Terrestrial ecosystems and the global biogeochemical silica cycle Daniel J.

Conley Department of Marine Ecology, National Environmental Research Institute, Roskilde, Denmark Most research on the global Si cycle has focused nearly exclusively on weathering or the oceanic Si cycle and has not explored the complexity of the terrestrial biogeochemical cycle. The global biogeochemical Si cycle is of great interest because of its impact on global CO2 concentrations through the combined processes of weathering of silicate minerals and transfer of CO2 from the atmosphere to the lithosphere. A sizable pool of Si is contained as accumulations of amorphous silica, or biogenic silica (BSi), in living tissues of growing plants, known as phytoliths, and, after decomposition of organic material, as remains in the soil. The annual fixation of phytolith silica ranges from 60–200 Tmol yr−1 and rivals that fixed in the oceanic biogeochemical cycle (240 Tmol yr−1). Internal recycling of the phytolith pool is intense with riverine fluxes of dissolved silicate to the oceans buffered by the terrestrial biogeochemical Si cycle, challenging the ability of weathering models to predict rates of weathering and consequently, changes in global climate. Consideration must be given to the influence of the terrestrial BSi pool on variations in the global biogeochemical Si cycle over geologic time and the influence man has had on modifying both the terrestrial and aquatic biogeochemical cycles. The silicon cycle Introduction The cycle of silicon (Si) cycle differs from the cycles of carbon, nitrogen and sulphur in that silicon does not have a gaseous phase. Furthermore, the solubility of silicon compounds in water is limited so most silicon is found in sedimentary or particulate form. Geochemical reactions are the main processes responsible for the formation of silicate rocks and their dissolution. Once in solution, however, silicon is cycled by biological activity. Silicon weathering in rocks and soil The earth is differentiated into the core, mantle and crust. The core is made up of the heavy elements, iron and nickel. The mantle forms a semifluid layer of less dense minerals with the composition of perovskite (Mg SiO3) and olivine (FeMgSiO4) while the crust, made up of lower density aluminosilicate minerals, 'floats' on the mantle. Although the Earth as a whole has a large iron component (35%), the composition of the crust is quite different with 28% silicon. In order to become available for biological activity, the silicate rocks must be broken down. This is achieved by weathering which may be (a) mechanical (physical processes of wind or ice) or (b) chemical (reaction with acidic and oxidising substances). The rate of chemical

are most susceptible to weathering. They promote weathering due to increased acidity and also by a process called chelation in which they combine with products of weathering to prevent the development of an equilibrium between dissolved products and mineral elements. 2NaAlSi3O8 + 2H2CO3 + 9H2O --> 2Na+ + 2HCO3.the ferromagnesian and the felsic series. The iron precipitates in the soil while the magnesium and silica are lost in runoff. Chemical reactions are generally accelerated by high temperature and precipitation such that weathering decreases from tropical forests > temperate forests > grasslands > deserts 2. if forms a second mineral with slightly higher resistance to weathering due to increased linkages between the crystals. 1. Consequently. An example of carbonic acid attack on silicate rock is weathering of the primary mineral Nafeldspar to the secondary mineral kaolinite with the loss of sodium and soluble silica (silicic acid). Looking at the concentrations of major elements in the continents and rivers indicates the large amount of silicon in rocks and soil.+ Al2Si2O5(OH)4 + 4H4SiO4 (The dominance of the bicarbonate anion in runoff indicates carbonation weathering. Remember that plant roots and soil microbes release CO2 into the air spaces in the soil leading to elevated concentrations of carbonic acid and increased weathering. fulvic. Minerals in each series that are found as isolated crystal units. of magnesium or aluminium in their crystalline structure. The dominant form of weathering is the carbonation reaction involving carbonic acid. The rate at which elements may be mobilised . Alternatively. olivine (FeMgSiO4) undergoes congruent dissolution in water to release Fe. such as Olivine and Ca-Feldspar. Mg and Si. this is called incongruent dissolution and further weathering will lead to the loss of more soluble silica. humic. Igneous and metamorphic rocks contain primary silicate minerals formed under high temperature and pressure deep in the earth. Both the ferromagnesian and felsic weathering series terminate in Quartz Si4O8 which has tetrahedral crystals linked in 3 dimensions and is therefore very resistant to chemical weathering. whereas carbonic acid drives chemical weathering in tropical forests where lower concentrations of fulvic acid remain after the decomposition of plant litter. microbes and fungi eg acetic. phenolic and oxalic. They are found in two classes . citric. Organic acids dominate weathering in cool temperate forests where decomposition processes are slow and incomplete. Organic acids dominate the acidity of the upper part of a soil profile while carbonic acid is important below. Acidity can also be increased in the soil by a range of organic acids released by plant roots.weathering varies with the (1) physical conditions of temperature and rainfall and (2) the mineral composition of the rocks. respectively. Therefore organisms exert biotic control over the geochemical process of rock weathering.) Because only some of the constituents are lost. As a mineral is weathered. chemical weathering during soil development leads to the loss of other constituents and the accumulation of quartz in the sand fraction. depending on the presence.

