment through the
acidification of soils. The toxic metals can then end up in the drinking water, crops, and fish, and are
then ingested by humans through consumption. If ingested in great quantities, these metals can

have toxic effects on human health. One metal, aluminum, is believed to be related to the
occurrence of Alzheimer's disease.
2. Increased concentrations of sulfur dioxide and oxides of nitrogen have been correlated to increased
hospital admissions for respiratory illness.
3. Research on children from communities that receive a high amount of acidic pollution show
increased frequencies of chest colds, allergies, and coughs.

Finally, acid deposition effects a number inanimate features of human construction. Buildings and
head stones that are constructed from limestone are easily attacked by acids, as are structures that
are constructed of iron or steel. Paint on cars can react with acid deposition causing fading. Many of
the churches and cathedrals in Europe are under attack from the effects of acidic deposition.

1. Why the hole in the atmospheric ozone layer above us?

2. What has been done about this?
3. Why should we worry about Ozone Layer Depletion?
Good life at the beach threatened?

What is Ozone? Ozone Layer?

Ozone (O3) is a highly-reactive from of oxygen.

Unlike oxygen (O2), ozone has a strong scent and is blue in color.

Ozone exists within both the tropospheric and stratospheric zones of the Earth's atmosphere

In the troposphere , ground level ozone is a major air pollutant and primary constituent of
photochemical smog

In the stratosphere, the ozone layer is an essential protector of life on earth as it absorbs harmful
UV radiation before it reaches the earth.

CFC's and ozone depletion

Chlorofluorocarbons are created and used in refrigerators and air

conditioners. These chlorofluorocarbons are not harmful to humans
and have been a benefit to us. Once released into the atmosphere,
chlorofluorocarbons are bombarded and destroyed by ultraviolet rays.
In the process chlorine is released to destroy the ozone molecules

Destruction of ozone by chlorine

Molecular oxygen is broken down in the stratosphere by solar radiation to yield atomic oxygen,
which then combines with molecular oxygen to produce ozone. The ozone is then destroyed by
chlorine atoms.
Ozone destruction by UV rays

UV

radiation

from

the

sun

releases the radicals Cl and ClO .

Ozone

is

highly

unstable

molecule so it readily donates its

extra oxygen molecule to free
radical species such as hydrogen,
bromine, and chlorine.

These compound species act as

catalysts in the breakdown of
ozone molecules.

The ozone depletion process

Responsibility for ozone damage each year

Global CFC production

Effects of UV rays on Aquatic Ecosystems

Ozone depletion causes increases in UV rays's effects on aquatic ecosystems by:
1. decreasing the abundance of phytoplankton affects the food stock for fishes and the absorption of
CO2
2. decreasing the diversity of aquatic organisms reduces food stock and also destroys several fish
and amphibians.
Effects of UV rays on Terrestrial Ecosystems

Damage to plant cell DNA molecules - makes plants more susceptible to pathogens and pests

Reductions in photosynthetic capacity in the plant - results in slower growth and smaller leaves

Causes mutations in mammalian cells and destroys membranes

Harmful effects of UV rays on people

Skin cancer

Premature aging (photoaging) of the skin (different from normal chronological aging)

Cataracts and eye disorders (corneal sunburn and blindness) Immune system damage
Correlation between Ozone depletion and skin diseases

The Ultraviolet Exposure Index

INDEX VALUES EXPOSURE
0 2 = Minimal
3 - 4 = Low

5 - 6 = Moderate
7 - 9 = High

10 + = Very High
Factors affecting UV exposure

Clouds cover - partly cloudy days do little to reduce UV exposure but rainy or substantially
overcast days reduce UV exposures

The time of day peak exposure time is 12:00 noon - 1:00 p.m. UV intensity is reduced by about
half at three hours before and three hours after the peak exposure time.
Factors affecting UV exposure..2

The time of year - more UV is received in the late spring and early summer and much less is
received in the late fall and early winter.

Life style determines a person's risk to UV exposure. Skiing, sunbathing, or swimming can lead to
extremely high exposures. Use of tanning parlors also increase risk.

Global Carbon Cycle

Carbon is exchanged between the active pools due to various processes photosynthesis and
respiration between the land and the atmosphere, and diffusion between the ocean and the
atmosphere.

