GEOCHEMICAL CYCLES

1. INTRODUCTION

The Earth is a system containing essentially a fixed

amount of each stable chemical atom or
element.

• Each element can exist in several different

reservoirs.
• Each element on Earth moves among
reservoirs in the solid Earth, oceans,
atmosphere and organisms as part of
geochemical cycles.

Movement of matter between reservoirs is driven by

the Earth’s internal and external sources of
energy.

These movements are often accompanied by a

change in the physical and chemical properties
of matter.

Carbon, for example, occurs in carbonate rocks,

such as limestones, in the atmosphere as carbon
dioxide gas, in water as dissolved carbon
dioxide and in all organisms as complex molecules
that control the chemistry of life.

Due to the complexities of the chemical

processes in the Earth System, the extensive
interconnections between cycles, and the wide
 range of time scales involved, in practice only
approximate forms of the cycles for key
elements have been constructed.

2. GEOCHEMICAL CYCLES

2.1 THE CARBON CYCLE

• The circulation of carbon and its compounds is one of

Earth's fundamental geochemical cycles.

• It involves the cycling of carbon through reservoirs in

the geosphere, atmosphere, hydrosphere and
biota over a wide range of space and time scales.
• This cycling has gone on throughout most of Earth's
history, and has greatly modified the composition
of Earth's atmosphere while producing great beds
of carbonate rocks in the geosphere.

The biota- living things - play key roles in the carbon

cycle.

• Carbon is used by plants in the form of carbon dioxide

(CO2) in photosynthesis to generate the
carbohydrates and the energy needed for their survival.
• In this process, carbon is withdrawn from the
atmosphere and locked up in complex molecules (the
oxygen is returned to the atmosphere).
• Animals - non-photosynthetic organisms - breathe
oxygen, consume carbon by eating plants and/or
other animals, and give back CO2 to the
atmosphere.
• When either type of organism dies, the organic matter
decays and the carbon in the complex molecules are
released, generally as CO2, methane, etc.
For practical purposes, the global carbon cycle can
be taken to consist of exchanges of carbon via three
geochemical loops that operate on vastly different
time scales as follows:

1) An atmosphere - terrestrial biosphere loop

• Terrestrial plants take up carbon via

photosynthesis – in the form of dioxide (CO2) -
from the atmosphere and store it in their tissues.
• Decaying organic matter and forest and grass
fires return it to the atmosphere as CO2, methane
(CH4), and other carbon compounds.

• Time scales range from seasonal to decadal

to centennial.
• On these time scales, the ocean exchanges only
a relatively small amount of carbon with the
atmosphere.

• Cutting down forests or plants may destabilize

the environment because of a net reduction in
global photosynthesis.
• As a consequence, less carbon is absorbed
from the atmosphere (and less oxygen is
returned to it).

2) A terrestrial biosphere-geosphere-
hydrosphere loop
• This loop involves the medium to long-term
storage of carbon via burial of organic
materials in swamps, marshes and estuaries.

• In the short term, this loop produces peat, and

so is connected to the atmosphere - terrestrial
biosphere loop.
• On a much longer time scale, the Earth’s
crustal processes bury some of this material and
alter it to produce kerogen, coals, oil and natural
gas.
• With the passage of more time, the Earth’s
crustal processes return these materials to Earth's
surface where "weathering" then returns the
stored carbon to the atmosphere as CO2 or CH4.

• The "natural" time scales in this loop range from

1,000's to 10's of millions of years.

• Humankind has short-circuited this loop,

connecting it to the atmosphere - terrestrial
biosphere loop via the burning of fossil fuels for
energy. Carbon is the principal element present in
"fossil fuels". The burning of these fuels again
releases carbon as CO or CO2.

The terrestrial carbon cycle

3) An atmosphere-geosphere-hydrosphere loop
• This loop involves accumulation of calcium
carbonate (CaCO3) in marine sediments.
• Carbon diffuses from the atmosphere into the
ocean.
• Marine plankton in the oceanic biosphere extract
dissolved CO2 from sea water to form shells
of calcite.
• When the plankton dies, their shells settle to
the sea floor where they accumulate in thick
layers.

• Weathering of rocks also removes CO2 from the

atmosphere; the resulting solution flows to the
ocean where it precipitates to form sediments.
• When the layers of sediment are compacted and
harden, they become limestone.

• These bottom sediments are ultimately

metamorphized, with much of the carbon returning
to the atmosphere via volcanoes.

• Time scales range from millions to 100's of

millions of years.

• Great amounts of limestone are also buried in

Earth's crust so that today, Earth's greatest
reservoir of carbon is found in crustal rocks,
especially in limestone.

The aquatic carbon cycle

Global carbon reservoirs, fluxes, and turnover times
are given in the figure below
Major reservoirs are underlined.

Turnover times (reservoir divided by largest flux to

or from reservoir) are in parentheses.
Sedimentary carbonates and kerogen are the
largest carbon reservoirs, followed by marine
dissolved inorganic carbon (DIC), soils, surface
sediments and the atmosphere.
• The living biomass reservoir is somewhat
smaller than the atmospheric carbon reservoir
and actively exchanges with the atmospheric
reservoir through photosynthesis and
respiration.

Important fluxes or transfers take place between

reservoirs.
• Turnover or residence times for the reservoirs
range from >>106 yr for kerogen in the
sediment reservoir, 103 -105 yr for peats and
soil carbon, about three years for atmospheric
CO2 and less than one year for ocean biomass.

