The Phosphorus Cycle

Phosphorus Properties
Atomic Number: 15
Melting Point: 111.5 F (44.15 C) Boiling Point: 536.9 F (280.5 C) Nonmetal, part of nitrogen group Found in nature in several allotropic forms; White, red & black. White created industrially Essential element for life Limiting Nutrient In nature, never encountered in pure form, mostly as phosphate Exists primarily as PO= First discovered in 1669, by Hennig Brand, when first isolated in a pure form from urine.

Credit: Greg Robson/Creative Commons, Andrei Marincas | Shutterstock

Phosphorus Properties Continued

Does not have a stable gaseous phase in atmosphere
Exists as Aerosols

Phosphorus is locked up is rock

3 Sources: Bedrock, Soil & Biomass 4 Components: Riverine sediment transport, Physical erosion, Exposure of P bearing rocks & tectonic uplift.

 Photosynthetic organisms utilize dissolved phosphorous, carbon and other esthetical nutrients to build their tissues using energy from the sun. Biological productivity is contingent upon the availability of phosphorous food web both from terrestrial and aquatic systems.

 The most common mineral on that contains phosphorus is Apatite Ca5(PO4)3(OH,F,Cl). Phosphate minerals with high concentrations of apatite are mined. Anthropogenic release of Phosphorus

Uses of Phosphorus
Fertilizers (Red) Pesticides (Red) Steel Production Military Applications
Incendiary bombs, smoke screening (White)
Photo courtesy of: http://news.naij.com/33525.html

Pyrotechnics (White) Household Products

Toothpaste, Detergents

Production of LEDs Soft Drinks China Baking Soda

Photo courtesy of: http://economicdevelopment.missouri.edu/features/2011/ampyrotechnics/index.php

Global Phosphorous Cycle

Phosphorous Cycle has 4 major components: Tectonic uplift Exposure of P bearing rocks Physical Erosion River

Terrestrial Phosphorus Cycle

Weathering of continental bedrock is the prime source of phosphorus soils which support vegetation growth. P-mineral in crustal rocks. Weathering reactions driven by exposure of minerals to natural acids from microbial activity.

Marine: Transport of Phosphorus

~20-40 % of P is suspended particulate matter is organic Inorganic forms are divided ferricoxyhydroxide (HFeO2) and Apatite . Continents to Ocean Groundwater seepage to coastal ocean poorly documented. Dissolved phosphorous in rivers occurs in both organic and inorganic forms. Riverine P depends on drainage basins

Phosphorous PH
At Low PH values and least soluble P phases are those that contain iron and aluminum Vivianite (Fe2+Fe2+2(PO4)28H2O) Strengite FePO42H2O Variscite AlPO42H20

Phosphorous PH
At high PH values least soluble P are in the mineral apatite. Phosphorus solubility is greatest at intermediate levels of PH found in natural waters

Phosphorus Cycling In Atmosphere

No stable gas phase Total Phosphorus exists as Aerosols Sources:
Mineral Aerosols (dust) 82% Biogenic Aerosols - 12%
Spores or pieces of plants emitted directly to the atmosphere.

Combustion Sources
Coal, Oil boilers, gasoline & diesel engines, incinerators

Sea Salt Aerosols

PO=

Volcanic Aerosols Very Small Amount from Swamps

PH

Phosphorus Cycling in Lithosphere

11th most abundant element in Earths crust
Most common mineral is Apatite

Mining of Phosphate Deposits

Mined for use in agriculture and industry
2005 17.5 million tons mined

Mines found in North American (especially Florida), Africa (Egypt, Morocco, Tunisia), Middle East (Isreal, Saudi Arabia, Jordan, Iraq), Australia Byproducts of mining phosphate
Cadmium, lead, nickel, copper, chromium & uranium If not managed correctly, these heavy elements can leach into groundwater & estuaries. Bioaccumulation of toxic substances

