INTRODUCTION

The greenhouse effect is

the rise in temperature
that the Earth
experiences because
certain gases in the
atmosphere (water
vapor, carbon dioxide,
nitrous oxide, and
methane, for example)
trap energy from the
sun.
The natural greenhouse effect causes the mean temperature of the
Earth's surface to be about 33oC warmer than it would be if natural
greenhouse gases were not present.
When concentrations of greenhouse gases increase, more infrared radiation
is returned toward the earth and the surface temperature rises.
Incoming Radiation
Some trace gases are known as “greenhouse" gases
because they function like the glass in a greenhouse
 Incoming radiation strikes the earth and some is
absorbed
 This heats the earth and the earth reradiates in the
infrared portion of the spectrum
Greenhouse Gas Properties
Greenhouse gases absorb infrared radiation
that corresponds to the vibrational and
rotational energy levels of their bonds
Normally these gases have three or more
atoms.

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What makes a gas greenhouse gas?
Able to absorb infrared light
Must have molecular vibration(s)
This excludes monoatomic gases as greenhouse
gases. (That is why argon, the third most abundant
atmospheric constituents is transparent to infrared
irradiation)
The molecular vibrations must be non-
symmetric, i.e. infrared active
Homonuclear diatomic molecules only have
symmetric vibrations. That’s why N2, O2 are not
greenhouse gases.
What are the major greenhouse gases?

H2O
CO2
CH4
N2O
O3
CFCs
SF6
Atmospheric window: 8000-12000nm
What determines the contribution of a
greenhouse gas to global warming?
Concentrations
H2O and CO2 are the two biggest contributors to the
atmospheric warming because of their higher
concentrations.
Lifetime
The longer-live a gas is, the higher the contribution.
e.g. N2O contribution > CH4
Effectiveness as an infrared absorber
For example, CFC-11 and CFC-12
The absorption spectra of CFC-
11 and CFC-12 coincides with
the atmospheric window
 Comparison of different greenhouse gases

CO2 CH4 CFC-11 CFC-12 N2O

Concentration ppm ppm ppt ppt ppb

Preindustrial (<1800) 280 0.8 0 0 288
Current 370 1.74 268 484 314

Atmospheric lifetime
50-100 10 45 130 114
(yr)

Per molecule of
radiative forcing 1 23 4,000 15,800 296
relative to CO2
The average atmospheric CO2 concentrations observed at Muana Loa, Hawaii
increased approximately 40 ppmv between 1958 and 1995. The small fluctuations
in the curve are seasonal variations due primarily to the withdrawal and
production of carbon dioxide by terrestrial life. Notice that minimum values
occur during the northern hemisphere summers (when global photosynthetic
activity is greatest) and maximum values occur six months later.
Carbon dioxide

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Sources and sinks of CO2
Sources
Natural: respiration of vegetation and soil detritus
Man-made: Fossil fuel combustion, deforestation
Sinks:
slow exchange of carbon between surface waters and
deep layers of ocean.
(Seawater is alkaline while CO2 is acidic  The oceans
are a vast reservoir of CO2).
 More than 80% of carbon dioxide emissions are caused by :
 Burning fossil fuels in industries
 Cutting down and burning trees
 Thermal power plants and automobiles.
Deforestation
Until 50 years ago most of the carbon dioxide from
deforestation was released from temperate zones
Now tropical deforestation is the largest source
Tropical forests are being burned and cut for
farming, mining and raising cattle
* Deforestation accounts for about 20 percent of the carbon dioxide
increase from human activities

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Automobile Exhaust
Burning One Gallon of Gasoline Generates 22
Pounds of Carbon Dioxide
When gasoline is burned, the carbon in it
combines with oxygen in the air to form carbon
dioxide
Because the oxygen adds weight, the newly
formed carbon dioxide weighs more than the
original unburned fuel

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Cars and Population Increase
There are over 600 million motor vehicles in
the world today
If present trends continue, the number of
cars on Earth will double in the next 30
years

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 Rate of increase: 0.9% annually

Atmospheric methane has increased steadily to present day levels; this increase is highly
correlated with human population growth and with related activities, including
agricultural practices.
Sources and sinks of methane

