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biogenic silica : ウィキペディア英語版
biogenic silica

Biogenic silica (bSi), also referred to as opal, biogenic opal, or amorphous opaline silica, forms one of the most widespread biogenic minerals. For example, microscopic particles of silica called phytoliths can be found in grasses and other plants. Silica is an amorphous metal oxide formed by complex inorganic polymerization processes. This is opposed to the other major biogenic minerals, comprising carbonate and phosphate, which occur in nature as crystalline iono-covalent solids (e.g. salts) whose precipitation is dictated by solubility equilibria.〔Coradin, T., Lopez, P.J. (2003). "Biogenic Silica Patterning: Simple Chemistry or Subtle Biology?" ChemBioChem 3: 1-9.〕 Chemically, bSi is hydrated silica (SiO2·''n''H2O), which is essential to many plants and animals.
==Silica in marine environments==
Silicate, or silicic acid (H4SiO4), is an important nutrient in the ocean. Unlike the other major nutrients such as phosphate, nitrate, or ammonium, which are needed by almost all marine plankton, silicate is an essential chemical requirement for very specific biota, including diatoms, radiolaria, silicoflagellates, and siliceous sponges. These organisms extract dissolved silicate from open ocean surface waters for the buildup of their particulate silica (SiO2), or opaline, skeletal structures (i.e. the biota’s hard parts).〔Boggs, S. (2005). "Principles of Sedimentology and Stratigraphy (4th Edition)". Pearson Education, Inc, 662p.〕〔DeMaster, D.J. (1981)."The supply and accumulation of silica in the marine environment". Geochimica et Cosmochimica Acta 45: 1715-1732.〕 Some of the most common siliceous structures observed at the cell surface of silica-secreting organisms include: spicules, scales, solid plates, granules, frustules, and other elaborate geometric forms, depending on the species considered.〔Ehrlich et al. (2010). "Modern Views on Desilicification: Biosilica and Abiotic Silica Dissolution in Natural and Artificial Environments ". Chem. Rev. 110: 4656-4689.〕
Five major sources of dissolved silica to the marine environment can be distinguished:〔
* Riverine influx of dissolved silica to the oceans: 4.2 ± 0.8 × 1014 g SiO2 yr−1
* Submarine volcanism and associated hydrothermal emanations: 1.9 ± 1.0 × 1014 g SiO2 yr−1
* Glacial weathering: 2 × 1012 g SiO2 yr−1
* Low temperature submarine weathering of oceanic basalts
* Some silica may also escape from silica-enriched pore waters of pelagic sediments on the seafloor
Once the organism has perished, part of the siliceous skeletal material dissolves, as it settles through the water column, enriching the deep waters with dissolved silica.〔 Some of the siliceous scales can also be preserved over time as microfossils in deep-sea sediments, providing a window into modern and ancient plankton/protists communities.〔 This biologic process has operated, since at least early Paleozoic time, to regulate the balance of silica in the ocean: Radiolarians (Cambrian/Ordovician-Holocene), diatoms (Cretaceous-Holocene), and silicoflagellates (Cretaceous-Holocene) form the ocean’s main contributors to the global silica biogenic cycle throughout geologic time. Diatoms account for 43% of the ocean primary production, and are responsible for the bulk of silica extraction from ocean waters in the modern ocean, and during much of the past fifty million years. In contrast, oceans of Jurassic and older ages, were characterized by radiolarians as major silica-utilizing phyla.〔 Nowadays, radiolarians are the second (after diatoms) major producers of suspended amorphous silica in ocean waters. Their distribution ranges from the Arctic to the Antarctic, being most abundant in the equatorial zone. In equatorial Pacific waters, for example, about 16,000 specimens per cubic meter can be observed.〔
Silicate cycling gained increasingly in scientific attention the past decade because of following reasons. Firstly, the modern marine silica cycle is widely believed to be dominated by diatoms for the fixation and export of particulate matter (including organic carbon), from the euphotic zone to the deep ocean, via a process known as the biological pump. As a result, diatoms, and other silica-secreting organisms, play a crucial role in the global carbon cycle, and have the ability to affect atmospheric CO2 concentrations on a variety of time scales, by sequestering CO2 in the ocean. This connection between ''biogenic silica'' and organic carbon, together with the significantly higher preservation potential of biogenic siliceous compounds, compared to organic carbon, makes opal accumulation records very interesting for paleoceanography and paleoclimatology. Secondly, biogenic silica accumulation on the sea floor contains lot of information about where in the ocean export production has occurred on time scales ranging from hundreds to millions of years. For this reason, opal deposition records provide valuable information regarding large-scale oceanographic reorganizations in the geological past, as well as paleoproductivity. At last, the mean oceanic residence time for silicate is approximately 10,000–15,000 yr. This relative short residence time, makes oceanic silicate concentrations and fluxes sensitive to glacial/interglacial perturbations, and thus an excellent proxy for evaluating climate changes.〔〔Cortese, G., Gersonde, R. (2004). "Opal sedimentation shifts in the World Ocean over the last 15 Myr". Earth and Planetary Science Letters 224: 509-527.〕
The remains of diatoms and other silica-utilizing organisms are found, as opal sediments within pelagic deep-sea deposits. Pelagic sediments, containing significant quantities of siliceous biogenic remains, are commonly referred to as siliceous ooze. Siliceous ooze are particularly abundant in the modern ocean at high latitudes in the northern and southern hemispheres. A striking feature of siliceous ooze distribution is a ca. 200 km wide belt stretching across the Southern Ocean. Some equatorial regions of upwelling, where nutrients are abundant and productivity is high, are also characterized by local siliceous ooze. Siliceous oozes are composed primarily of the remains of diatoms and radiolarians, but may also include other siliceous organisms, such as silicoflagellates and sponge spicules. Diatom ooze occurs mainly in high-latitude areas and along some continental margins, whereas radiolarian ooze are more characteristic of equatorial areas. Siliceous ooze are modified and transformed during burial into bedded cherts.〔
Diatoms in both fresh and salt water extract silica from the water to use as a component of their cell walls. Likewise, some holoplanktonic protozoa (Radiolaria), some sponges, and some plants (leaf phytoliths) use silicon as a structural material. Silicon is known to be required by chicks and rats for growth and skeletal development. Silicon is in human connective tissues, bones, teeth, skin, eyes, glands and organs.
BSi is silica that originates from the production out of dissolved silica. BSi can either be accumulated "directly" in marine sediments (via export) or be transferred back into dissolved silica in the water column.
Increasingly, isotope ratios of oxygen (O18:O16) and silicon (Si30:Si28) are analysed from BSi preserved in lake and marine sediments to derive records of past climate change and nutrient cycling (De La Rocha, 2006; Leng and Barker, 2006). This is a particularly valuable approach considering the role of diatoms in global carbon cycling. In addition, isotope analyses from BSi are useful for tracing past climate changes in regions such as in the Southern Ocean, where few biogenic carbonates are preserved.

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