Phosphorite

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Guano mining in the Central Chinchua Islands

Phosphorite, phosphate rock or rock phosphate is a non-detrital sedimentary rock which contains high amounts of phosphate bearing minerals. The phosphate content of phosphorite is at least 15 to 20%, which is a large enrichment over the typical sedimentary rock content of less than 0.2%.[1] The phosphate is present as fluorapatite Ca5(PO4)3F (CFA) typically in cryptocrystalline masses (grain sizes < 1 μm) referred to as collophane.[1] It is also present as hydroxyapatite Ca5(PO4)3OH, which is often dissolved from vertebrate bones and teeth, whereas fluorapatite can originate from hydrothermal veins. Other sources also include chemically dissolved phosphate minerals from igneous and metamorphic rocks. Phosphorite deposits often occur in extensive layers, which cumulatively cover tens of thousands of square kilometres of the Earth's crust.[2]

Limestones and mudstones are common phosphate bearing rocks.[3] Phosphate rich sedimentary rocks can occur in dark brown to black beds, ranging from centimeter sized laminae to beds that are several meteres in thickness. Although these thick beds can exist they are rarely only composed of phosphatic sedimentary rocks. Phosphatic sedimentary rocks are commonly accompanied by or interbedded with shales, cherts, limestone, dolomites and sometimes sandstone.[3] These layers contain the same textures and structures as fine grained limestones and may represent diagenetic replacements of carbonate minerals by phosphates.[1] They also can be composed of peloids, ooids, fossils, and clasts that are made up of apatite. There are some phosphorites that are very small and have no distinctive granular textures. This means that their textures are similar to that of collophane, or fine micrite-like texture. Phosphatic grains may be accompanied by organic matter, clay minerals, silt sized detrital grains, and pyrite. Peloidal or pelletal phosphorites occur normally; whereas oolitic phosphorites are not common.[3]

Phosphorites are known from Proterozoic banded iron formations in Australia, but are more common from Paleozoic and Cenozoic sediments. The Permian Phosphoria Formation of the western United States represents some 15 million years of sedimentation. It reaches a thickness of 420 metres and covers an area of 350,000 km2.[1] Commercially mined phosphorites occur in France, Belgium, Spain, Morocco, Tunisia and Algeria. In the United States phosphorites have been mined in Florida, Tennessee, Wyoming, Utah, Idaho and Kansas.[4]

Classification of phosphatic sedimentary rocks

(1) Pristine: Phosphates that are in pristine conditions have not undergone bioturbation. In other words the word pristine is used when phosphatic sediment, phosphatized stromatolites and phosphate hardgrounds have not been disturbed.[5]

(2) Condensed: Phosphatic particles, laminae and beds are considered condensed when they have been concentrated. This is helped by the extracting and reworking processes of phosphatic particles or bioturbation.[5]

(3) Allochthonous: Phosphatic particles that were moved by turbulent or gravity-driven flows and deposited by these flows.[5]

Phosphorus cycle, formation and accumulation

The heaviest accumulation of phosphorus is mainly on the ocean floor. Phosphorus accumulation occurs from atmospheric precipitation, dust, glacial runoff, cosmic activity, underground hydrothermal volcanic activity, and deposition of organic material. However, the primary inflow of dissolved phosphorus is from continental weathering, brought out by rivers to the ocean.[6] It is then processed by both micro- and macro-organisms. Diatomaceous plankton, phytoplankton, and zooplankton process and dissolve phosphorus in the water. The bones and teeth of certain fish (e.g. anchovies) absorb phosphorus and are later deposited and buried in the ocean sediment.[7]

Depending on the pH and salinity levels of the ocean water, organic matter will decay and releases phosphorus from sediment in shallow basins. Bacteria and enzymes dissolve organic matter on the water bottom interface, thus returning phosphorus to the beginning of its biogenic cycle. Mineralization of organic matter can also cause the release of phosphorus back into the ocean water.[7]

Depositional environments

Phosphates are known to be deposited in a wide range of depositional environments. Normally phosphates are deposited in very shallow, near shore marine or low energy environments. This includes environments such as supratidal zones, littoral or intertidal zones, and most importantly estuarine.[7] Currently, areas of oceanic upwelling cause the formation of phosphates. This is because of the constant stream of phosphate brought from the large, deep ocean reservoir (see below). This cycle allows continuous growth of organisms.[5]