Carbon Pools

Carbon is stored on our planet in the following major pools:

as organic molecules in living and dead organisms found in the biosphere;

as the gas carbon dioxide in the atmosphere;

as organic matter in soils;

in the lithosphere as fossil fuels and sedimentary rock deposits such as limestone, dolomite and
chalk;

in the oceans as dissolved atmospheric carbon dioxide and as calcium carbonate shells in marine
organisms.
Microorganisms are strongly involved in the carbon cycle, mediating crucial biochemical reactions
discussed later in this section.
Photosynthetic algae are the predominant carbon-fixing organisms in water; as they consume CO2,
the pH of the water is raised enabling precipitation of CaCO3 and CaCO3, MgCO3.
Organic carbon fixed by microorganisms is transformed by biogeochemical processes to fossil
petroleum, kerosene, coal, and lignite. Microorganisms degrade organic carbon from biomass,
petroleum, and xenobiotic sources, ultimately returning it to the atmosphere as CO2.

Photosynthesis in which algae, higher plants, and photosynthetic bacteria use light energy to fix
inorganic carbon in a high-energy organic form:

Respiration in which organic matter is oxidized in the presence of molecular O2 (aerobic respiration)
or anaerobic respiration, which uses oxidants other than O2, such as NO3- or SO42-

Degradation of biomass by bacteria and fungi. Biodegradation of dead organic matter consisting
predominantly of plant residues prevents accumulation of excess waste residue and converts organic
carbon, nitrogen, sulfur, and phosphorus to simple organic forms that can be utilized by plants.
It is a key part of the biogeochemical cycles of these elements and also leaves a humus residue that
is required for optimum
physical condition of soil.
Biodegradation of organic matter, such as occurs in treatment of municipal wastewater by reactions
represented in a general sense by,

Methane production by methane-forming bacteria, such as Methanobacterium, in anoxic (oxygenless) sediments, plays a key role in local and global carbon cycles as the final step in the anaerobic
decomposition of organic matter. It is the source of about 80% of the methane entering the
atmosphere.

Microbial methane production is a fermentation reaction, defined as an oxidation-reduction process

in which both the oxidizing agent and reducing agent are organic substances.
Bacterial utilization and degradation of hydrocarbons. The oxidation of higher hydrocarbons under
aerobic conditions by Micrococcus, Pseudomonas, Mycobacterium, and Nocardia is an important
environmental process by which petroleum wastes are eliminated from water and soil.
The initial step in the microbial oxidation of alkanes is conversion of a terminal CH3 group to a
CO2group followed by oxidation,

wherein carbon atoms are removed in 2-carbon fragments. The overall process leading to ring
cleavage in aromatic hydrocarbons is the following in which cleavage is preceded by addition of
OH to adjacent carbon atoms:
Where is nitrogen found in the environment?

The largest single source of nitrogen is in the atmosphere.

How does atmospheric nitrogen get changed

into a form that can be used by most living
organisms?

By traveling through one of the four processes in the Nitrogen Cycle!

The first process in the nitrogen cycle is

Nitrogen Fixation!

What is nitrogen fixation and what does it

mean to say nitrogen gets fixed?

Nitrogen Fixation is the process that causes the strong two-atom nitrogen molecules found in the
atmosphere to break apart so they can combine with other atoms.

Nitrogen gets fixed when it is combined with oxygen or hydrogen.

There are three ways that nitrogen gets fixed!

Atmospheric

Fixation

(Only 5% to 8% of the Fixation

Process)
The enormous energy of lightning
breaks nitrogen molecules apart and
enables

the

nitrogen

atoms

to

combine

with

oxygen

forming

nitrogen

oxides

(N2O).

Nitrogen

oxides

dissolve

in

rain,

forming

nitrates. Nitrates (NO3) are carried to

the ground with the rain.

Industrial

Fixation

Under great pressure, at a

temperature of 600 degrees
Celcius, and with the use of a
catalyst, atmospheric nitrogen
(N2)

and

hydrogen

are

combined to form ammonia

(NH3). Ammonia can be used
as a fertilizer.

Biological Fixation
(where MOST nitrogen fixing is completed)
There are two types of Nitrogen Fixing Bacteria

Free Living Bacteria

Highly specialized bacteria live in the soil and have the ability to combine atmospheric
nitrogen with hydrogen to make ammonia (NH3).

