Introduction to Meteorology

Evolution and Composition of the

atmosphere

Leila M. V. Carvalho
 In the beginning…
4.5 billion years ago: formation of our solar system from gas and dust
(nebula) generated from supernova explosion

http://www.aerospaceweb.org/question/astronomy/q0247.shtml
THE SOLAR SYSTEM
 PLANETS OF THE SOLAR SYSTEM – NOT TO SCALE
TERRESTRIAL PLANETS (OR ROCKY PLANETS)
Mercury Venus Earth Mars

GAS PLANETS (OR JOVIAL PLANETS)

Jupiter Saturn Neptune Uranus
 Earth first atmosphere
Artist impression of the giant impact
that created the Moon. The sizes of
the proto-Earth and the impactor are
comparable with the results of
computer simulations from the 90's.
More recent simulations show the
Earth-Moon system could also have
resulted from a relatively smaller
impactor
http://en.wikipedia.org/wiki/Earth%27s_atmosphere#Evolution_of_Earth.27s_atmosphere
• The original atmosphere was primarily
helium (He) and hydrogen (H).
• Heat from the still-molten crust, the
sun, and a probably enhanced solar
wind, dissipated this atmosphere.
• Gravity is important to keep an
atmosphere. H, He have low molecular
weight and may have achieved the
escape velocity (the velocity necessary
to escape gravity)
• Other explanations: gases would have
been removed by collision between the
growing Earth and other large bodies
(failed planets). The tremendous
energy released may have ejected the
early atmosphere
• This theory explains the origin of the
Moon and the tilting of the Earth axis
to 23o
(http://www.psrd.hawaii.edu/Dec98/OriginEarthMoon.html)
 The second atmosphere 4.4 billion years ago…
• About 4.4 billion years ago, the surface had cooled
enough to form a crust.
• Many volcanoes released steam, carbon dioxide, and
ammonia. This led to the early "second atmosphere",
which was primarily carbon dioxide and water
vapor, with some nitrogen but virtually no oxygen.
• Additional water was imported by collisions,
probably with asteroids ejected from the asteroid
belt under the influence of Jupiter's gravity.
• As it cooled much of the carbon dioxide was
dissolved in the seas and precipitated out as
carbonates.
• Simulations run at the University of Waterloo and
University of Colorado suggest that it may have had
up to 40% hydrogen.
• It is generally believed that the greenhouse effect,
caused by high levels of carbon dioxide and methane,
kept the Earth from freezing.

Early Earth - The First Billion Years : Lava flowing from Earth's partially
molten interior spread over the Earth's surface and solidified to form a
thin crust, the rain evaporating on contact with the hot ground. As the
temperature dropped, the oceans formed.
Life and the formation of the third
atmosphere
• CYANOBACTERIAS existed approximately 3.3 billion
years ago and were the first oxygen-producing
evolving phototropic organisms.
• They were responsible for the initial conversion of
the Earth's atmosphere from an anoxic state to an
oxic state (that is, from a state without oxygen to a
state with oxygen) during the period 2.7 to 2.2
billion years ago.
• They were the first to carry out oxygenic
Cyanobacterias photosynthesis, and were able to produce oxygen
while sequestering carbon dioxide in organic
molecules, playing a major role in oxygenating the
atmosphere. This is often referred to as the Oxygen
Catastrophe. (oxygen was toxic to the microscopic
anaerobic organisms dominant then.)
• The increase in the concentration of oxygen in the
atmosphere required time because iron and other
elements in the Earth's crust reacted with oxygen,
removing it from the atmosphere.
 The third atmosphere:
• Photosynthesizing plants later evolved and continued
releasing oxygen and sequestering carbon dioxide.
Cambrian Period: 543-490 Million Yrs • As oxygen was released, it reacted with ammonia to release
nitrogen.
• Bacteria also converted ammonia (NH3) into nitrogen, but
most of the nitrogen currently in the atmosphere resulted
from sunlight-powered photolysis of ammonia
Siberia • As more plants appeared, the levels of oxygen increased
Laurentia Gondwana significantly, while carbon dioxide levels dropped.
Baltica • At first the oxygen combined with various elements, but
eventually oxygen accumulated in the atmosphere,
contributing to Cambrian explosion and further evolution.
Oxygen increases: The ozone layer is formed, life can migrate to
the continents

•With the appearance of an ozone

layer life-forms were better protected
from ultraviolet radiation. - life over
continents (450 mi years ago)
•Between 200 and 250 million years
ago, up to 35% of the atmosphere was
oxygen (as found in bubbles of ancient
atmosphere preserved in amber).
•This modern atmosphere has a
composition which is enforced by
oceanic blue-green algae as well as
geological processes.