Supratidal zones: Supratidal environments are part of the tidal flat system where the presence of strong wave activity is nonexistent. Tidal flat systems are created along open coasts and relatively low wave energy environments. They can also develop on high energy coasts behind barrier islands where they are sheltered from the high energy wave action. Within the tidal flat system, the supratidal zone lies in a very high tide level. However, it can be flooded by extreme tides and cut across by tidal channels. This is also subaerially exposed, but is flooded twice a month by spring tides.[8]

Littoral environments/ intertidal zones: Intertidal zones are also part of the tidal flat system. The intertidal zone is located within the mean high and low tide levels. It is subject to tidal shifts, which means that it is subaerially exposed once or twice a day. However, it is not exposed long enough to withhold vegetation. The zone contains both suspension sedimentation and bed load.[8]

Estuarine environments: Estuarine environments, or estuaries, are located at the lower parts of rivers that stream into the open sea. Since they are in the seaward section of the downed valley system they receive sediment from both marine and fluvial sources. These contain facies that are affected by tide and wave fluvial processes. From the top, the estuary is considered to stretch from in the landward limit of tidal facies to the seaward limit of costal facies. Phosphorites are often deposited in fjords within estuarine environments. These are estuaries with shallow sill constrictions. During Holocene sea-level rise, these estuaries built a U shaped valley profile formed by drowning the glacially eroded valleys.[8]

The most common occurrence of phosphorites are related to strong marine upwelling of sediments. Upwelling is caused by deep water currents that are brought up to coastal surfaces where a large deposition of phosphorites may occur. This type of environment is the main reason why phosphorites are commonly associated with silica and chert. Estuaries are also known as a phosphorus “trap”. This is because coastal estuaries contain a high productivity of phosphorus from marsh grass and benthic alge which allow an equilibrium exchange between living and dead organisms.[9]

Types of phosphorite deposition

(1) Nodular phosphorites: These are spherical concentrations that are randomly distributed along the floor of continental shelves. Most phosphorite grains are sand size although particles greater than 2mm may be present. These larger grains, referred to as nodules, can range up to several tens of centimeters in size.

(2) Bioclastic phosphates or bone beds: Bone beds are bedded phosphate deposits that contain concentrations of small skeletal particles and coprolites.[3] Some also contain invertebrate fossils like brachiopods and become more enriched in P2O5 after diagentic processes have occurred. Bioclastic phosphates can also be cemented by phosphate minerals.[7]

(3) Phosphatization: Phosphatization is a type of rare diagenetic processes. It occurs when fluids that are rich in phosphate are leached from guano.[3] These are then concentrated and reprecipitated in limestone. Phosphatized fossils or fragments of original phosphatic shells are important components within some these deposits.

Tectonic and oceanographic settings of marine phosphorites

(1) Epeiric sea phosphorites: Epeiric sea phosphorites are within marine shelf environments. These are in a broad and shallow cratonic setting. This is where granular phosphorites, phosphorite hardgrounds, and nodules occur.[5]

(2) Continental margin phosphorites: Convergent, passive, upwelling, non-upwelling. This environment accumulates phosphorites in the form of hardgrounds, nodules and granular beds.[9] These accumulate by carbonate fluorapatite percipitaion during early diagenesis in the upper few tens of centimeters of sediment. There are two different environmental conditions in which phosphorites are produced within continental margins. Continental margins can consist of organic rich sedimentation, strong coastal upwelling, and pronounced low oxygen zones. They can also form in conditions such as oxygen rich bottom waters and organic poor sediments.[5]

(3) Seamount phosphorites: These are phosphorites that occur in seamounts, guyots, or flat topped seamounts, seamount ridges. These phosphories are produced in association with iron and magnesium bearing crusts. In this setting the productivity of phosphorus is recycled within an iron oxidation reduction phosphorus cycle. This cycle can also form glauconite which is normally associated with modern and ancient phosphorites.[5]

(4) Insular phosphorites: Insular phosphorites are located in carbonate islands, plateaus, coral island consisting of a reef surrounding a lagoon or, atoll lagoon, marine lakes. The phosphorite here originates from guano. Replacement of deep sea sediments precipitates, that has been formed in place on the ocean floor.[5]

Production and use

Phosphorite mine near Oron, Negev, Israel.

Deposits which contain phosphate in quantity and concentration which are economic to mine as ore for their phosphate content are not particularly common. The two main sources for phosphate are guano, formed from bird droppings, and rocks containing concentrations of the calcium phosphate mineral, apatite.