The major long-term sink for carbon is burial in deep

sea sediments. Protection of photosynthetically fixed
organic carbon from oxidation by photosynthetic
oxygen (respiration), and has permitted
accumulation of oxygen in the atmosphere and
ocean over geologic time. The carbon cycle is
completed by weathering of marine shales or by
combustion of fossil fuels
2.2 THE NITROGEN CYCLE

The nitrogen cycle is the circulation of the

element nitrogen and its compounds through
the Earth System.

On short time scales, much of this cycle involves

metabolic processes of living organisms.
A schematic representation of the nitrogen cycle is
shown here:

The Global nitrogen reservoirs, fluxes and turnover

times are given below
Major reservoirs are underlined.

Turnover times (reservoir divided by largest flux to

or from reservoir) are in parentheses.
 • As with oxygen, the atmosphere, which
contains 78% N2, is the largest nitrogen
reservoir.

• Other gaseous nitrogen species important in

ozone chemistry have short lifetimes and are of
local importance.

Nitrous oxide, an important long-lived greenhouse

gas, is photolyzed in the stratosphere.
• The thermodynamically stable form of nitrogen
in the presence of oxygen is not N2, but NO3-.

However, conversion of relatively inert N2 to other

forms is limited by the microbially mediated nitrogen
fixation rate and fixed nitrogen is rapidly
incorporated into living tissue.

Microbially mediated denitrification completes the

nitrogen cycle.
2.3 THE OXYGEN CYCLE

Global oxygen reservoirs, fluxes and turnover times

are given in the figure below.
Major reservoirs are underlined. Turnover times
(reservoir divided by largest flux to or from
reservoir) are in parentheses. 2
The atmosphere is the largest oxygen reservoir
and has the longest turnover time.

The atmospheric oxygen reservoir is ~200-fold

larger and has a turnover time >106-fold longer than
the next largest reservoirs, the ocean dissolved
oxygen reservoir and long-lived plants.

The major source of oxygen is photosynthesis, but

this is almost exactly balanced by respiration. Note
that ocean sediments are shown as an oxygen
source, because the long-term storage of organic
carbon in ocean sediments prevents oxidation and
allows accumulation of oxygen in the atmosphere.
2.4 THE PHOSPHORUS CYCLE

Inputs: Fertilizer P mined from phosphate deposits.

Phosphate is found in the mineral apatite.

A schematic representation of the phosphorus cycle:

Global phosphorus reservoirs, fluxes and turnover

times are given in the figure below.
Major reservoirs are underlined. Turnover times
(reservoir divided by largest flux to or from
reservoir) are in parentheses.

Note that the phosphorus cycle has no

atmospheric component, and is restricted to
solid and liquid phases.
The major sink is burial in marine sediments.
Marine phosphorite deposits are mined and
reintroduced to the cycle by man's activities.

2.5 THE SULPHUR CYCLE

Sulfur is one of the components that make up

proteins and vitamins.
• Proteins consist of amino acids that contain
sulfur atoms.
• Sulfur is important for the functioning of
proteins and enzymes in plants and animals that
depend upon plants for sulfur.
• Plants absorb sulfur when it is dissolved in
water.
• Animals will consume these plants, so that they
will take up enough sulfur to maintain their
health.

Most of the earth's sulfur is tied up in rocks and

salts or buried deep in the ocean in oceanic
sediments.

Sulfur can also be found in the atmosphere.

It enters the atmosphere through both natural and

human sources.
• Natural recourses can be for instance volcanic
eruptions, bacterial processes, evaporation from
water, or decaying organisms.
• When sulfur enters the atmosphere through
human activity, this is mainly a consequence
 of industrial processes where sulfur dioxide
(SO2) and hydrogen sulphide (H2S) gases are
emitted on a wide scale.

When sulfur dioxide enters the atmosphere it will

react with oxygen to produce sulfur trioxide gas
(SO3), or with other chemicals in the atmosphere, to
produce sulfur salts.
• Sulfur dioxide may also react with water to
produce sulphuric acid (H2SO4).
• Sulphuric acid may also be produced from
demethylsulphide, which is emitted to the
atmosphere by plankton species.

All these particles will settle back onto earth, or react

with rain and fall back onto earth as acid
deposition.

The particles will than be absorbed by plants

again and are released back into the
atmosphere, so that the sulfur cycle will start over
again.
A schematic representation of the sulfur cycle:
References:

http://www.ess.uci.edu/~reeburgh/figures.html

Jaffe, D. A., 1992, The Nitrogen Cycle. pp. 263-284.

In: Global Biogeochemical Cycles, S. S. Butcher, R.
J. Charlson, G. H. Orians & G. V. Wolfe, eds.,
Academic Press, San Diego.
Sšderlund, R. and B. H. Svensson, 1976, The global
nitrogen cycle. Ecol. Bull. (Stockholm) 22:23-73.
Jahnke, R. A.,1992, The Phosphorus Cycle, pp. 301-
315. In: Global Biogeochemical Cycles, S. S.
Butcher, R. J. Charlson, G. H. Orians & G. V. Wolfe,
eds., Academic Press, San Diego.
Berner, E. K. and R. A. Berner, 1996, Global
Environment, Water Air and Geochemical Cycles,
376 pp., Prentice-Hall, Upper Sattle River, NJ.