Courtesy of http://en.wikipedia.org/wiki/File:Train_loaded_with_phosphate_rock,_Metlaoui_Tunisia-4298B.jpg

 Phosphorus deposits on ocean floor

Via decomposition, deposition, mineralization Sedimentation

Phosphorus bearing rocks can be recycled into mantle at subduction zones or uplifted Uplift causes rock to become exposed and erode due to physical
and chemical weathering

As the rock erodes phosphorus is released into the soil

 Phosphorus Soil Reservoir

Soil reservoir (up to 50 cm depth) 46x10;? g P, only ~13.8x10;? g is labile Small fraction of total P available to biota Relative amounts vary amongst different soils Recycling of organic P extremely important Major regulator of bio-productivity in weathered soils.

Availability
Weathering of phosphate minerals Weathering of sedimentary rock Soil microbes, mycorrhizae, & plants roots increase P availability Mineralization: organic P released by microbes via decomposition Fertilizers Very small percentage is deposited from the atmosphere

 Limitations
Sorption most important process limiting P availability Sorptive binding of P to Fe & Al oxides make P unavailable Leached from soil Immobilization: available P taken up by microbes Less weathered soils have a more even limitation based on both P and Nitrogen

Phosphorus is lost from terrestrial systems due to run-off Enhanced by anthropogenic activity Also lost through crop harvesting

Terrestrial P Cycle

Phosphorus Cycling in Hydrosphere

Primarily transported to ocean through rivers as a result of weathering and small percentage from leaching.
On average 0.1% PO (Diphosphorous tetroxide)

River Transport
Dissolved and particulate phases Primarily particulate phase in river system Phosphorus enters the ocean in dissolved phase.

Exists as organic and inorganic

20-40% Phosphorus is organic Inorganic forms are ferric oxyhydroxides & Apatite Flux estimates for riverine discharges range between 27x 10;: mol/year for inorganic and 2.9x10;: mol/year for organic phosphorus. Difficult to calculate exact river discharge flux due to anthropogenic input (ex. Deforestation, leaching from fertilizers)

Lakes
Phosphorus from soil erosion and decomposition of organic matter.

 4 processes serve as Phosphorous removal mechanisms

Organic matter burial decomposition P-sorption & precipitation with clays and iron hydroxide particles.
Phosphorus can be absorbed onto shells made of CaCO via iron oxyhydroxide coating.

Burial of Phosphate particles Hydrothermal processes

Vent fluids contain large amounts of reduced Fe. Quickly oxidizes to form ferric oxyhydroxides Efficient in scavenging dissolved phosphorus

Phosphorus Cycling in Hydrosphere Continued

Non-point runoff causes an influx of Phosphorous into lakes and estuaries that can cause eutrophication.
Algae blooms caused by excess of nutrients

Minor sink Phosphorus uptake through seawater & oceanic crust interactions associated with hydrothermal activity on ocean floor. Marine Sediments
A sink for phosphorus in ocean Less than 1% of phosphorus that reaches the ocean floor gets buried Organic Phosphorus subject to break down via microbial respiration
Marine respiration Redfield ration 106C:1P

Phosphorus Cycling in Biosphere

Phosphorus us an essential element to all life Structural and functional component of all organisms
Provides the phosphate-ester backbone of DNA & RNA Crucial in transmission of chemical energy through ATP molecule Structural constitute in phosphoprotiens and phospolipids in cell membranes, teeth and bones. Acts as a pH buffer in blood.

Uptake of Phosphorous by plants through soil.

Phosphorous deficiency can cause color changes in plants
Photosynthesis restricted

Can cause plants to die off Decomposition returns phosphorous into soil

Uptake of Phosphorous by organisms

Marine organisms can secrete Phosphorous through flocculation Animals eat algae and other organisms
Die, decompose, phosphorous returned to ocean system.

Deficiency
Affect plant growth and rate of photosynthesis Research on bean plant culture removal of phosphate from the nutrient rich solution affected growth of bean plants.

