The early atmosphere

Scientists believe that the Earth was formed about 4.5 billion years ago. Its early atmosphere was
probably formed from the gases given out by volcanoes. It is believed that there was intense volcanic
activity for the first billion years of the Earth's existence.
The early atmosphere was probably mostly carbon dioxide with little or no oxygen. There were smaller
proportions of water vapour, ammonia and methane. As the Earth cooled down, most of the water vapour
condensed and formed the oceans.

Evolution Of The Atmosphere: Composition, Structure And Energy

I inhale great draughts of space,
The east and west are mine, and the north and the south are mine
I am larger, better than I thought,
I did not know I held so much goodness - all seems beautiful to me.
- Song of the Open Road, Walt Whitman

1. The Earliest Atmosphere, Oceans, and Continents

After loss of the hydrogen, helium and other hydrogen-containing gases from early Earth due to
the Sun's radiation, primitive Earth was devoid of an atmosphere. The first atmosphere was
formed by outgassing of gases trapped in the interior of the early Earth, which still goes on
today in volcanoes.
For the Early Earth, extreme volcanism occurred during differentiation, when massive heating
and fluid-like motion in the mantle occurred. It is likely that the bulk of the atmosphere was
derived from degassing early in the Earth's history. The gases emitted by volcanoes today are
in Table 1 and in Figure.
Composition of volcanic
gases for three volcanoes

Volcanic outgassing

Oxygen in the Atmosphere

Stromatolite and Banded-iron Formation (BIF)

Life started to have a major impact on the environment once photosynthetic organisms evolved.
These organisms, blue-green algae (picture of stromatolite, which is the rock formed by these
algae), fed off atmospheric carbon dioxide and converted much of it into marine sediments
consisting of the shells of sea creatures.
While photosynthetic life reduced the carbon dioxide content of the atmosphere, it also started

to produce oxygen. For a long time, the oxygen produced did not build up in the atmosphere,
since it was taken up by rocks, as recorded in Banded Iron Formations (BIFs; picture) and
continental red beds. To this day, the majority of oxygen produced over time is locked up in the
ancient "banded rock" and "red bed" formations. It was not until probably only 1 billion years
ago that the reservoirs of oxidizable rock became saturated and the free oxygen stayed in the
air.
The oxidation of the the mantle rocks may have played an important role in the rise of oxygen.
It has been hypothesized the the change from predominantly submarine to subaerial volcanoes
may have also led to a reduction in volcanic emission of reduced gases.
Once oxygen had been produced, ultraviolet light split the molecules, producing the ozone UV
shield as a by-product. Only at this point did life move out of the oceans and respiration
evolved. We will discuss these issues in greater detail later on in this course.
Early Oceans
The Early atmosphere was probably dominated at first by water vapor, which, as the
temperature dropped, would rain out and form the oceans. This would have been a deluge of
truly global proportions an resulted in further reduction of CO2. Then the atmosphere was
dominated by nitrogen, but there was certainly no oxygen in the early atmosphere. The
dominance of Banded-Iron Formations (BIFs; see picture) before 2.5Ga indicates that Fe
occurred in its reduced state (Fe2+). Whereas reduced Fe is much more soluble than oxidized
Fe (Fe3+), it rapidly oxidizes during transport. However, the dissolved O in early oceans reacted
with Fe to form Fe-oxide in BIFs. As soon as sufficient O entered the atmosphere, Fe takes the
oxidized state and is no longer soluble. The first occurrence of redbeds, a sediments that
contains oxidized iron, marks this major transition in Earth's atmosphere.

Cumulative history of O2 by
photosynthesis over geologic
time. The start of free O is likely
earlier than shown.

Early Continents
Lava flowing from the partially molten interior spread over the surface and solidified to form a
thin crust. This crust would have melted and solidified repeatedly, with the lighter compounds
moving to the surface. This is called differentiation. Weathering by rainfall broke up and altered
the rocks. The end result of these processes was a continental land mass, which would have
grown over time. The most popular theory limits the growth of continents to the first two billion
years of the Earth.

2. Evolution of the Present Atmosphere

The evolution of the atmosphere could be divided into four separate stages:

1.
2.
3.
4.

Origin
Chemical/ pre-biological era
Microbial era, and
Biological era.

and the first three steps were discussed in detail. The composition of the present
atmosphere however required the formation of oxygen to sufficient levels to sustain
life, and required life to create the sufficient levels of oxygen. This era of evolution of
the atmosphere is called the "Biological Era."
The Biological Era - The Formation of Atmospheric Oxygen

The biological era was marked by the simultaneous decrease in atmospheric carbon
dioxide (CO2) and the increase in oxygen (O2) due to life processes. We need to
understand how photosynthesis could have led to maintenance of the ~20% presentday level of O2. The build up of oxygen had three major consequences that we should
note here.
Firstly, Eukaryotic metabolism could only have begun once the level of oxygen had built up to about 0.2%, or
~1% of its present abundance. This must have occurred by ~2 billion years ago, according to the fossil record.
Thus, the eukaryotes came about as a consequence of the long, steady, but less efficient earlier photosynthesis
carried out by Prokaryotes.