Ancient Amphibians:
http://news.nationalgeographic.com/news/bigphoto
s/10940810.html
 http://www.chem.arizona.edu/prise/w8/historylife2.pdf

•O2 does not remain naturally free in an atmosphere but tends to

be consumed by inorganic chemical reactions, and by animals,
bacteria, and even land plants at night. CO2 tends to be produced
by respiration and decomposition and oxidation of organic matter.
•O2 would vanish within a few million years by chemical reactions,
and CO2 dissolves in water and would be gone in millennia if not
replaced. Both are maintained by biological productivity and
geological forces seemingly working hand-in-hand to maintain
reasonably steady levels over millions of years.
PRESENT ATMOSPHERE:
BEFORE THE INDUSTRIAL
REVOLUTION
O2:21%
N2: 78%

% per volume

Water vapor H2O : 0-4% (Variable)

Carbon dioxide: CO2 : 0.03%
(Variable)
Steady state and residence
time definitions
Steady state and residence time:
Consider a gas that is constantly being cycled between
the atmosphere and the Earth’s surface physical
processes (volcanic eruptions, biological processes, etc)
or by chemical processes (reaction between gases).
If we consider the atmosphere as a reservoir for this gas,
the concentration of the gas will remain constant so long
as the
input rate = output rate : concentration of the gas is in
a steady state.

Individual molecules stay in the atmosphere for only a finite

period of time before they are removed by whatever output
processes are active. The average length of time that
individual molecules of a given substance remain in the
atmosphere is called the residence time

These two figures are schematically showing gases with

high and low residence time. If arrows are indicating the
rate that a substance enters and exits the atmosphere in
a steady state, which figure represents the long
residence time?
Permanent and variable gases in the atmosphere

Constitute
approximately
99.999% of the
atmosphere and
occur in nearly
constant proportion
throughout the
atmosphere’s
lowest 80km:
HOMOSPHERE

What does it mea

n?
 How to compute the residence time?
• Divide the mass of the substance
in the atmosphere (in kilograms) Consider a box or reservoir
by the rate at which the substance Fout
enters and exits the atmosphere
(in kilograms per year). m X
L

m m
 i.e.  
input or output Fout  L  D

τ= Residence time (yr)

• Thus everything else being equal, m= mass (kg)
gases that are rapidly exchanged Fout=Flux outside the volume (or reservoir)
L= chemical loss (kg/yr) – % of m converting into X
between Earth’s surface and the
D= Deposition (kg/yr)
atmosphere have brief residence
times, as do gases that have
relatively low atmospheric
concentrations.
 Example
• The mass of nitrogen in the atmosphere is 4 x 1018 kg, and its sinks from the
atmosphere include (i) biological nitrogen fixation by bacteria, 2 x 1011 kg yr-1; (ii)
production of NO in thunderstorms, 7 x 1010 yr-1; (iii) chemical synthesis of
ammonia, 5 x 1010 kg yr-1 (all data refer to loss of nitrogen). Calculate the
residence time of nitrogen in the atmosphere.

