Silicification
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In geology, silicification is a process in which
silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is one of the most complex and abundant f ...
-rich fluids seep into the voids of Earth materials, e.g., rocks, wood, bones, shells, and replace the original materials with silica (SiO2). Silica is a naturally existing and abundant compound found in organic and
inorganic An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemistry''. Inor ...
materials, including Earth's crust and mantle. There are a variety of silicification mechanisms. In silicification of wood, silica permeates into and occupies cracks and voids in wood such as vessels and cell walls. The original organic matter is retained throughout the process and will gradually decay through time. In the silicification of carbonates, silica replaces carbonates by the same volume. Replacement is accomplished through the dissolution of original rock minerals and the
precipitation In meteorology, precipitation is any product of the condensation of atmospheric water vapor that falls from clouds due to gravitational pull. The main forms of precipitation include drizzle, rain, rain and snow mixed ("sleet" in Commonwe ...
of silica. This leads to a removal of original materials out of the system. Depending on the structures and composition of the original rock, silica might replace only specific mineral components of the rock. Silicic acid (H4SiO4) in the silica-enriched fluids forms lenticular, nodular, fibrous, or aggregated
quartz Quartz is a hard, crystalline mineral composed of silica (silicon dioxide). The Atom, atoms are linked in a continuous framework of SiO4 silicon–oxygen Tetrahedral molecular geometry, tetrahedra, with each oxygen being shared between two tet ...
,
opal Opal is a hydrated amorphous form of silicon dioxide, silica (SiO2·''n''H2O); its water content may range from 3% to 21% by weight, but is usually between 6% and 10%. Due to the amorphous (chemical) physical structure, it is classified as a ...
, or
chalcedony Chalcedony ( or ) is a cryptocrystalline form of silica, composed of very fine intergrowths of quartz and moganite. These are both silica minerals, but they differ in that quartz has a trigonal crystal structure, while moganite is monoclinic ...
that grows within the rock. Silicification happens when rocks or organic materials are in contact with silica-rich surface water, buried under
sediment Sediment is a solid material that is transported to a new location where it is deposited. It occurs naturally and, through the processes of weathering and erosion, is broken down and subsequently sediment transport, transported by the action of ...
s and susceptible to
groundwater Groundwater is the water present beneath Earth's surface in rock and Pore space in soil, soil pore spaces and in the fractures of stratum, rock formations. About 30 percent of all readily available fresh water in the world is groundwater. A unit ...
flow, or buried under volcanic ashes. Silicification is often associated with
hydrothermal Hydrothermal circulation in its most general sense is the circulation of hot water (Ancient Greek ὕδωρ, ''water'',Liddell, H.G. & Scott, R. (1940). ''A Greek-English Lexicon. revised and augmented throughout by Sir Henry Stuart Jones. with th ...
processes. Temperature for silicification ranges in various conditions: in burial or surface water conditions, temperature for silicification can be around 25°−50°; whereas temperatures for siliceous fluid inclusions can be up to 150°−190°. Silicification could occur during a syn- depositional or a post-depositional stage, commonly along layers marking changes in
sedimentation Sedimentation is the deposition of sediments. It takes place when particles in suspension settle out of the fluid in which they are entrained and come to rest against a barrier. This is due to their motion through the fluid in response to th ...
such as
unconformities An unconformity is a buried erosion surface, erosional or non-depositional surface separating two Rock (geology), rock masses or Stratum, strata of different ages, indicating that sediment deposition was not continuous. In general, the older layer ...
or bedding planes.


Sources of silica

The sources of silica can be divided into two categories: silica in organic and inorganic materials. The former category is also known as biogenic silica, which is a ubiquitous material in animals and plants. The latter category is the second most abundant element in Earth's crust.
Silicate mineral Silicate minerals are rock-forming minerals made up of silicate groups. They are the largest and most important class of minerals and make up approximately 90 percent of Earth's crust. In mineralogy, the crystalline forms of silica (silicon dio ...
s are the major components of 95% of presently identified rocks.