Figure 1. Photolysis of water vapor and carbon dioxide produce hydroxyl and atomic oxygen, respectively, that,
in turn, produce oxygen in small concentrations. This process produced oxygen for the early atmosphere before
photosynthesis became dominant.
Oxygen increased in stages, first through photolysis (Figure 1) of water vapor and carbon dioxide by ultraviolet
energy and, possibly, lightning:
H2O -> H + OH
produces a hydroxyl radiacal (OH) and
CO2 -> CO+ O
produces an atomic oxygen (O). The OH is very reactive and combines with the O
O + OH -> O2 + H
The hydrogen atoms formed in these reactions are light and some small fraction excape to space allowing the O2
to build to a very low concentration, probably yielded only about 1% of the oxygen available today.

Secondly, once sufficient oxygen had accumulated in the stratosphere, it was acted on by sunlight to form
ozone, which allowed colonization of the land. The first evidence for vascular plant colonization of the land dates
back to ~400 million years ago.
Thirdly, the availability of oxygen enabled a diversification of metabolic pathways, leading to a great increase in
efficiency. The bulk of the oxygen formed once life began on the planet, principally through the process of
photosynthesis:
6CO2 + 6H2O <--> C6H12O6 + 6O2
where carbon dioxide and water vapor, in the presence of light, produce organics and oxygen. The reaction can
go either way as in the case of respiration or decay the organic matter takes up oxygen to form carbon dioxide
and water vapor.
Life started to have a major impact on the environment once photosynthetic organisms evolved. These
organisms fed off atmospheric carbon dioxide and converted much of it into marine sediments consisting of the
innumerable shells and decomposed remnants of sea creatures.
While photosynthetic life reduced the carbon dioxide content
of the atmosphere, it also started to produce oxygen. The
oxygen did not build up in the atmosphere for a long time,
since it was absorbed by rocks that could be easily oxidized
(rusted). To this day, most of the oxygen produced over time
is locked up in the ancient "banded rock" and "red bed" rock
formations found in ancient sedimentary rock. It was not
until ~1 billion years ago that the reservoirs of oxidizable
rock became saturated and the free oxygen stayed in the
air. The figure illustrates a possible scenario.
We have briefly mentioned the difference between reducing
(electron-rich) and oxidizing (electron hungry) substances.
Oxygen is the most important example of the latter type of
substance that led to the term oxidation for the process of
transferring electrons from reducing to oxidizing materials.
This consideration is important for our discussion of
atmospheric evolution, since the oxygen produced by early
photosynthesis must have readily combined with any
available reducing substance. It did not have far to look!

Cumulative history of O2 by photosynthesis

through geologic time.

We have been able to outline the steps in the long drawn out
process of producing present-day levels of oxygen in the
atmosphere. We refer here to the geological evidence.

Banded Iron Formations

When the oceans first formed, the waters must have dissolved enormous quantities of reducing iron ions, such
as Fe2+. These ferrous ions were the consequences of millions of years of rock weathering in an anaerobic
(oxygen-free) environment. The first oxygen produced in the oceans by the early prokaryotic cells would have
quickly been taken up in oxidizing reactions with dissolved iron. This oceanic oxidization reaction produces Ferric
oxide Fe2O3 that would have deposited in ocean floor sediments. The earliest evidence of this process dates back
to the Banded Iron Formations, which reach a peak occurrence in metamorphosed sedimentary rock at least 3.5
billion years old. Most of the major economic deposits of iron ore are from Banded Iron formations. These
formations, were created as sediments in ancient oceans and are found in rocks in the range 2 - 3.5 billion years
old. Very few banded iron formations have been found with more recent dates, suggesting that the continued
production of oxygen had finally exhausted the capability of the dissolved iron ions reservoir. At this point
another process started to take up the available oxygen.

Red Beds
Once the ocean reservoir had been exhausted, the newly created oxygen found another large reservoir reduced minerals available on the barren land. Oxidization of reduced minerals, such as pyrite FeS 2 ,
exposed on land would transfer oxidized substances to rivers and out to the oceans via river flow. Deposits
of Fe2O3 that are found in alternating layers with other sediments of land origin are known as Red Beds,
and are found to date from 2.0 billion years ago. The earliest occurrence of red beds is roughly
simultaneous with the disappearance of the banded iron formation, further evidence that the oceans were

cleared of reduced metals before O2 began to diffuse into the atmosphere.