m 4  1018
   1.3  10 7 yr
output 2  10  7  10  5  10
11 10 10
Water Vapor
Water vapor from satellite
 Water vapor
• Water vapor is not the same as droplets – it is a gas
• Main source: evaporation
• Concentration decreases rapidly with altitude
• Most atmospheric water vapor: lowest 5km (3mi) of the
atmosphere in quantities the vary from 1-4 %
• Outside tropics it does not exceed 2%
• It is constantly cycled between the planet and the atmosphere
in the so called hydrological cycle.
• Water evaporates from river, oceans lakes, ice sheets, and
underground water (removed from the soil sometimes by
vegetation)
 Question to discuss with your
partner:
• What in your opinion is the most important
role of tropical rainforests such as the Amazon
forest (justify your answer):
• A) contribution for the Earth input of O2
• B) contribution for input H2O vapor
• C) (A) and (B) are correct
• D) Neither (A) or (B) is correct
 Carbon dioxide
• CO2 currently accounts for about
0.038% of the atmosphere’s
volume.
• When a gas occupies such a small
proportion of the atmosphere, we
often express its content as part
per million (ppm) - today 380 ppm.
• Sources: plant, animal respiration,
decay of organic material, volcanic
eruptions, natural anthropogenic
(human produced) combustion.
• CO2 is removed by photosynthesis
by plants
• CO2 gas a residence time of about How do you explain the cycles observed
150 yrs. for CO2?
 = +1.6 + 6.3 -2.3 -2.3 = 3.3 GtC

Vegetation 600 Ocean 39,000 GtC

Soil 2,000 GtC
Metric ton:
Reservoir 1,000 kilograms (2,205 pounds)
Reservoir
Unity of flux: metric ton/year
Gigatons: 109 ton = 1012 kg
 Methane CH4
• about 3.5 billion years ago—there was 1,000
times as much methane in the atmosphere
as there is now. The earliest methane was
released into the atmosphere by volcanic Less industrial
activity.
production and
• With life and increase in O2 methane decrease of
decreased (reaction with OH). wet lands
• With industrialization the rate of increase (drought)
accelerated so that values have more than
doubled over the last 200yrs (~ 1.7 ppm in
1999)
• The residence time for methane is about 10
yrs.
• The current input of CH4 is approximately
equal to its natural removal
• CH4 is a very efficient greenhouse gas
 Hum… it seems something else happened these past years that
might change the trends observed before and potentially cause
a climate shift (if persisted).
From the following article
A sleeping giant?
Nature Reports Climate Change (2009)
Published online: 5 March 2009
doi:10.1038/climate.2009.24

Could this increase be because methane has

been released in the atmosphere because
global warming has released the methane that
was trapped under the permafrost?
The average atmospheric concentration
of methane shot up suddenly in 2007, If that is true, the increase of methane, an
having remained stable for a decade. efficient greenhouse gas, might increase global
Data shown are from the Advanced warming and cause important climate shifts
Global Atmospheric Gases Experiment
and the Australian Commonwealth
Scientific and Industrial Research
Organisation, courtesy of Matt Rigby

http://www.nature.com/climate/2009/0904/full/climate.2009.24.html
 What is ‘greenhouse’ effect?
CO2, CH4, H20
IR - heat

UV, VIS
 Ozone O3
• Ozone is observed in the stratosphere (above 20km) and in
the troposphere (~below 12 km)
• In the stratosphere ~ 25km at concentration of 15ppm (that
is 15 out of every one million molecules is ozone), is essential
for life on Earth!
• In the lower atmosphere occur in highly polluted urban
areas and association with forest burning. Can cause
irritation to lungs, eyes, and damage to vegetation.
• Concentration in polluted urban areas up to 0.15 ppm (that is,
15 out of every 100 million molecules are ozone)
 But… how is ozone formed in the stratosphere ?
http://www.ccpo.odu.edu/SEES/ozone/oz_class.htm
NASA
2. Ozone and oxygen atoms
are continuously being
1. Oxygen molecules
interconverted as solar UV
are photolyzed,
breaks ozone and the oxygen
yielding 2 oxygen
atmom reacts with another
atoms (SLOW)
oxygen molecule (FAST)

O2

This interconversion process

3. Ozone is lost by the reaction of the oxygen atom or converts UV radiation into
the ozone molecule with each other, or some other Thermal energy, heating the
trace gas such as chorine (SLOW) stratosphere
 Typical reaction in the Stratosphere
UV solar radiation
1) Production of O2 + hc/λ --> O + O λ ≤ 240nm (wave length )
free oxygen h = Plank Constant
c = speed of light
O3 + hc/λ --> O2 + O
O + O2 + M --> O3 + M
The M is another molecule (typically N2 or O2, the two most abundant
molecules in the atmosphere). It carries away the extra energy of this reaction.
This process of absorption is an extremely efficient, ultraviolet radiation is
effectively screened out before it reaches Earth's surface.