Symbiotic

Relationship

Bacteria

Bacteria live in the roots of legume family plants

and provide the plants with ammonia (NH3) in
exchange for the plants carbon and a protected
home.

Most atmospheric nitrogen (N2) is fixed and changed to ammonia (NH3). Ammonia is highly toxic
to many organisms. Can plants use ammonia?
Very few plants can use ammonia (NH3)

but, fortunately the

second process
Ammonification can help!

What is ammonification?
Ammonification: Bacteria decomposers break down amino acids from dead animals and wastes into
nitrogen ammonium.

Why is ammonification necessary?

Because plants cannot use the organic forms of nitrogen that are in the soil as a result of:
(1)
wastes
(manure
and
sewage)
(2) compost and decomposing roots and leaves

How does ammonification occur?

Microorganisms convert the organic nitrogen to ammonium. The ammonium is either taken up by
the plants (only in a few types of plants) or is absorbed into the soil particles. Ammonium (NH4) in
the soil is stored up to later be changed into inorganic nitrogen, the kind of nitrogen that most
plants can use.

What happens to ammonium (NH4) stored in the soil?

It travels through the

third process
of the nitrogen cycle called Nitrification!

First we will quickly run through a

general overview of the Nitrification
Process

Nitrifying bacteria in the ground first combine ammonia with oxygen to form nitrites. Then another
group of nitrifying bacteria convert nitrites to nitrates which green plants can absorb and use!

Now we will take a closer look at the

Nitrification Process

Nitrification is a biological process during

which nitrifying bacteria convert toxic
ammonia

to

less

harmful

nitrate.

Nitrification aids in the decomposition of

nitrogenous material and thus in the
recycling of nitrogen atoms since the
decontamination

of

organic

nitrogen

produces ammonia that is subsequently

oxidized to nitrate by nitrification.

There two bacterial species involved.

Nitrosomonas

sp.

Bacteria

oxidize

ammonia into nitrite, while Nitrobacter

bacteria convert nitrite to nitrate, with
both species utilizing the energy released
by the reactions.
Ammonia can be used by some plants.
Most nitrogen taken up by plants is
converted by chemoautotrophic bacteria
from ammonia, which is highly toxic to
many organisms, first into nitrite (NO2-),
and then into nitrate (NO3-). This process
is called nitrification, and these bacteria
are known as nitrifying bacteria.
Nitrifiers such as Arthrobacter (heterotroph), Aspergillis (heterotroph), and Nitrosomonas
(autotroph) are delicate organisms and extremely susceptible to a variety of inhibitors. They are
extremely slow growing, unlike many bacteria that can double their numbers every hour or so. In
order to thrive, nitrifying bacteria need a relatively clean environment with a steady supply of
ammonia and oxygen.
Nitrification is a Two Step Process

1. First Step: Ammonium Oxidation

The microorganisms involved are called the
ammonia oxidizers. Nitrosomonas is the most
extensively studied and usually the most
numerous in soil. Nitrosospira is an aquatic
nitrifier.
Nitrosomonas
Nitrosospira
Nitrosococcus
Nitrosolobus

Ammonia-Oxidizing Bacteria:
These organisms are chemoautotrophs, growing with ammonia as the energy and CO2 as the main
carbon source. Species are distributed in a great variety of soils, oceans, brackish environments,
rivers, lakes, and sewage disposal systems.
2. Second step: Nitrite Oxidation
Microorganism involved: Nitrobacter
These bacteria comprise a diverse group of rod, ellipsoidal, spherical, and spiral-shaped cells. At
least one strain of Nitrobacter has been described that can grow by anaerobic respiration
(denitrification).
Nitrite-oxidizing bacteria are found in aerobic, but occasionally also in anaerobic, environments
where organic matter is mineralized. They are widely distributed in soils, fresh water, brackish
water, seawater, mud layers, sewage disposal systems, and inside stones of historical buildings and
rocks. They are also found inside corroded bricks and on concrete surfaces such as in cooling towers
and highway-automobile tunnels.

How

does

nitrogen

re-enter

the

atmosphere in the nitrogen cycle?

Through the fourth process called denitrification!

What does denitrification do?

Denitrification converts nitrates (NO3) in the soil to atmospheric nitrogen (N2) replenishing the
atmosphere.

How

does

denitrification

the
process

work?