Biology

Biogenic silica is the major source of silica for diagenesis. One of the prominent examples is the presence of silica in
phytolith Phytoliths (from Greek language, Greek, "plant stone") are rigid, microscopic mineral deposits found in some plant tissues, often persisting after the decay of the plant. Although some use "phytolith" to refer to all mineral secretions by plants, ...
s in the leaves of plants, i.e. grasses, and Equisetaceae. Some suggested that silica present in phytoliths can serve as a defense mechanism against the herbivores, where the presence of silica in leaves increases the difficulty in digestion, harming the fitness of herbivores. However, evidence on the effects of silica on the wellbeing of animals and plants is still insufficient. Besides,
sponge Sponges or sea sponges are primarily marine invertebrates of the animal phylum Porifera (; meaning 'pore bearer'), a basal clade and a sister taxon of the diploblasts. They are sessile filter feeders that are bound to the seabed, and a ...
s are another biogenic source of naturally occurring silica in animals. They belong to the
phylum In biology, a phylum (; : phyla) is a level of classification, or taxonomic rank, that is below Kingdom (biology), kingdom and above Class (biology), class. Traditionally, in botany the term division (taxonomy), division has been used instead ...
Porifera Sponges or sea sponges are primarily marine invertebrates of the animal phylum Porifera (; meaning 'pore bearer'), a Basal (phylogenetics) , basal clade and a sister taxon of the Eumetazoa , diploblasts. They are sessility (motility) , sessile ...
in the classification system. Silicious sponges are commonly found with silicified sedimentary layers, for example in the Yanjiahe Formation in South China. Some of them occur as
sponge spicule Spicules are structural elements found in most sponges. The meshing of many spicules serves as the sponge's skeleton and thus it provides structural support and potentially defense against predators. Sponge spicules are made of calcium carbo ...
s and are associated with microcrystalline quartz or other carbonates after silicification. It could also be the main source of precipitative beds such as cherts beds or cherts in petrified woods.
Diatom A diatom (Neo-Latin ''diatoma'') is any member of a large group comprising several Genus, genera of algae, specifically microalgae, found in the oceans, waterways and soils of the world. Living diatoms make up a significant portion of Earth's B ...
s, an important group of
microalgae Microalgae or microphytes are microscopic scale, microscopic algae invisible to the naked eye. They are phytoplankton typically found in freshwater and marine life, marine systems, living in both the water column and sediment. They are unicellul ...
living in marine environments, contribute significantly to the source of diagenetic silica. They have cell walls made of silica, also known as diatom frustules. In some silicified sedimentary rocks, fossils of diatoms are unearthed. This suggests that diatoms frustules were sources of silica for silicification. Some examples are silicified limestones of
Miocene The Miocene ( ) is the first epoch (geology), geological epoch of the Neogene Period and extends from about (Ma). The Miocene was named by Scottish geologist Charles Lyell; the name comes from the Greek words (', "less") and (', "new") and mea ...
Astoria Formation in Washington, silicified
ignimbrite Ignimbrite is a type of volcanic rock, consisting of hardened tuff. Ignimbrites form from the deposits of pyroclastic flows, which are a hot suspension of particles and gases flowing rapidly from a volcano, driven by being denser than the surrou ...
in El Tatio Geyser Field in Chile, and Tertiary siliceous sedimentary rocks in western pacific deep sea drills. The presence of biogenic silica in various species creates a large-scale marine silica cycle that circulates silica through the ocean. Silica content is therefore high in active silica upwelling areas in the deep-marine sediments. Besides, carbonate shells that deposited in shallow marine environments enrich silica contents at
continental shelf A continental shelf is a portion of a continent that is submerged under an area of relatively shallow water, known as a shelf sea. Much of these shelves were exposed by drops in sea level during glacial periods. The shelf surrounding an islan ...
areas.