What happens if Chlorine , Bromine or Fluor (more reactive) take part in this reaction?

Ex: ClO (chlorine monoxide) O2 + hc/λ --> O + O

ClO + O --> O2 + Cl
Cl + O3 --> O2 + ClO
Net: O3 + O3 --> 3 O2
 Discussion
WHY THE O3 PEAK IS
OBSERVED AROUND 30Km
AND NOT ABOVE, WHERE
SOLAR RADIATION IS HIGHER,
OR BELOW, WHERE THE
DENSITY OF O2 IS HIGHER?

Did you know that Dobson Unit (DU) is a measure of the "thickness" of the
ozone layer? Imagine that all of the overhead ozone molecules (spread over
the depth of the stratosphere) could be brought down to the surface (at standard
temperature and pressure). This "layer" of ozone would only be about 3
millimeters (mm) thick, equivalent to the height of two stacked pennies. This
amount of ozone has a Dobson Unit value of 300 DU (approximately the global
average of total ozone).
But… what is the ozone hole? Why does it occur? Is it caused
by natural or is it anthropogenic induced ?

O2

LOW HIGH OZONE

During the winter of the SH
polar regions do not receive
solar radiation and therefore
by the beginning of the
spring there is a minimum
in the stratospheric ozone.
(therefore, the minimum
ozone is a natural feature)

However, remember that if

chlorine, bromine or flour
are present, then when free
oxygen that begins to form
during spring, combines
with these components.
The result is less total ozone
and the increase in the
ozone hole over polar
stratosphere
 Aerosols
• Definition: small solid particles and liquid droplets in
the air (excluding cloud droplets and precipitation).
• Can be formed by human or natural processes.
• Normal concentration: 10,000 particles per cubic
centimeter over land surface (~ 17,000 particles per
cubic inch)
• Size : below 0.1 μm (Aitken nuclei) Fine aerosols
– 0.1 – 1.0 μm (large particle)
– > 1 μm = giant particle Coarse aerosols
 Effects in the atmosphere and society

Dust Storm – Texas 1935 Smog in NY city

Caused by burning of fossil fuels,

Reduce visibility, solar radiation at the surface,
coal and industrial activity
Serious impacts on health
Reduce visibility, solar radiation at
the surface,
Serious impacts on health
 Did you know?
On average, each breath a person takes brings into the lungs about
1000cm3 (1 liter, or 64in.3) of air. Given the average size and concentration of
aerosols, each of us draws about 1 trillion aerosols into our lungs several
times each minute, or about two table spoons of solid each day!
 Discussions and conclusions…
• Earth had three atmospheres: the composition of the third one is
completely linked to the existence of life in our planet 21% O2 and 78% N2
• The ozone layer formed only recently (~ 7 mi yrs)
• Green house gases have been important to maintain the temperature of
earth above freezing.
• Human activity has increased the amount of greenhouse gases in the
atmosphere
• The ozone hole is a natural feature of the atmosphere. Its increase over
time is due to human activity (input of chlorine and bromine that reacts
with free oxigen)
• Aerosols are important component of the atmosphere (they may be of
natural sources or human produced)
Training a few concepts…
How was the 2010 SH ozone hole
compared with previous years?
 http://www.esrl.noaa.gov/gmd/dv/spo_oz/spototal.html

Record low: October 1993 Pinatubo released more Chlorine in the atmosphere
 Important concepts
Ultraviolet radiation is divided into three components: UV-A
(315 to 400 nm), UV-B (280 to 315 nm) and UV-C (less than
280 nm). The shorter wavelengths that comprise UV-B are
the most dangerous portion of UV radiation that can
reach ground level

Atmospheric ozone shields life at the surface from most of

the UV-B and almost all of the UV-C

All forms of UV radiation are reduced by cloud cover.

Persistent lack of cloud cover in some regions (e.g. Australia
and South Africa) increases the danger from UV radiation
compared to similar latitudes in the Northern Hemisphere
Why do we observe values so close to zero here???
January 3, 2011 : total ozone estimated by UV