The sedimentary silicon distribution reflects the rate at which silica rains down onto the seafloor. opal. its degree of preservation and the rate of accumulation of other particles. Fossil evidence suggests that they originated during. and are one of the most common types of phytoplankton. including the minerals. This article focuses mainly on the Si-O anions. After death the siliceous cell walls (frustules) sink towards the seafloor but the rate of dissolution is slow. and thousands of minerals are examples of silicates. The silica signal in coastal upwelling and continental shelf regions is diluted by other particles. and each can form compounds .through weathering varies: Ca>Na>Mg>K>Si>Fe>Al>P as elements become less soluble and form more precipitates. and are commonly used in studies of water quality. Diatoms are producers within the food chain. Sediments with a high silion content are observed beneath the Equatorial Pacific upwelling region. Silicates comprise the majority of the earth's crust. The availability of dissolved silica varies geographically with high concentrations in upwelling regions of the oceans. or before. the Bering Sea and the subpolar Southern Ocean. Most diatoms are unicellular. past and present. as well as the other terrestrial planets.g. the early Jurassic Period. zigzags (e. Portland cement. These frustules show a wide diversity in form. but hexafluorosilicate ([SiF6]2−) and other anions are also included. In the oceans. especially in the cold depths. Meridion). Silicate compounds. diatom uptake maintains low concentrations of silicic acid (also called 'silicate' or 'dissolved silica') in surface waters as a result of the production of biogenic silica (opal).g. although they can exist as colonies in the shape of filaments or ribbons (e.g. A silicate is a compound containing a silicon bearing anion. Diatom communities are a popular tool for monitoring environmental conditions.g. For example. Fragillaria). Phytoplankton species composition varies according to nutrient availability adding P to a nutrient poor lake stimulates diatom growth which may deplete Si supply and favour a shift to other plankton species such as green algae. hence the group name. A characteristic feature of diatom cells is that they are encased within a unique cell wall made of silica (hydrated silicon dioxide) called a frustule. lakes and the ocean The silicon in freshwater and oceanic systems is taken up by diatoms. which are relatively large phytoplankters. Myriad silicate anions can exist. Diatoms[1] are a major group of algae. consist of silicate anions whose charge is balanced by various cations. rocky moons. and asteroids. Diatom species dominance is also susceptible to the Si concentration so subtle shifts in the biogeochemistry of the environment can alter the distribution and abundance of species and the productivity of a natural ecosystem. Asterionella). but usually consist of two asymmetrical sides with a split between them. Silicon in rivers. Sand. fans (e. They incorporate it into their cell wall (frustule) in the form of the mineral. Tabellaria). so most regeneration is at the seafloor where a substantial fraction is also buried. variations in the Si:P ratio are thought to control the relative dominance of the diatom genera Asterionella and Cyclotella in lakes. The great majority of silicates are oxides. or stellate colonies (e.

solutions of silicates usually observed as mixtures of condensed and partially protonated silicate clusters. Instead. and both are elusive as are all of the intermediate species. The anion SiO44. such as the industrially important catalysts called zeolites. double chains. the tetrahedra are joined together in various ways. Hence this class of compounds is very large. but most commonly.centres. Commonly the silicate anions are chains. sheets. even SiO2 adopts this geometry in the mineral stishovite. [edit]Occurrence in solution Main article: Sodium silicate Silicates are well characterized as solids. a dense polymorph of silica found in the lower mantle of the Earth.with many different cations. These tetrahedra sometimes occur as isolated SiO44. Structural principles In the vast majority of silicates. silicon is well known to also adopt higher coordination numbers. Octahedral coordination by 6 oxygen centres is observed. Both minerals and synthetic materials fit in this class. being surrounded by 4 oxygen centres. and three-dimensional frameworks. In these structures.[1] [edit]Silicates with non-tetrahedral silicon Although the tetrahedron is the common coordination geometry for silicon compounds. At very high pressure. All such species have negligible solubility in water at normal conditions. Si(OH)4. the chemical bonds to silicon conform to the octet rule. but are less commonly observed in solution. . including silicate minerals. such as pairs (Si2O76-) and rings (Si6O1812-). The nature of soluble silicates is relevant to understanding biomineralization and the synthesis of aluminosilicates. A well known example of such a high coordination number is hexafluorosilicate (SiF62-). Octahedral Si in the form of hexahydroxysilicate ([Si(OH)6]2−) is observed in thaumasite[citation needed] a mineral occurring rarely in nature but sometimes observed amongst other calcium silicate hydrate artificially formed in cement andconcrete submitted to a severe sulfate attack.is the conjugate base of silicic acid. the Si occupies a tetrahedral environment. This structure is also formed by shock during meteorite impacts.