Sources
Natural: end-product of the metabolism from an
anaerobic bacteria, methanogen.
Natural wetlands, fermentation, termites, biomass
burning, ocean/fresh water
Man-made: rice paddies, gas drilling and transmission,
landfills, coal mining, biomass burning, enteric
fermentation (domestic animals)
Sink: OH+ CH4 CH3. + H2O
Adding Methane
Each year we add 350 to 500 million tons
of methane to the air mainly by:
 Raising livestock
 Coal mining and drilling for oil and natural
gas
 Rice cultivation
 Disposing of garbage in landfills
 Burning forests and fields

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New Source of Methane
In 2006, research has shown that permafrost
melting in the arctic is releasing methane trapped
in formerly frozen sediments
Permafrost melting is the result of global warming

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Potential Source of
Methane
A great deal of natural gas is trapped as a
solid clathrate complex
These methane clathrates are found in bands
under the coastal sediments offshore from
continents in a number of areas
They represent a possibly large new source of
energy
Utilization of this resource may result in
large releases of methane

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Animals and Methane

Bacteria in the gut of cattle break down

the food these animals eat, converting
some of it to methane gas
Cattle can belch up to a half-pound of
methane a day
Sheep, goats, buffalo and camels also
belch methane
Rapidly growing world population
produces greater demand for meat and
dairy products
Number of cattle has doubled in the
past 40 years

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Nitrous Oxide
Nitrous oxide is released naturally from oceans and
by bacteria in soils
Each year we add 7 to 13 million tons of nitrous oxide
to the atmosphere mainly by:
 Using nitrogen-based fertilizers
 Disposing of human and animal wastes
 Automobile exhausts

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Sources and sinks of N2O
Sources:
denitrification process for energy production by
anaerobic bacteria.
Nitrification process (NH4+ NO3-) natural

Fertilizer use
Biomass burning
Man-made
Combustion
Unknown sources
Sink: Photolysis in the stratosphere
Chemical Fertilizers
Nitrogen-based fertilizer use has doubled in the
past 15 years
Nitrogen fertilizers provide nutrients for crops
When these fertilizers break down in the soil,
nitrous oxide is released into the air

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Sewage
Human and animal wastes release nitrous oxide
Sewage treatment plants may be a major source
of this gas
Animal feed lots also contribute

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Rate of increase 0.25%/year
Use of fertilizer increases both nitrification and denitrification 
increase N2O production
 Fluorocarbons
 Fluorocarbons come almost entirely from human activities
 They are manufactured by humans for refrigeration and other uses
 Some fluorocarbons, including chlorofluorocarbons (CFCs),CFC along
with chlorine and bromine containing compounds also involve in
acceleration of ozone hole formation .
 It also result in increasing the amount of hydrogen peroxide in the
atmosphere and induce acid rain

Sources
No natural sources
Synthetic chemicals
Sink: Photolysis in the stratosphere.
The global air temperature at the Earth's surface has increased about 0.5 oC during
the past century
Consequences of global warming
Sea level rise
Beach erosion
Coastal wetland loss
Loss of low-lying territories
Water resources change
Precipitation pattern shift
Increases instances of heavy precipitation
New burdens on water capture, storage and
distribution system to be expected.
Effects on agriculture
 Changes in the length of growing season
 Growth of undesirable plant species
Consequences of global warming (Continued)
Effects on air quality
 Increase in reaction rates and concentrations of certain
atmospheric species increase in O3 in urban areas
 More droughts widespread forest fire worsen air quality
 Change in how pollutants are dispersed.
Impacts on human health
 Changes in patterns of sickness and death.
 Respiratory problems affected by air quality change
Biodiversity
 Some species may grow too quick and overshoot their
reproductive period (e.g. reef corals)
 Forest could be devastated if the rate of climate change outpaced
the rate at which forest species could migrate.
Change in the pattern of ocean current
Is the temperature rise due to human activities?
Or is it part of the natural variation?
When greenhouse gases,
aerosols, and changes in solar
irradiance are used as inputs into
general circulation models,
predicted temperatures are very
close to those observed.