Phosphate rock is mined, beneficiated, and either solubilized to produce wet-process phosphoric acid, or smelted to produce elemental phosphorus. Phosphoric acid is reacted with phosphate rock to produce the fertilizer triple superphosphate or with anhydrous ammonia to produce the ammonium phosphate fertilizers. Elemental phosphorus is the base for furnace-grade phosphoric acid, phosphorus pentasulfide, phosphorus pentoxide, and phosphorus trichloride. Approximately 90% of phosphate rock production is used for fertilizer and animal feed supplements and the balance for industrial chemicals.

Froth flotation is used to concentrate the mined phosphorus to rock phosphate. The mined ore slurry is treated with fatty acids to cause calcium phosphate to become hydrophobic.

For general use in the fertilizer industry, phosphate rock or its concentrates preferably have levels of 30% phosphorus pentoxide (P2O5), reasonable amounts of calcium carbonate (5%), and <4% combined iron and aluminium oxides. Worldwide, the resources of high-grade ore are declining, and the beneficiation of lower grade ores by washing, flotation and calcining is becoming more widespread.

In addition to phosphate fertilisers for agriculture, phosphorus from rock phosphate is also used in animal feed supplements, food preservatives, anti-corrosion agents, cosmetics, fungicides, ceramics, water treatment and metallurgy.[10]

The US is the world's leading producer and exporter of phosphate fertilizers, accounting for about 37% of world P2O5 exports.[11] The world’s total economic demonstrated resource of rock phosphate is 18 Gt, which occurs principally as sedimentary marine phosphorites.[10]

China, the United States and Morocco are the world's largest miners of phosphate rock, with a production of 77MT, 29.4MT and 26.8MT (including 2.5MT in Western Sahara) respectively in 2012 while Global production reached 195MT.[12] Other countries with significant production include Brazil, Russia, Jordan and Tunisia. Historically, large amounts of phosphates were obtained from deposits on small islands such as Christmas Island and Nauru, but these sources are now largely depleted.

References

  1. ↑ 1.0 1.1 1.2 1.3 Blatt, Harvey and Robert J. Tracy, Petrology, Freeman, 1996, 2nd ed. pp. 345–349 ISBN 0-7167-2438-3
  2. ↑ C.Michael Hogan. 2011. Phosphate. Encyclopedia of Earth. Topic ed. Andy Jorgensen. Ed.-in-Chief C.J.Cleveland. National Council for Science and the Environment. Washington DC
  3. ↑ 3.0 3.1 3.2 3.3 3.4 Prothero, Donald R. and Schwab, Fred (22 August 2003). Sedimentary Geology. Macmillan. pp. 265–269. ISBN 978-0-7167-3905-0. Retrieved 15 December 2012. 
  4. ↑ Klein, Cornelis and Cornelius S. Hurlbut, Jr., Manual of Mineralogy, Wiley, 1985, 20th ed., p. 360, ISBN 0-471-80580-7
  5. ↑ 5.0 5.1 5.2 5.3 5.4 5.5 5.6 5.7 Middleton V. Gerald, 2003 Encyclopedia of Earth Sciences series. Encyclopedia of Sediment and Sedimentary Rocks. Kluwer Academic Publishers. Dordrect, Boston, London. pp 131, 727, 519–524.
  6. ↑ Delaney, M.L. (1998). "Phosphorus Accumulation in Marine Sediments and Oceanic Phosphorus Cycle". Biogeochemical cycles 12 (4): 563–572. doi:10.1029/98GB02263. 
  7. ↑ 7.0 7.1 7.2 7.3 Baturin, G.N, Phosphorites on the Sea Floor: Origin, Composition and Distribution. Elsevier. 1981, New York, pp. 24–50 ISBN 044441990X.
  8. ↑ 8.0 8.1 8.2 Boggs, Sam, Jr. (2006). Principles of Sedimentology and Stratigraphy (4th ed.), Pearson Education Inc., Upper Saddle River, NJ, pp. 217–223 ISBN 0321643186
  9. ↑ 9.0 9.1 Pevear, D. R. (1966). "The estuarine formation of United States Atlantic Coastal Plain phosphorite". Economic Geology 61 (2): 251–256. 
  10. ↑ 10.0 10.1 Phosphate AIMR Report 2008. ga.gov.au
  11. ↑ US Geological Survey Minerals Yearbook 2006 Rock Phosphate
  12. ↑ IFA 2012 statistics
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