69mm. melilite group.[SinO3n]2n−. Cyclosilicates (rings) . crystallization.236 pixels/μm. amphibole group.13 by 0. e. is a soft. metamorphism. sedimentary rock made up of the frustules(shells) of single cell diatoms. weathering and diagenesis. a wide variety of silicate minerals occur in an even wider range of combinations as a result of the processes that form and re-work the crust. Inosilicates (single chain) . On Earth. . [edit]Mineralogy Mineralogically.g. known as tests. SiO2. e. Silica. tourmaline group. from silica. Living things also contribute to the silicate cycle near the Earth's surface. or silicon dioxide.[SinO3n]2n−. is sometimes considered a silicate. siliceous.g. Silica is found in nature as the mineral quartz. These processes include partial melting. e. although it is the special case with no negative charge and no need for counter-ions. fractionation. Main article: Silicate minerals In geology and astronomy. pyroxene group. silica synthesised in the diatom cell by thepolymerisation of silicic acid.g. A type of plankton known as diatoms construct theirexoskeletons. and its polymorphs. epidote. silicate minerals are divided according to structure of their silicate anion into the following groups:[2][3]      Nesosilicates (lone tetrahedron) .Silicate rock and minerals Diatomaceous earth. the entire image covers a region of approximately 1. e. e.[SiO4]4−. as viewed under a microscope. Sorosilicates (double tetrahedra) .g. This image of diatomaceous earth particles in water is at a scale of 6.g. The tests of dead diatoms are a major constituent of deep ocean sediment.[Si2O7]6−. the term silicate is used to denote types of rock that consist predominantly of silicate minerals.[Si4nO11n]6n−. Diatom cell walls are made up of biogenic silica. olivine. Inosilicates(double chain) .

Balec.1002/anie. ^ Hurlbut. doi:10.A. 3. feldspars. London: Longman IS 2. but these sediments are converted back to silicates during the subduction process. so Venus now has a high-density carbon dioxide atmosphere. ISBN ISBN 0-471-80580-7 The carbonate-silicate geochemical cycle[1][2] is the naturally occurring reversible chemical reaction with summary equation CaSiO3+CO2<=>CaCO3+SiO2. 1.g. Therefore.g. W.A. Kinrade "The Structure of Silicate Anions in Aqueous Alkaline Solutions" Angewandte Chemie International Edition 2007.. Klein. ^ Deer.Rivers carry dissolved materials to the ocean. Raymond J. 5. Equilibrium of the carbonate-silicate reaction is generally shifted in the favor of carbonate formation under near surface temperature and pressure conditions. (1992). Note that tectosilicates can only have additional cations if some of the silicon is replaced by a lower-charge cation such as aluminium. perhaps in subduction zones. J. R.[AlxSiyO2(x+y)]x−. Cornelis (1985).Precipitation of calcium carbonate and silica occurs when the ocean becomes supersaturated. Al for Si substitution is common.200702986 1. 4.[3] This process is far from being aclosed loop. Wiley. Pages 8148 -8152. The carbonate-silicate cycle is suspected as a reason for the ice ages. e. Stephen D. Volume 46. 2. Knight. in Earth history generally the formation of carbonates significantly outpaces formation of silicates. e. which effectively counterswater vapor and carbon dioxide short-term positive feedback. & Zussman. [edit]References ^ Christopher T. G. at the Earth's surface silicates are converted to carbonate sediments. zeolites. Tectosilicates (3D framework) . Manual of Mineralogy. because it can create negative feedback on the global temperature with a typical time scale of a few million years.  Phyllosilicates (sheets) .. but shifts to silicate formation at temperatures above 300 °C.Metamorphism occurs as sediments are deeply buried. Howie. micas and clays.). quartz. also these compounds are also extracted by marine organisms to make shells which also settle to the bottom.Carbonic acid breaks down silicate rock during weathering..[Si2nO5n]2n−. Cornelius S. (20th edition ed. An introduction to the rock forming minerals (2nd edition ed. During .Carbon dioxide dissolves in water to form carbonic acid.). The situation is opposite for Venusdue to higher temperatures. effectively dissipating primordial carbon dioxide rich atmosphere.

The concentrations of both nutrients are homeostatically controlled by the phytoplankton. While theoretically superior. notably their high sinking rates. with silicic acid abundance controlling the fraction of the total produced by diatoms. silicate materials are reformed and carbon dioxide is released through volcanoes. allowing the persistence and numerical dominance of the other algae. make them important to the export flux of carbon into the ocean interior. The model agrees reasonably with observed distributions of nutrients and with their biogeochemical fluxes... The role of diatoms in regulating the ocean's silicate cycle Among phytoplankton the diatoms are strong competitors and contribute significantly to total global primary production. Analysis finds that primary production in the model is ultimately controlled by phosphate. they utilize silicic acid (=silicate) to construct their cell walls and are controlled by its availability and distribution. Aspects of their life history. 1998] is also examined. . Unlike the majority of other phytoplankton. the diatoms are held in check by the availability of silicic acid.metamorphism. The model's treatment of the “silica pump" hypothesis [Dugdale and Wilkerson. Sensitivity analyses using more ecologically detailed variants of the model find that these results are generally robust. and resist perturbations.

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