Phosphorus

Phosphorous was recognized as a distinct substance by Hennig Brand in 1669 when he

prepared it in a pure form from urine
Limiting Nutrient More on that Later
Does not have a stable gaseous phase in Earths Atmosphere.
Phosphorus is locked up in rock
o 3 Pools: Bedrock, soil & biomass
o 4 components: Tectonic uplift, exposure of P bearing rocks, physical erosion &
riverine sediment transport.
Conversion of phosphorus by geochemical and biochemical reactions are required
Microbial activity in soils and sediments influences the concentration and chemical form
of phosphorous

Phosphorus cycling in the Atmosphere
Insignificant Gaseous Phases (PH3)
Total Phosphorus exists are Aerosols
Sources for Phosphorus in atmosphere:
o Mineral Aerosols - Dust (82%)
o Combustion Sources
Coal Combustion
Oil Boilers
Gasoline Engines
Diesel Engines
Incinerators
o Sea Salt Aerosols
PO
o Volcanic Aerosols
o Biogenic Aerosols (12%)
Spores or bits of plants directly emitted to atmosphere

Phosphorus cycling in the Hydrosphere
Primarily transported to ocean through continental weathering., which contains on
average 0.1% PO
o Transported via riverine fluxs as dissolved and particulate phases.
Particulate phase in riverine system.
Phosphorus that enters the ocean from riverine system is in dissolved
phase.
o Atmospheric deposition of aerosols in ocean is minor flux.
4.5 x 10 mol P yr -

Non point runoff causes an influx of P into rivers and estuaries causing eutrophication.
Exists as both organic and inorganic form
o 20-40% of Phosphorus is organic
o Inorganic forms are ferric oxyhydroxides & Apatite
o Flux estimates using average riverine discharges range between 27 and 49 10
mol/year for Inorganic Phosphorus and 2.9 10 mol/year for Organic Phosphorus.
o Difficult to pinpoint Riverine exact flux due to deforestation and use of
fertilizers.
Phosphorus can enter the ocean via low temperature reactions between seawater and
seafloor basalts.
A minor sink for P is uptake through seawater - oceanic crust interactions associated with
hydrothermal activity on the oceans floor
Marine Sediments
o A sink for phosphorus in ocean
o Less than 1% of Phosphorus that reaches the ocean floor gets buried
4 process serve as P removal mechanisms
o Organic Matter burial largest transport via biological uptake
o P-sorption & precipitation with clays and iron hydroxide particles P is absorbed
onto shells made of CaCO3 via iron oxyhydroxide coatings.
o Phosphorite burial burial of phosphorite particles
o Hydrothermal processes hydrothermal vent fluids contain a large amount of
reduced iron that quickly oxidize to form ferric oxyhydroxides in sea water. These
oxyhydroxides are efficient in scavenging dissolved phosphorus.
Phosphorus Sources: 20,000-80,000 year residence time
Phosphorus Sink: 9,300-29,100 years residence time


Phosphorus cycling in the Lithosphere
Phosphorus 11
th
most abundant element in Earths crust.
Limitations - Sorption is most important process limiting P availability
o Sorptive binding of P to Fe and Al oxides makes it unavailable
o Leached from soil due to weathering
o Immobilization: available P taken up by microbes competition with plants
P is a major regulator in more weathered soils
Less weathered soils have a more even limitation based on both P and N
Loss of P from terrestrial systems via runoff enhanced by anthropogenic activity
Availability
o Most terrestrial P derived from weathering of calcium phosphate minerals
o Soil microbes, mycorrhizae, plants roots increase P availability
o Mineralization: organic P released by microbes via decomposition
o Recycling of organic P is extremely important in soils
o Seaspray and soil dust also provide P for soils
Soil
o In most soils, only small fraction of total P is available to biota
o Soil reservoir (to 50cm depth): 46 x 10
15
g P only 13.8 x 10
15
is labile
o Relative amounts can vary greatly amongst different soils


Phosphorus in Biosphere
Essential Element to all life
Structural and Functional component of all organisms
o Provides the phosphate-ester backbone of DNA & RNA
o Crucial in transmission of chemical energy through ATP molecule
o Structural constitute in phosphoproteins and phospholipids in cell membranes,
teeth, and bones.
o pH buffer in blood
Photosynthesis
o When respiration is restricted due to P shortage, sugars are not converted to
energy and accumulate in plant tissue. P deficiency leads to purple coloration and
stunted growth.

Current Uses
Concentrated phosphoric acids have become a critical part of agriculture and farm
production. Phosphoric acids may contain as much as 75 percent phosphorus pentoxide
(P2O5) content and are used as fertilizers. Large agricultural businesses around the
world have increased demand for fertilizer resulting in record phosphate production.
Phosphoric acid is also used in soft drinks. Calcium phosphate also known as bone-
ash is used in creating chinaware and to produce mono-calcium phosphate that is used
in baking powder.

History
o Initially crop production relied on natural levels of soil phosphorus and the
addition of locally available organic matter like manure and night soil (human
excrement collected at night)This is what was used until the 17th and 18th century
where famines in Europe created a need for other sources of phosphorus. In the
early 19th century England began importing large quantities of bones from other
countries.

o There were also agricultural improvements including crop rotation, improved
handling of manure, and introduction of new crops such as clover which could fix
nitrogen from the atmosphere.

o Around the mid to late 19th century the use of local organic matter was replaced
by phosphorus material from more distant sources. Mining of guano and
phosphate rich rock had begun.

o Application of the highly concentrated mineral fertilizers helped with the
phosphorus deficiency in the soils, improved agricultural output in many
countries and introduced new crop varieties.

o Some people say that existing rock phosphate reserves could be exhausted in the
next 50 to 100 years. Responses to this scarcity problem include higher prices,
more efficient resource use, the introduction of alternatives and recovery of the
resource after use.

The more current situation

o Although soil levels in Europe and North America are said to have surpassed
critical phosphorus levels and demand for phosphorus has stabilized in these
regions, the same cannot be said for developing and emerging economies.

o It's estimated that there will be 2-2.5 billion new mouths to feed by 2050 mainly
in the developing world and global food production will need to increase about
70% to meet this global demand.

o The increasing concern of oil scarcity and climate change has led to a sharp
increase in biofuel production.

o The biofuel industry competes with food production for grains, productive lands
and phosphorus fertilizers.

o Approximately 50-100 years remain of current known reserves.

o Another thing to keep in mind is that each ton of phosphate processed from
phosphate rock generates 5 tons of phosphogypsum, which is a toxic byproduct

o Phosphogypsum cannot be used in most countries due to unacceptably high
radiation levels, which is causing the stockpiles to grow by over 110 million tons
each and have a risk of leakage to groundwater.


Human Impacts
o Deforestation & widespread cultivation caused increase riverine particulate P-
flux.
o Dams decrease sediment loads therefore decrease P-flux to the ocean.