Finally after another 1.5 billion years or so, the red bed reservoir became exhausted too (although it is
continually being regenerated through weathering) and oxygen finally started to accumulate in the atmosphere
itself. This signal event initiated eukaryotic cell development, land colonization, and species diversification.
Perhaps this period rivals differentiation as the most important event in Earth history.
The oxygen built up to today's value only after the colonization of land by green plants, leading to efficient and
ubiquitous photosynthesis. The current level of 20% seems stable.

The Oxygen Concentration Problem.

Why does present-day oxygen sit at 20%? This is not a trivial
question since significantly lower or higher levels would be
damaging to life. If we had < 15% oxygen, fires would not burn, yet
at > 25% oxygen, even wet organic matter would burn freely.

The Early Ultraviolet Problem

The genetic materials of cells (DNA) is highly susceptible to damage
by ultraviolet light at wavelengths near 0.25 m. It is estimated that
typical contemporary microorganisms would be killed in a matter of
seconds if exposed to the full intensity of solar radiation at these
wavelength. Today, of course, such organisms are protected by the
atmospheric ozone layer that effectively absorbs light at these short
wavelengths, but what happened in the early Earth prior to the
significant production of atmospheric oxygen? There is no problem
for the original non-photosynthetic microorganisms that could quite
happily have lived in the deep ocean and in muds, well hidden from sunlight. But for the early photosynthetic
prokaryotes, it must have been a matter of life and death.
It is a classical "chicken and egg" problem. In order to become photosynthetic, early microorganisms must have
had access to sunlight, yet they must have also had protection against the UV radiation. The oceans only provide
limited protection. Since water does not absorb very strongly in the ultraviolet a depth of several tens of meters
is needed for full UV protection. Perhaps the organisms used a protective layer of the dead bodies of their
brethren. Perhaps this is the origin of the stromatolites - algal mats that would have provided adequate
protection for those organisms buried a few millimeters in. Perhaps the early organisms had a protective UVabsorbing case made up of disposable DNA - there is some intriguing evidence of unused modern elaborate
repair mechanisms that allow certain cells to repair moderate UV damage to their DNA. However it was
accomplished, we know that natural selection worked in favor of the photosynthetic microorganisms, leading to
further diversification.

Fluctuations in Oxygen
The history of macroscopic life on Earth is divided into three great eras: the Paleozoic, Mesozoic and Cenozoic.
Each era is then divided into periods. The latter half of the Paleozoic era, includes the Devonian period, which
ended about 360 million years ago, the Carboniferous period, which ended about 280 million years ago, and the
Permian period, which ended about 250 million years ago.
According to recently developed geochemical models, oxygen levels are believed to have climbed to a maximum
of 35 percent and then dropped to a low of 15 percent during a 120-million-year period that ended in a mass
extinction at the end of the Permian. Such a jump in oxygen would have had dramatic biological consequences
by enhancing diffusion-dependent processes such as respiration, allowing insects such as dragonflies, centipedes,
scorpions and spiders to grow to very large sizes. Fossil records indicate, for example, that one species of
dragonfly had a wing span of 2 1/2 feet.
Geochemical models indicate that near the close of the Paleozoic era, during the Permian period, global
atmospheric oxygen levels dropped to about 15 percent, lower that the current atmospheric level of 21 percent.
The Permian period is marked by one of the greatest extinctions of both land and aquatic animals, including the
giant dragonflies. But it is not believed that the drop in oxygen played a significant role in causing the extinction.
Some creatures that became specially adapted to living in an oxygen-rich environment, such as the large flying
insects and other giant arthropods, however, may have been unable to survive when the oxygen atmosphere
underwent dramatic change.

3. Composition of the Present Atmosphere

Comparison to Other Planets
The overall composition of the earth's atmosphere is summarized below along with a comparison to the
atmospheres on Venus and Mars - our closest neighbors.

SURFACE
PRESSURE

VENUS

EARTH

MARS

100,000 mb

1,000 mb

6 mb

COMPOSITION
CO2

>98%

0.03%

96%

N2

1%

78%

2.5%

Ar

1%

1%

1.5%

O2

0.0%

21%

2.5%

H2O

0.0%

0.1%

0-0.1%

(more on Mars)

(more on Earth)

(more on Mars)

The variations in concentration from the Earth to Mars and Venus result from the different processes that
influenced the development of each atmosphere. While Venus is too warm and Mars is too cold for liquid water
the Earth is at just such a distance from the Sun that water was able to form in all three phases, gaseous, liquid
and solid. Through condensation the water vapor in our atmosphere was removed over time to form the oceans.
Additionally, because carbon dioxide is slightly soluble in water it too was removed slowly from the atmosphere
leaving the relatively scarce but unreactive nitrogen to build up to the 78% is holds today.
Current Composition
The concentrations of gases in the earth atmosphere is now known to be (ignoring water vapor, which varies
between near zero to a few percent):