Denitrifying bacteria live deep in soil and in aquatic sediments where conditions make it difficult for
them to get oxygen. The denitrifying bacteria use nitrates as an alternative to oxygen, leaving free
nitrogen gas as a byproduct. They close the nitrogen cycle!

Other ways that nitrogen returns to the atmosphere

SULFUR CYCLE
Sulfur reservoirs
Driving forces for sulfur transformation
Sulfur in the atmosphere
Sulfur in rivers
Sulfur in the ocean
Global sulfur cycle
Sulfur budget for the ocean
Pyrite formation in sediments
Diagenetic modelling

Sulphur Cycle

Global Sulfur Cycle

Valence states: +6 (SO42-) to -2 (sulfides)

Original pool - pyrite FeS2

Reservoirs,1018 g S:
Deep oceanic rocks 2375 820
Sediments 78001700
Freshwater 0.0030.002
Ice 0.0060.002
Atmosphere 3.6
Sea 128055
Organic 5.62x 10-3
Driving Forces: Microbial Transformation
Anaerobic conditions:
sulfate

reduction:

(Desulfovibrio

sp.

or

Desulfotomaculum sp.))
bacteria produce a variety of gases: hydrogen sulfide (H2S), dimethyl-sulfide (CH3)2S, carboxyl
sulfide COS

H2S reacts with Fe2+ to precipitate FeS, which can be converted to pyrite FeS2:

H2S diffuses though zone of F3+

sulfur-based photosynthesis (thought to be one of first forms of photosynthesis on the

Earth)
Plant uptake:

assimilatory SO42- reduction and incorporation of carbon-bounded sulfur into the amino acids
cysteine and methionine.
Aerobic conditions:
reduced sulfur compounds oxidized by microbes, oxidation usually coupled to reduction of CO2 in
relations of S-based chemosynthesis.
Sulfur in the Atmosphere

Gaseous component

no sulfur gas is a long-lived or major constituent of the atmosphere, oxidation of SO42-

short

residence time, all expressions in g S

Aerosols

particles < 1um are held a loft by Brownian motion

long transport

sources: volcanic eruptions, ocean, water evaporates from bubbles, the salt crystallizes to form seasalt aerosols
Sources of Sulfur in the Atmosphere
Eriksson (1960) - SO42- deposition on land from ocean 4x1012 g S ,
Jung (1960) - SO42- in rainfall in land 73x1012 g S,

other sources as sea.

Volcanic eruptions

average over many years 12-30x1012 g S

e.g. Tambora (Indonesia) in 1815, 1816 - year without summer in England, USA, Canada, 50x1012 g
S

Soil dust

Biogenic gases

H2S, dimethyl-sulfide (CH3)2S, carbonyl sulfide COS

Anthropogenic emissions

without human effects, net transport through the atmosphere carries S from sea to land
Sulfur in Rivers

Natural river load

from

and gypsum, rainfall

weathering

of

pyrite

Human activities affect the transport of S in rivers

28% of the current content of S in rivers is derived from air pollution, mining, erosion, and the other
human activities

the current transport is supposed to be about double that of pre-industrial conditions

Marine sulfur cycle

Ocean is large source of aerosols (sea salts) that contains SO42-.

Most of the flux is re-deposited in the ocean in precipitation and dry-fall

Dimethyl-sulfide (CH3)2S or DMS is the major biogenic gases emitted from sea

annual flux is about 15

mean residence time about 1-2 days - most of S from DMS is also re-deposited in the ocean

The net transport of S from sea to land is about 20x1012 g S/yr. Ocean receives a net input of S.

Global Sulfur Cycle

Sulfur budget for the ocean

Marine sulfur cycle

Content 12x1020 g S/ yr., residence time > 3 000 000 years.

Major marine sinks: metallic sulfides precipitated at hydro-thermal vents, biogenic pyrites, the
formation of organic sulfur.
Dimethylsulfid(CH3)2S or DMS
DMS is the major one of biogenic gases emitted from sea

Mean residence time is about 1-2 days - most of S from DMS is also re-deposited in the ocean

Is produced during decom-position of dimethyl-sulfonpropionate (DMSP) from dying phytoplankton

Only small fraction lost into the atmosphere

DMS and climate

oxidation of DMS to sulfate aerosols increases the abundance of cloud condensation nuclei

to

greater cloudiness

layer of sulfate aerosols (known as Junge layer) is about 20-25 km altitude, source: SO2 and
carbonyl sulfate COS

clouds over sea reflect incoming sunlight

production of DMS - net primary production.