When greenhouse gases are

the only input, predicted
temperature are higher than
those observed.
The state of climate change science
The Earth’s natural greenhouse effect is
required to support life on earth.
Aerosol particles are important in formation of
clouds.
Human activities are contributing to increases
in greenhouse gases and aerosol loading.
The Earth’s surface has warmed during the last
century and is projected to continue warming.
Effect of Greenhouse
Gases
Chart shows how
much warming
could be caused by
each of the gases
that human activities
release

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A Global Problem
An increase in global temperature would bring
changes to the entire planet, and therefore to
every nation
This makes it an international issue which needs
worldwide study and responses
Individual countries are each responsible for their
own greenhouse gas production

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CONTROL MEASURES
 Reducing the consumption of fossil fuels.
 Afforestation.
 Eco friendly alternative CFC.
 CO2 pumped into underground.
 Bioremediation
Global Warming
The Earth’s temperature increases as result of the build-up
of heat-trapping (i.e. “greenhouse”) gases.

A higher frequency of extreme climatic events (drought,

floods) is predicted.

Coastal flooding due to rising sea level: potential

salinization of fresh groundwater supplies

Change in plant and animal populations

 increase of some species, potentially “pests & pathogens”
 loss of agricultural crops
Predictions Based on Present Rate of
Global Warming Gas Emission
Global Mean Temperature Rise of 0.3 °C per decade

Non-uniform temperature rise (greater increase in

polar regions)

Sea-level rise of 6 cm per decade

Non-uniform increase in rainfall

Greenhouse Effect vs. Global
warming
 The greenhouse effect is large (tens of °C) and has a firm scientific basis.
(Venus has a HUGE greenhouse effect.)

 Global warming results from perturbing the greenhouse effect: It is a smaller

(tenths of °C) effect which requires careful measurement over several decades.
As a result, it is still debated in the scientific community. (Note that the
mean global temperature 10,000 years ago during the last ice age was only 4°C
less than it is now)

 Dilemma
 Invest resources now but later determine the that the global warming
effect is negligible
OR
 Do nothing now, but later find that small steps taken today would have
had a dramatic improvement on the earth’s climate
IPCC - “..emissions resulting from human
activities are substantially increasing
concentrations of greenhouse gases..”
1988 1992
UN Rio Conf. - “..levels of CO2 to
be reduced to earlier levels by
2000..”
US Climate Change Action Plan -
“..control emissions of HFCs and
PFCs..”
1993 today
DuPont’s Sale Policy - phase out supply of C2F6 if
solutions to reducing emissions of this PFC are not
sufficiently mature by year-end 1999.
EPA MOU - commits signatories to (company-blind)
reporting of estimated PFC emissions to the EPA on an
annual basis and striving to reduce their PFC emissions.
Atmospheric Lifetime, 
Compounds are eventually broken down through chemical
reactions in the atmosphere.
Typically, the rate of loss is proportional to concentration, c,
dc 1 
    c
dt  
(first order kinetics)
c
 exp( t  )
c0

LIFETIME = TIME TO REDUCE CONCENTRATION BY 37%

(1/e)
Unstable compounds are highly reactive -> short lifetimes
Stable compounds are unreactive -> long lifetimes
Global Warming Potential (GWP)
 Global-warming potential (GWP) is a relative measure of how much
heat a greenhouse gas traps in the atmosphere. It compares the
amount of heat trapped by a certain mass of the gas in question to the
amount of heat trapped by a similar mass of carbon dioxide.
GWP is expressed as a factor of carbon dioxide (whose GWP is
standardized to 1)
The substances subject to restrictions under the Kyoto protocol either are
rapidly increasing their concentrations in Earth's atmosphere or have a
large GWP.
The GWP depends on the following factors:
 the absorption of infrared radiation by a given species
 the spectral location of its absorbing wavelengths
 the atmospheric lifetime of the species
Thus, a high GWP correlates with a large infrared absorption and a long
atmospheric lifetime.
 GWP is based on a number of factors, including the radiative
efficiency (infrared-absorbing ability) of each gas relative to that of
carbon dioxide, as well as the decay rate of each gas (the amount
removed from the atmosphere over a given number of years) relative
to that of carbon dioxide.
 The radiative forcing capacity (RF) is the amount of energy per unit
area, per unit time, absorbed by the greenhouse gas, that would
otherwise be lost to space. It can be expressed by the formula:

where the subscript i represents an interval of 10

inverse centimeters. Absi represents the integrated infrared
absorbance of the sample in that interval, and Fi represents the
RF for that interval
For a given gas, the GWP is

 an index of the potential to cause radiation forcing

 relative to releasing the same mass of CO2

 cumulative, integrating between the present and a future time

Calculation of GWP
The total outgoing IR absorbed by compound i
 at any instant, is proportional to ai*ci
 ai is the radiation forcing efficiency per molecule i
 ci is the concentration of molecule i
 over time, ci will decrease
 defined such that GWPCO2 = 1 ITH
 ai ci dt
0
GPWi  ITH
 aCO2 cCO2 dt
0

