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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.

A cycle describes the distribution, transport and


behavior of elements through the reservoirs.

Like a circle, a cycle does not have a beginning


or end and can move in any direction.

If the element primarily cycles between the


reservoirs but excluding organisms then it follows
the geochemical cycle.
If the element passes through all the reservoirs and
also between organisms then it traces a
biogeochemical cycle.

Basic Concepts

• Reservoirs
- There are usually physical states, chemical
forms and locations in the cycle in which
nature stores the various chemical elements.
-A source or place of residence for elements in a
geochemical cycle
- Elements are bound up in a particular space.
- Elements reside as specific forms
- Usually expressed in terms of the mass in
gigatons (Gt), (billions of metric tons)

• Flux
- Movement of elements into or out of a
reservoir.
-The fluxes or movements between these
reservoirs are often accompanied by a
change in the physical and chemical
properties of matter.
• Transfer mechanisms
- Processes that move elements between
reservoirs
- They usually involve a physical process
and a chemical reaction
• Transfer rate
- Usually expressed in terms of Gt
(gigatons, billions of metric tons) per
year

• Residence time in a reservoir


- The average time an atom of an element
or molecule of a compound, remains in a
reservoir, of each reservoir.
- Using quantitative data about a cycle, we can
calculate residence time
- Estimated by dividing the amount of the
element in that reservoir by the transfer
rates in and out of it.

Some Stores and Transfer Pathways in a


Geochemical Cycle
Movement of matter between reservoirs is driven by
the Earth’s internal and external sources of
energy.
Carbon, for example, occurs in

• carbonate rocks, such as limestone,

• the atmosphere as carbon dioxide gas

• water as dissolved carbon dioxide and

• all organisms as complex molecules that


control the chemistry of life.

The residence time for atmospheric carbon dioxide


is 760 Gt divided by 60 Gt per year or ~13 years.
(Amount of the element in a reservoir divided by the
transfer rates in and out).

Due to the

• complexities of the chemical processes in


the Earth System,

• extensive interconnections between cycles,


and

• 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.
A box model depicting the relative sizes of the
carbon cycle reservoirs and fluxes

In a box model the figure is not intended to depict a


visual representation of the cycle and its
components, but a quantitative feeling for the
relative sizes.
• Size of cycle reservoirs
• Reservoirs are simply boxes scale to the stock of
the particular reservoir.
• Rates of cycle fluxes.
• Fluxes are drawn as arrows of varying thickness.
Biota

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 die, 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.

• All life requires nitrogen-compounds, e.g.,


proteins and nucleic acids.
Nitrogen States
N2 Elemental nitrogen "N2" is a gaseous form of
N.
NH3: Ammonia "NH3" is a gaseous form of N
derived from the breakdown of organic
matter, especially animal waste, and some
surface-applied fertilizers.
NO: Nitric oxide, a gaseous form of N, is found in
the atmosphere. It is derived from de-
nitrification, automobile exhaust, and industrial
processes.
N20: Nitrous oxide, a gaseous form of N, is found
in the atmosphere. It is derived from de-
nitrification, automobile exhaust, and industrial
processes

NH4+: Ammonium "NH4+" is attracted to soil


particles. It can be absorbed by plants. Most
ammonium is readily transformed to nitrate.
NO3 : Nitrate "NO3-" is not attracted to soil
-

particles. Nitrate can be absorbed by plants or


moved through the soil past the rooting zone
Fertilizer: Plant nutrients that are added to the soils.

Volatilization: Ammonium or urea changed to


ammonia which as a gas is released
into the air.

Animal Wastes: Animal excreta applied to soil for


nutrients

Organic Matter: Decomposed plant or animal


material.

Immobilization: Inorganic N used by


microorganisms changed into its
organic form

Mineralization Slow release of nutrients from


organic material.
Biological Fixation
Legumes (plants) make or "fix" N.
Special bacteria live on the roots of legumes. Receive
"food" in the form of carbohydrates from plants and,
in return, use nitrogen (N2) and changes it to organic
forms for plants

Nitrification Ammonia (NH4+) is changed to nitrate


(NO3-) by soil bacteria

De-nitrification: Nitrate (NO3-) is changed to


gaseous forms of nitrogen [elemental nitrogen (N2),
nitrous oxide (N2O), nitric oxide (NO)] by soil bacteria
when the soil is very wet (saturated).

Crop Uptake and Removal: The loss of nutrients


from the system when crops are harvested and part
of the plant is removed from the field.
• Most organisms cannot use elemental nitrogen

• Plants must secure their N in "fixed" form, i.e.,


incorporated in compounds such as:
o nitrate ions (NO3−)
o ammonia (NH3)
o urea (NH2)2CO

• Animals secure their N (and all other)


compounds from plants (or animals that have fed
on plants)

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.

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.

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.

2.4 THE PHOSPHORUS CYCLE


• P cannot be found in air in the gaseous state.
• P mainly cycles through water, soil and sediments.
• Hydrosphere - mostly dissolved PO43- (phosphate ion)
• P is mined from phosphate deposits.
• P is found in the mineral apatite, Ca(PO4)3(OH, Cl, F)

Soil

Phosphorus exists in many different forms in soil.


These can be grouped into four general forms:
(1) Inorganic P
(2) Organic P,
(3) Adsorbed P
(4) Primary mineral P

The P cycle in Fig. 1 shows the P forms and


pathways

The general P transformation processes are:

• Weathering and precipitation


Soils naturally contain P-rich minerals, which are
weathered over long periods of time.
Phosphorus can undergo precipitation when
inorganic P reacts with dissolved iron, aluminum,
manganese (in acid soils), or calcium (in alkaline
soils) to form phosphate minerals.
• Mineralization and immobilization
Mineralization is the microbial conversion of
organic P to H2PO4- or HPO42-, known as
orthophosphates.
Immobilization occurs when P forms are
consumed by microbes, turning the P into
organic P forms. The microbial P will become
available over time as the microbes die.

• Adsorption and desorption


Adsorption is the chemical binding of P to soil
particles.
Desorption is the release of adsorbed P from its
bound state into the soil solution.
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.
2.5 THE SULPHUR/SULFUR CYCLE
A schematic representation of the sulfur cycle:
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


anthropogenic sources.
• Natural sources 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 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.

Sulfur behaves very much like nitrogen, as far


as the way plants and microorganisms use
sulfur in the environment.

The organic forms of S must be mineralized by


soil microorganisms
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.