global cooling

if higher NPP is associated with warmer sea surface, then DMS-flux would have negative feedback
on global warming
Pyrite Formation in Sediments
Sulfate reduction :
Two steps reaction

Recently

In strictly anoxic sediments

In salt sediments
Pyrite
(after Berner 1972)

Formation

in

Sediments

Persistent Organic Pollutants

Humans are exposed daily to numerous chemicals that can harm their health

Many harmful organic compounds are stable in the environment (atmosphere, water, soil, food
chain) for long periods Persistent Organic Pollutants (POPs)
- Characterised by stability, mobility, and bioaccumulation
- Harmful to human health and produce ecological damage

Stockholm Convention (May 2001): over 90 countries promised to reduce or eliminate the
production, use, and release of 12 key POPs the dirty dozen.
12 Key POPs the dirty dozen
The Dirty Dozen are produced for use as insecticides, fungicides, chemical additives, or are
inadvertently produced during combustion. A biocide is a substance toxic to varying degrees to life
forms:
Either synthesised deliberately to target and kill specific organisms general name pesticide
Or may be inadvertently produced
Pesticides: insecticide, bactericide, fungicide, herbicide
A pesticide designed to eliminate all types of living organisms is called a fumigant or sterilant

POP

Use

Structure

Aldrin

Crop insecticide (corn,

cotton)

Chlordane

Crop

insecticide

(vegetables,

citrus,

cotton, potatoes)
DDT

Crop

insecticide

(cotton)
(dichloro-diphenyltrichloroethane)
Dieldrin

Crop

insecticide

(cotton, corn)
Endrin

Crop

insecticide

(cotton, grains)
Heptachlor

Insecticide

(termites

and soil insects)

Hexachlorobenzene

Fungicide

for

seed

treatment
Mirex

Insecticide

(termites,

fire ants)
Toxaphene

Insecticide

(livestock,

crops)
PCBs

Industrial
(paint

chemical
and

plastic

additive)
Dioxins

Unintentionally
produced

during

combustion
Furans

Unintentionally
produced

during

combustion

Organic biocides
Fate of biocides in the environment:
Chemical stability (rate it degrades to other compounds)
Mobility (mechanism and rate of transport)
Rapid degradation mobility less of an issue
Different degradation mechanisms may operate as the pesticide moves to a new environment

Degradation products may have biocidal properties:

Usually reduced toxicity, but sometimes toxicity is enhanced
Polychlorinated Hydrocarbons
All the Dirty Dozen are polychlorinated hydrocarbons
They are stable and do not readily degrade to less toxic forms
Persist in the environment for a long time and can bioaccumulate through the food chains
Insoluble in water, soluble in fats
Polychlorinated hydrocarbons of particular concern are:

Pesticide production

Few pesticides were available before 1940:

Some natural insect poisons extracted from plants
Early insecticides were nicotine sulfate obtained from tobacco, retenone from the tropical derris
plant and garlic oil
A few inorganic compounds of lead and arsenic

Large scale use of pesticides began after WWII with the introduction of DDT
DDT
At its introduction it seemed to be an ideal insecticide:
Cheap to produce
Apparently non-toxic to humans and other mammals
Did not breakdown easily continued to kill insects for a long time after application

DDT A Short History

1874 First synthesised by Othmar Zeidler - dichlorodiphenyltrichloroethane (DDT)

1939 Paul Hermann Mller discovered insecticidal properties of DDT
1940s Rapid development in WW2 to combat malaria, typhus, and other mosquito-borne diseases
in military & civilian populations
- Following WW2, extensive use of DDT contributed to eradication of malaria in America & Europe
1948 Mller awarded Nobel Prize

1950s A WHO campaign to eradicate malaria was based on extensive spraying with DDT a
marked reduction in malaria mortality rate was found
mortality rate dropped from 192 to 7 per 100,000
- increasing resistance to DDT was found in pests
DDT A Short History
1950s Marked decline of bird populations, especially raptors like the peregrine falcon, osprey, and
eagles, were observed
1962 Rachel Carson publishes Silent Spring, raising American awareness of the ecological effects
& health risks of DDT and start of modern environmental movement.