Impacts On Other Cycles

Carbon Cycle
Redfield ratio needs for respiration 106C:16N:1P

Nitrogen Cycle
Phosphorus is essential for Rhizobium bacteria to convert atmospheric N (N) into Ammonium (NH)

Iron Cycle
Upon decomposition of organic matter, the iron redox cycle provides an effective means of trapping phosphate in sediments

Sulfur Cycle
In fresh water systems, low SO< (sulfate), Phosphorus is strongly absorbed by elements in sediments. Lakes High SO< from acid rain and pyrite mining will have an anion exchange reaction which drives Phosphorous into solution.

Chemistry
Phosphoric Acid Disassociation ka= 2.4 x 10;= = *PO=+*H++ = (8.86x10?)(10=) [H PO] [H PO] = (8.86x10?)(10=) = *H PO=+ (Hydrogen Phosphate) = 1.057 x 10<@ (4.2x 10;= ) Low Concentration [PO=] 7PPM = Mg/Liter Ocean Water pH= 8.3 Conversion= 7x 10= g x 1 Mole PO= = 8.86x10? Mol L; (Low) Liter 79 g 70 PPM -> 70 x 10= x 1 Mole PO= = (8.86x10>)(10) = 1.057 x 10<? (High) Liter 79 g (4.2x 10;= ) River-Lakes Rainwater pH=5.65 *H PO=] = (8.86x10>)(10?@?) = Low Concentration 4.2 x 10<= (4.2x 10;= ) *Comparison of the high concentrations of HPO< is in the order of 2 magnitudes.

One can work backwards to obtain Phosphoric Acid

HPO HPO + *H++ HPO HPO< + [H+] HPO< PO= + [H+] ka = *HPO+ [H+] [HPO ] ka = *HPO<+ *H+] [HPO+ ka = *PO=+ *H+] [HPO<+ ka = 7.5 x 10= Molar ka = 6.2 x 10 Molar ka = 4.2 x 10;= Molar

Choosing High *PO=+ 10 PPM pH=5.65 Terrestrial Water Sources

*HPO<+*H++ = (8.86x10>)(10?@?) = 3.20 x 10 Molar *HPO+ ka=6.2x10 6.2x10 *HPO+ [H+] = (3.20 x 10)(10?@?) = 9.55x10 Molar *HPO+ ka=7.5x10= 7.5x10= Choosing pH=8.3 Ocean water with High *PO=+ 70PPM (1.057x10<?)(10=) = 8.54 x 10>= Molar *HPO+ 6.2x10 (8.54x 10>)(10=) = 5.71 x 10?? Molar *HPO+ 7.4x10 *Observed changes in concentrations have been simplified excluding affects of salinity and other competing ions.

Gibbs Free Energy All data derived from standard state thermodynamic data tables

Ca(PO)OH + 4HCO 5Ca<+(aq) + 3HPO<(aq) + 4HCO(aq)+HO (l) [Hydroxyapatite] -6338.3 kJ mol; + 4(-623.14) 5(-552.8) + 3(0) + 4(-586.8) + (-237.14) Gf = Gf Products - Gf Reactants = (-2764) + (-2347.20) + (-237.14) (-6338.3) + (-2492.56) = (-5348.34) + 8830.86 = 3482.52 kJ/mol Empirical Evidence Endothermic Process Al+(aq) + HPO<(aq) + 2H0 (l) AlPO + 2HO (l) + H+ 0 + 0 + 2(-237.14) (-2097.8) + 2(-237.14) + 0 Gf= Gf Products - Gf Reactants = (-2097.80) +(-474.28) (-474.28) = (-2572.08) + 474.28 = - 2097.80 kJ/mol Exothermic

White Phosphorus Reaction

White phosphorus ignites spontaneously on a filter paper.