CONSTITUENT

CHEMICAL SYMBOL

MOLE PERCENT

Nitrogen

N2

78.084

Oxygen

O2

20.947

Argon

Ar

0.934

Carbon Dioxide

CO2

0.035

Neon

Ne

0.00182

Helium

He

0.00052

Methane

CH4

0.00017

Krypton

Kr

0.00011

Hydrogen

H2

0.00005

Nitrous Oxide

N2O

0.00003

Xenon

Xe

0.00001

Ozone

O3

trace to 0.00080

The unit of percentage listed here are for comparison sake. For most atmospheric studies the concentration is
expressed as parts per million (by volume). That is, in a million units of air how may units would be that species.
Carbon dioxide has a concentration of about 350 ppm in the atmosphere (i.e. 0.000350 of the atmosphere or
0.0350 percent).
Greenhouse Gases

Radiative Properties
Objects that absorb all radiation incident upon them are called "blackbody"
absorbers. The earth is close to being a black body absorber. Gases, on the
other hand, are selective in their absorption characteristics. While many
gases do not absorb radiation at all some selectively absorb only at certain
wavelengths. Those gases that are "selective absorbers" of solar energy
are the gases we know as "Greenhouse Gases."
The interactive activity to the right allows you to visualize how each
greenhouse gas selectively absorbs radiation. Wien's Law states that the
Click to interactively explore
wavelength of maximum emission of radiation is inversely proportional to
Selective Absorbers.
the object's temperature. Using that law we know that the wavelength of
-6
maximum emission for the Sun is about 0.5 m (1 m = 10 m) and the
wavelength for maximum emission by the Earth is about 10 m. In the
activity to the right see where the greenhouse gases absorb relative to those two important wavelengths.

Sources and Sinks

Greenhouse Gases (apart from water vapor) include:

Carbon Dioxide
Chlorofluorocarbons (CFCs)
Methane

Nitrous Oxide
Ozone

and each have different sources (emission mechanisms) and sinks (removal mechanisms) as outlined below.

Carbon Dioxide
Sources Released by the combustion of fossil fuels (oil, coal, and natural
gas), flaring of natural gas, changes in land use (deforestation,
burning and clearing land for agricultural purposes), and
manufacturing of cement
Sinks Photosynthesis and deposition to the ocean.
Importance Accounts for about half of all warming potential caused by human
activity.

Methane
Sources Landfills, wetlands and bogs, domestic livestock, coal mining, wet
rice growing, natural gas pipeline leaks, biomass burning, and
termites.
Sinks Chemical reactions in the atmosphere.
Importance Molecule for molecule, methane traps heat 20-30 times more
efficiently than CO2. Within 50 years it could become the most
significant greenhouse gas.

Nitrous Oxide
Sources Burning of coal and wood, as well as soil microbes' digestion..
Sinks Chemical reactions in the atmosphere.
Importance Long-lasting gas that eventually reaches the stratosphere where it
participates in ozone destruction.

Sources

Ozone

Sources Not emitted directly, ozone is formed in the atmosphere through

photochemical reactions involving nitrogen oxides and
hydrocarbons in the presence of sunlight.
Sinks Deposition to the surface, chemical reactions in the atmosphere.
Importance In the troposphere ozone is a pollutant. In the stratosphere it
absorbs hazardous ultraviolet radiation.

Chlorofluorocarbons (CFCs)
Sources Used for many years in refrigerators, automobile air conditioners,
solvents, aerosol propellants and insulation.
Sinks Degradation occurs in the upper atmosphere at the expenses of the
ozone layer. One CFC molecule can initiate the destruction of as
many as 100,000 ozone molecules.
Importance The most powerful of greenhouse gases in the atmosphere one
molecule of CFC has about 20,000 times the heat trapping power
on a molecule of CO2.

4. Summary
We developed a few useful tools for the study of biogeochemical cycles. These include the concepts of the
reservoir, fluxes, and equilibria.

Atmospheric evolution progressed in four stages, leading to the current situation. The atmosphere has
not always been as it is today - and it will change again in the future. It is closely controlled by life and,
in turn, controls life processes. Complex feedback mechanisms are at play that we do not yet
understand.

Oxygen became a key atmospheric constituent due entirely to life processes. It built up slowly over time,
first oxidizing materials in the oceans and then on land. The current level (20%) is maintained by
processes not yet understood.

Sometime just before the Cambrian, atmospheric oxygen reached levels close enough to today's to allow
for the rapid evolution of the higher life forms. For the rest of geologic time, the oxygen in the
atmosphere has been maintained by the photosynthesis of the green plants of the world, much of it by
green algae in the surface waters of the ocean.

Selective absorbers in our atmosphere keep the surface of the earth warmer than they would be without

an atmosphere.