1970s-80s ban on DDT use in Western countries; recovery of affected bird populations
DDT use continued in developing countries, but widespread spraying discontinued. Insecticide
impregnated bednets and indoor spraying favoured.
2001 Stockholm convention, restricting DDT use to health crises
DDT
Chemical stability: DDT degrades to DDE (dichlorodiphenyldichloroethene)

DDE is less toxic than DDT but more resilient in the environment
DDT has a broad spectrum of activity. It was banned in several countries in the 1970s because of
ecological considerations
Still used extensively to reduce insect-transmitted diseases:
yellow fever, sleeping sickness, typhus, malaria and others
Persistent in the environment and resistant to complete degradation by microorganisms
Photodegradation can occur
Readily adsorbed onto sediments and soil
Most DDT that enters water becomes firmly attached to soil particles
Readily taken up by microorganisms and is therefore passed on through the food chain
Normally stored in fatty tissue
The Effect of DDT on Ecosystems

Mean levels of DDT (ng/g in fat) in the Lake Kabira

(Berg. 1992) .

DDT Environmental Levels and Human Exposure

Air: when DDT is sprayed, any that fails to reach its target can drift away. Vaporisation from treated
fields can be detected for more than 6 months after application. It can drift up to 1000 km
Environmental levels:
Nonagricultural areas: < 1 2.4 ng m-3
Agricultural communities: 1 22 ng m-3
Communities with anti-mosquito programmes: up to 8.5 g m-3

Water: highest level recorded 0.84 mg/L (USA: 1964 1968)

Over 90% of DDT in the general population comes from food
Acute exposure: Acute toxicity of DDT is high in insects and lower in mammals. Large doses causes
focal necrosis of liver cells in several species. It increases liver tumours in mice
Human exposure: Can affect the nervous system. Acute intoxication by DDT can lead to symptoms
such as nausea, vomiting, paraesthsia, dizziness, confusion, tremors and in severe cases convulsions
All the symptoms are rare
No evidence that DDT has reproductive or teratogenic effects
All epidemiological studies in humans have indicated that DDT is not carcinogenic
Pollutant Formation in Combustion Systems

NOx Formation
Thermal NOx
Prompt NOx
Fuel NOx

Carbon Monoxide (CO)

Volatile Organic Compounds (VOC)

Polycyclic Aromatic Hydrocarbons (PAH), Soot and Submicron Particulates (solid-phase pollutants)

Sulphur Compounds
NOx formation
What is NOx?

NOx = Oxides of Nitrogen which are produced by combustion:

Nitric Oxide (NO)
Nitrogen Dioxide (NO2)

Nitrous Oxide (N2O)

Nitric Oxide (NO)

Highly reactive due to lone electron at N atom

Not particularly toxic

Major precursor of photochemical smog (NO NO2)

It is produced by most of combustion systems

Nitrogen Dioxide ( NO2)

Brown, poisonous gas

Emissions of NO2 from most combustion < 10% of NOx

Adverse health effects include: lung irritation, bronchitis, pneumonia and a lowering respiratory
resistance

Ambient limit = 120ppb [NEPC, 1998]

Significant direct emissions of NO2 occur from processes involving premixed flames:
- Indoor gas appliances (20-100% of NOx)
- Gas turbines yellow/brown plumes
Nitrous Oxide (N2O)

Relatively inert

Uses: Dental anaesthetic

Strong absorber of infrared radiation (~300 x CO2)

Stability = long atmospheric residence times (~150 yrs)

Hence, potentially significant greenhouse gas

Long life-time also allows its transportation into stratosphere and participates in ozone depletion

Only significant from low-temperature processes (eg. Fluidised bed combustion)

Sources of Nitrogen

Formation of NOx requires a source of nitrogen

Two sources of nitrogen:

a. Molecular nitrogen from air (1/2 N2 (from air) +1/2 O2 NO)
Thermal or Zeldovich Mechanism.
Prompt-Fenimore Mechanism (HC + N2).
Other minor mechanisms
b. Nitrogen chemically bound within fuel
Fuel NOx,

Most of NOx in the form of NO

Thermal NO

One of the most important issues for combustion engineers is: 'What are my NOx emissions?'

In most cases, unusually high NOx emissions are due to NO formed by the Thermal (Zeldovich)
mechanism

Thermal NO mechanism involves the attack of molecular nitrogen (N2) and atomic nitrogen (N) by
oxygen (O2) and oxygen-containing radicals (O, OH). This can occurs in oxygen rich mixture.