The integrated time horizon (ITH) is typically chosen as

100 years. Sometimes 20 or 500 year horizons are
considered.
Importance of time horizon
Substance's GWP depends on the timespan over which the
potential is calculated. A gas which is quickly removed
from the atmosphere may initially have a large effect but
for longer time periods as it has been removed becomes
less important. Thus methane has a potential of 34 over
100 years but 86 over 20 years; conversely
sulfur hexafluoride has a GWP of 22,800 over 100 years but
16,300 over 20 years (IPCC TAR). The GWP value depends
on how the gas concentration decays over time in the
atmosphere.
Values
GWP time horizon
GWP values and lifetimes
from 2013 IPCC AR5 p714
Lifetime (years)
(with climate-carbon 20 years 100 years
feedbacks)

Methane 12.4 86 34
HFC-134a
13.4 3790 1550
(hydrofluorocarbon)
CFC-11 (chlorofluorocarbon) 45.0 7020 5350
Nitrous oxide 121.0 268 298
Carbon tetrafluoride (CF4) 50000 4950 7350
 GWP time horizon

GWP values and

lifetimes from 2007
Lifetime
IPCC AR4 p212
(years) 20 years 100 years 500 years
(2001 IPCC TAR in
parentheses)

Methane 12         (12) 72         (62) 25         (23) 7.6       (7)

Nitrous oxide 114       (114) 289       (275) 298       (296) 153       (156)

HFC-23 12,200  
270       (260) 12,000   (9400) 14,800   (12,000)
(hydrofluorocarbon) (10,000)

HFC-134a
14         (13.8) 3,830     (3,300) 1,430     (1,300) 435       (400)
(hydrofluorocarbon)

32,600  
Sulfur hexafluoride 3200     (3,200) 16,300   (15,100) 22,800   (22,200)
(32,400)
Comparison of Lifetimes &
GWPs
Gas Atm. Lifetime GWP
(years) (100 ITH)
CF4 50,000 6,500
C 2 F6 10,000 9,200
C 3 F8 5,600 6,950
SF6 3,200 23,900
NF3 740 13,100
CHF3 * 264 11,700
CO 2 50-200 1

data on NF3 from Air Products all others from IPCC ‘95

*CHF3 is technically not a perfluorinated compound, but is often included on this list
because of its widespread use and PFC-like atmospheric behavior.
Although water vapour has a significant influence with regard to
absorbing infrared radiation (which is the green house effect; see
greenhouse gas), its GWP is not calculated. Its concentration in the
atmosphere mainly depends on air temperature. There is no
possibility to directly influence atmospheric water vapour
concentration.
The values given in the table assume the same mass of compound is
released. This must not be confused with chemical reactions in
which masses change from reactants to products. For instance,
burning methane to carbon dioxide would indeed reduce the global
warming impact, but by a smaller factor than the one given in the
table because the mass of methane burning is lesser than the mass
of carbon dioxide released (ratio 1:2.75). If you started with 1
tonne of methane which has a GWP of 25, after combustion you
have 2.75 tonnes of CO2, each tonne of which has a GWP of 1. The
effect of this burning is to reduce the Global warming effect of
the gas released in the ratio 25:2.75 or by about 9. Similarly, for
each tonne of methane burned to CO2, the release of tonne CO2
equivalent is reduced by 25 – 2.75 = 22.25.
Observations
 PFCs are potent greenhouse gases which are long-lived and
strong infrared radiation absorbers.
The semiconductor industry uses PFCs with high GWPs.
Lifetimes for some PFCs approach that for known human
civilization. For all intents and purposes, they are permanent.
These compounds may have other effects in addition to global
warming.
Tabulated lifetimes and GWPs are updated periodically as
atmospheric measurements and models improve. The 1994
IPCC values typically changed 10 to 35 % from the 1992 report.
Uncertainty in 1994 values is estimated to be ±35%.
Releasing one molecule of C2F6 today has the same GWP as the
releasing of 9,200 molecules of CO2 when considered over a 100
year integrated time horizon!