P (white) + 5O --> PO

Current Issues
Soil levels in Europe and North America have surpassed critical phosphorus levels and demand for phosphorus has stabilized in these regions Estimated 2-2.5 billion new mouths to feed by 2050 mainly in developing world Global food production will need to increase about 70% to meet this global demand Increase in popularity of meat and dairy based diets have led to increase in phosphorus demand As well as increasing concern of oil scarcity and climate change has led to a sharp increase in biofuel production Biofuels is found to consume about 2% of the global inorganic P fertilizer production.

Approximately 50-100 years remain of current known reserves

Remaining phosphate reserves are under the control of a handful of countries, China, the U.S and Morocco.

Current Issues
Close to 100% of phosphorus eaten is excreted Global population excretes around 3 million tons of phosphorus in urine and in feces and are becoming phosphorus hot spots Recycle phosphorus from human waste Each person excrete 1.2 grams of Phosphorus a day. Trapping this can produce ~3 million tons per year. One method is to extract struvite (magnesium ammonium phosphate) from waste at sewage treatment plants and processing into pellets. Urine separating toilets and latrines already deployed in Europe. Installed in Durban, South Africa. Peepoo, single use, self sanitizing, biodegradable bag that captures human waste (yes, your poop) and can be used and sold as fertilizer 2-4 weeks later. Over fertilization of agricultural soils is common in the northern hemisphere and contributes to excess discharge into water bodies and causes eutrophication 25% of the 1 billion tons of phosphorus mined since 1950 has ended up in bodies of water and buried in landfills. Toxic byproduct of each ton of phosphate processed from phosphate rock generates 5 tons of phospho-gypsum Cannot be used in most countries due to high radiation levels, which grow by over 110 million tons each stockpile. Risk of leakage to groundwater.

What Can We Do?

No quick fix to the problem Phosphorus can be recovered from food production and consumption system and reused as fertilizer Development on research of struvite In some urban areas in Pakistan and Asia more than 25% of vegetables are being fertilized with wastewater from cities. About 200 million farmers worldwide use wastewater to irrigate crops 67% of global yields of farmed fish are fertilized by wastewater If urine is not mixed with fecal matter, it can be used safely through storage Urine is essentially sterile and could provide more than half the phosphorus required to fertilize cereal crops. Ex. In Sweden, two municipalities have mandated that all new toilets be urine diverting Local farmers collect urine about once a year as liquid fertilizer Another approach is the addition of microbial inoculants to increase soil phosphorus availability.

Eutrophication
Globally estimated that annual accumulation of phosphorus in Earth's freshwater and terrestrial ecosystems has almost quadrupled. Under natural conditions eutrophication can be centuries-long aging process but when human caused can happen in a few years. Eutrophication studied since the turn of the twelfth century but not recognized as widespread international problem until the 1950-60s. Efforts to reduce phosphorus inputs into aquatic ecosystems by diverting sewage and cutting off point sources

By 1990's phosphates were also removed from detergents

Yet eutrophication persisted..

Eutrophication continued..
This was due to non point pollution sources Currently non point runoff is main source of phosphorus to most aquatic systems Ex. Hypoxic zone in the Gulf of Mexico caused by grain growing states of the midwest, carried to the gulf by the Mississippi River. The leakage of phosphorus from agricultural land has caused harmful algal blooms and this is a large concern for people Became the largest motivation to take measures to efficiently use phosphorus.

Harmful Algal Blooms

Algal populations that grow extensively and may produce harmful toxins Non toxic blooms are also hazardous because they suffocate fish, blocking light and depleting oxygen from water

Consuming these algal contaminated shellfish may result in many illnesses.

They have cultural and economic implications, specifically in coastal communities dependent on harvesting seafood and tourism In the U.S alone there have been an economic impact estimate of $82 million each year.

China July 2011

China July 2013

In Addition
Despite of the continually depleting reserves of phosphorus it is still used for reasons other than food production or alternative energy sources Pyrotechnics although recently decreased, the amounts used still is effective in creating environmental problems Chemical weapons