First identified by Zeldovich (1946) and extended by Fenimore and Jones (1957)

Described by the following reactions:

N2 + O NO + N (R.1)
N + O2 NO+O (R.2)
N + OH NO + H (R.3)

Westenberg (1971) invoked the steady-state approximation and determined that the maximum NO
formation rate is given by:

Hence, [NO] depends on:

-Temperature (the higher the temp, strongly the higher the NO formed) high temp environment
-O2 concentration (the higher the oxygen conc, the higher the NO formed) oxygen-rich
environment
-Residence time

Prompt NO
Fenimore (1971) observed an additional formation of NO which could not be explained by the
thermal mechanism

NO formed close to the burner (hence - "prompt' NO)

Effect is not observed under very fuel-lean conditions or in systems with H2 or CO as fuel

Mechanism involves the attack of N2 by hydrocarbon fuel fragments, mainly CH radicals and
C-atoms.

The Prompt-Fenimore mechanism is initiated mainly by R.4 (the formation of HCN) with a lesser
contribution from R.5:
CH + N2 HCN + N (R.4)
C + N2 CN + N (R.5)

HCN is subsequently oxidised to NO (see diagram)

Prompt mechanism dominates for hydrocarbon combustion in fuel-rich, in both premixed and
diffusion flames

Minor Mechanisms
1. N2O-Intermediate Mechanism:

It occurs under fuel-lean, low-temperature conditions

Minor source of NO in most practical combustors

Mechanism is given by:

O + N2 + M N2O + M (R.6)
O + N2O NO + NO (R.7)
H + N2O NO + NH (R.8)
2. NNH-Intermediate Mechanism:

It is observed under laboratory conditions

H2 and CH4 (high H) fuel-rich, laminar premixed flames

Yet to be definitely observed in practical combustors

Mechanism is given by:

H + N2 NNH
NNH + O NO + NH

(R.9)
(R.10)

Fuel-NO
1. The Nature of Fuel-Nitrogen:

Nitrogen in coal (and oil) originates in the plant material from which the fuel is formed

Plants contain nitrogen in the form of proteins, amino acids, alkaloids, chlorophyll and porphyrins

These were transformed, during the coalification process, into polycyclic aromatic compounds with
pyridinic, pyrrolic or other functional groups

Nitrogen content of coals typically vary between 1-2.5 wt% and is largely independent of rank

2. Coal Combustion and the Release of Fuel-Nitrogen:

First stage of coal combustion is rapid devolatilisation of the coal

Devolatilisation: volatile components such as light hydrocarbons and tars are released and then
oxidised in the gas~phase at very short timescales (< 10 ms)

The solid product of coal pyrolysis is the char which is oxidised at much slower timescales (~ 1s)

Fuel-nitrogen is released during both pyrolysis and char combustion but in very different ways

Partitioning of fuel-nitrogen between the volatiles and char depends on pyrolysis conditions
(normally approx. equal)
3. Nitrogen released with the volatiles:

Nitrogen contained within the volatiles is released as, or rapidly converted to compounds such HCN,
NH3 or HNCO

These simple nitrogenous species then react in the gas phase to form either NO, N 2O or, under
fuel-rich conditions to N2 (see next slide)

Relative amounts of NO, N2O and N2 depends strongly on the local O2 concentration during pyrolysis
and temperature

NOx formation is reduced if volatiles are released under fuel-rich conditions

Pulverised-fuel combustors - NOx control techniques include: low-NOX burners, flue gas recirculation
(fuel-lean) and air staging

NO emissions are reduced in these techniques by changes in stoichiometry and/or temperature near
the burner thus reducing both volatile-NO and thermal-NO (important to take into account in
combustion)

. Char combustion and the Fate of Char-Nitrogen:

The fate of char-nitrogen is still leading edge research

Primary product of char-N oxidation is NO

However, both HCN and HNCO are observed at low temperatures (Ashman et al., 2000)

NO may be reduced to N2 by direct reaction with the char surface or by a char-catalysed reaction
with CO

Effective techniques aimed specifically at controlling char-NO are not available

5. In principle, NOx is reduced if it is reacted with C or CxHy concept of reburn
Summary of NOx Formation

Copy from Module 2_Carbon Monooxide in the atmosphere.