Geology

The major component of the Earth's
upper mantle The upper mantle of Earth is a very thick layer of rock inside the planet, which begins just beneath the crust (geology), crust (at about under the oceans and about under the continents) and ends at the top of the lower mantle (Earth), lower man ...
is silica (SiO2), which makes it the primary source of silica in hydrothermal fluids. SiO2 is a stable component. It often appears as quartz in
volcanic rock Volcanic rocks (often shortened to volcanics in scientific contexts) are rocks formed from lava erupted from a volcano. Like all rock types, the concept of volcanic rock is artificial, and in nature volcanic rocks grade into hypabyssal and me ...
s. Some quartz that is derived from pre-existing rocks, appear in the form of sand and detrital quartz that interact with seawater to produce siliceous fluids. In some cases, silica in siliceous rocks are subjected to
hydrothermal alteration Metasomatism (from the Greek μετά ''metá'' "change" and σῶμα ''sôma'' "body") is the chemical alteration of a Rock (geology), rock by hydrothermal and other fluids. It is traditionally defined as metamorphism which involves a change in t ...
and react with seawater at certain temperatures, forming an acidic solution for silicification of nearby materials. In the
rock cycle The ''rock cycle'' is a basic concept in geology that describes transitions through geologic time among the three main rock types: sedimentary, metamorphic, and igneous. Each rock type is altered when it is forced out of its equilibrium cond ...
, the chemical weathering of rocks also releases silica in the form of silicic acid as
by-product A by-product or byproduct is a secondary product derived from a production process, manufacturing process or chemical reaction; it is not the primary product or service being produced. A by-product can be useful and marketable or it can be cons ...
s. Silica from weathered rocks is washed into waters and deposit into shallow-marine environments.


Mechanisms of silicification

The presence of hydrothermal fluids is essential as a medium for geochemical reactions during silicification. In the silicification of different materials, different mechanisms are involved. In the silicification of rock materials like carbonates, replacement of minerals through hydrothermal alteration is common; while the silicification of organic materials such as woods is solely a process of permeation.


Replacement

The replacement of silica involves two processes: 1) Dissolution of rock minerals 2) Precipitation of silica It could be explained through the carbonate-silica replacement. Hydrothermal fluids are undersaturated with carbonates and
supersaturated In physical chemistry, supersaturation occurs with a solution when the concentration of a solute exceeds the concentration specified by the value of solubility at equilibrium. Most commonly the term is applied to a solution of a solid in a ...
with silica. When carbonate rocks get in contact with hydrothermal fluids, due to the difference in gradient, carbonates from the original rock dissolve into the fluid whereas silica
precipitate In an aqueous solution, precipitation is the "sedimentation of a solid material (a precipitate) from a liquid solution". The solid formed is called the precipitate. In case of an inorganic chemical reaction leading to precipitation, the chemic ...
out of it. The carbonate that dissolved is therefore pulled out from the system while the silica precipitated recrystallizes into various silicate minerals, depending on the silica phase. The
solubility In chemistry, solubility is the ability of a chemical substance, substance, the solute, to form a solution (chemistry), solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form su ...
of silica strongly depends on the temperature and pH value of the environment where pH9 is the controlling value. Under a condition of pH lower than 9, silica precipitates out of the fluid; when the pH value is above 9, silica becomes highly soluble.


Permeation

In the silicification of woods, silica dissolves in hydrothermal fluid and seeps into
lignin Lignin is a class of complex organic polymers that form key structural materials in the support tissues of most plants. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidit ...
in cell walls. Precipitation of silica out of the fluids produces silica deposition within the voids, especially in the cell walls. Cell materials are broken down by the fluids, yet the structure remains stable due to the development of minerals. Cell structures are slowly replaced by silica. Continuous penetration of siliceous fluids results in different stages of silicification i.e. primary and secondary. The loss of fluids over time leads to the cementation of silicified woods through late silica addition. The rate of silicification depends on a few factors: 1) Rate of breakage of original cells 2) Availability of silica sources and silica content in the fluid 3) Temperature and pH of silicification environment 4) Interference of other diagenetic processes These factors affect the silicification process in many ways. The rate of breakage of original cells controls the development of the mineral framework, hence the replacement of silica. Availability of silica directly determines the silica content in fluids. The higher the silica content, the faster silicification could take place. The same concept applies to the availability of hydrothermal fluids. The temperature and pH of the environment determine the condition for silicification to occur. This is closely connected to the burial depth or association with volcanic events. Interference of other diagenetic processes could sometimes create disturbance to silicification. The relative time of silicification to other geological processes could serve as a reference for further geological interpretations.


Examples


Volcanic rocks

In the Conception Bay in Newfoundland, Southeastern coast of Canada, a series of Pre-Cambrian to Cambrian-linked volcanic rocks were silicified. The rocks mainly consist of rhyolitic and basaltic flows, with crystal tuffs and breccia interbedded. Regional silicification was taken place as a preliminary alteration process before other geochemical processes occurred. The source of silica near the area was from hot siliceous fluids from rhyolitic flow under a static condition. A significant portion of silica appeared in the form of white chalcedonic quartz, quartz veins as well as granular quartz crystal. Due to the difference in rock structures, silica replaces different materials in rocks of close locations. The following table shows the replacement of silica at different localities:


Metamorphic rocks

In the Semail Nappe of Oman in the United Arb Emirates, silicified
serpentinite Serpentinite is a metamorphic rock composed predominantly of serpentine group minerals formed by serpentinization of mafic or ultramafic rocks. The ancient origin of the name is uncertain; it may be from the similarity of its texture or color ...
was found. The occurrence of such geological features is rather unusual. It is a pseudomorphic alteration where the protolith of serpentinite was already silicified. Due to tectonic events, basal serpentinite was fractured and groundwater permeated along the faults, forming a large-scale circulation of groundwater within the strata. Through hydrothermal dissolution, silica precipitated and crystallized around the voids of serpentinite. Therefore, silicification can only be seen along groundwater paths. The silicification of serpentinite was formed under the condition where groundwater flow and carbon dioxide concentration are low.


Carbonates

Silicified carbonates can appear as silicified carbonate rock layers, or in the form of silicified karsts. The
Paleogene The Paleogene Period ( ; also spelled Palaeogene or Palæogene) is a geologic period and system that spans 43 million years from the end of the Cretaceous Period Ma (million years ago) to the beginning of the Neogene Period Ma. It is the fir ...
Madrid Basin in Central Spain is a foreland basin resulted from the Alpine uplift, an example of silicified carbonates in rock layers. The lithology consists of carbonate and detritus units that were formed in a lacustrine environment. The rock units are silicified where cherts, quartz, and opaline minerals are found in the layers. It is conformable with the underlying evaporitic beds, also dated from similar ages. It is found that there were two stages of silicification within the rock strata. The earlier stage of silicification provided a better condition and site for the precipitation of silica. The source of silica is still uncertain. There are no biogenic silica detected from the carbonates. However, microbial films in carbonates are found, which could suggest the presence of diatoms.
Karst Karst () is a topography formed from the dissolution of soluble carbonate rocks such as limestone and Dolomite (rock), dolomite. It is characterized by features like poljes above and drainage systems with sinkholes and caves underground. Ther ...
s are carbonate caves formed from a dissolution of carbonate rocks such as
limestone Limestone is a type of carbonate rock, carbonate sedimentary rock which is the main source of the material Lime (material), lime. It is composed mostly of the minerals calcite and aragonite, which are different Polymorphism (materials science) ...
s and
dolomites The Dolomites ( ), also known as the Dolomite Mountains, Dolomite Alps or Dolomitic Alps, are a mountain range in northeastern Italy. They form part of the Southern Limestone Alps and extend from the River Adige in the west to the Piave Va ...
. They are usually susceptible to groundwater and are dissolved in these drainage. Silicified karsts and cave deposits are formed when siliceous fluids enter karsts through faults and cracks. The Mid-Proterozoic Mescal Limestone from the Apache Group in central Arizona is classic examples of silicified karsts. A portion of the carbonates are replaced by cherts in early diagenesis and the remaining portion is completely silicified in later stages. The source of silica in carbonates are usually associated with the presence of biogenetic silica; however, the source of silica in Mescal Limestone is from weathering of overlying
basalt Basalt (; ) is an aphanite, aphanitic (fine-grained) extrusive igneous rock formed from the rapid cooling of low-viscosity lava rich in magnesium and iron (mafic lava) exposed at or very near the planetary surface, surface of a terrestrial ...
s, which are extrusive
igneous rock Igneous rock ( ), or magmatic rock, is one of the three main rock types, the others being sedimentary and metamorphic. Igneous rocks are formed through the cooling and solidification of magma or lava. The magma can be derived from partial ...
s that have high silica content.


Silicified woods

Silicification of woods usually occur in terrestrial conditions, but sometimes it could be done in aquatic environments. Surface water silicification can be done through the precipitation of silica in silica-enriched hot springs. On the northern coast of central Japan, the Tateyama hot spring has a high silica content that contributes to the silicification of nearby fallen woods and organic materials. Silica precipitates rapidly out of the fluids and opal is the main form of silica. With a temperature of around 70 °C and a pH value of around 3, the opal deposited is composed of silica spheres of different sizes arranged randomly.


Early silicification

Mafic A mafic mineral or rock is a silicate mineral or igneous rock rich in magnesium and iron. Most mafic minerals are dark in color, and common rock-forming mafic minerals include olivine, pyroxene, amphibole, and biotite. Common mafic rocks include ...
magma dominated the seafloor at around 3.9 Ga during the
Hadean The Hadean ( ) is the first and oldest of the four geologic eons of Earth's history, starting with the planet's formation about 4.6  billion years ago (estimated 4567.30 ± 0.16 million years ago set by the age of the oldest solid material ...
-
Archean The Archean ( , also spelled Archaean or Archæan), in older sources sometimes called the Archaeozoic, is the second of the four geologic eons of Earth's history of Earth, history, preceded by the Hadean Eon and followed by the Proterozoic and t ...
transition. Due to rapid silicification, the
felsic In geology, felsic is a grammatical modifier, modifier describing igneous rocks that are relatively rich in elements that form feldspar and quartz.Marshak, Stephen, 2009, ''Essentials of Geology,'' W. W. Norton & Company, 3rd ed. It is contrasted ...
continental crust Continental crust is the layer of igneous, metamorphic, and sedimentary rocks that forms the geological continents and the areas of shallow seabed close to their shores, known as '' continental shelves''. This layer is sometimes called '' si ...
began to form. In the Archean, the continental crust was composed of tonalite–trondhjemite–granodiorite (TTG) as well as granite–
monzonite Monzonite is an igneous intrusive rock, formed by slow cooling of underground magma that has a moderate silica content and is enriched in alkali metal oxides. Monzonite is composed mostly of plagioclase and alkali feldspar. Syenodiorite is an ...
syenite suites. The Mount Goldsworthy in the Pilbara Craton located in Western Australia holds one of the earliest silicification example with an Archean clastic meta-sedimentary rock sequence, revealing the surface environment of the Earth in the early times with evidence from silicification and hydrothermal alteration. The unearthed rocks are found to be SiO2 dominant in terms of mineral composition. The succession was subjected to a high degree of silicification due to hydrothermal interaction with seawater at low temperatures. Lithic fragments were replaced with microcrystalline quartz and
protolith A protolith () is the original, unmetamorphosed rock from which a given metamorphic rock is formed. For example, the protolith of a slate is a shale or mudstone. Metamorphic rocks can be derived from any other kind of non-metamorphic rock and ...
s were altered during silicification. The condition of silicification and the elements that were present suggested that the surface temperature and carbon dioxide contents were high during either or both syn-deposition and post-deposition. The Barberton Greenstone Belt in South Africa, specifically the Eswatini Supergroup of around 3.5–3.2 Ga, is a suite of well-preserved silicified volcanic-sedimentary rocks. With the composition ranging from ultramafic to felsic, the silicified volcanic rocks are directly beneath the bedded chert layer. Rocks are more silicified near the bedded chert contact, suggesting a relationship between chert deposition and silicification. The silica altered zones reveal that hydrothermal activities, as in seawater circulation, actively circulate the rock layers through fractures and fault during the deposition of bedded chert. The seawater was heated up and therefore picked up silicious materials from underneath volcanic origin. The silica enriched fluids bring about silicification of rocks through seeping into porous materials in the syn-depositional stage at a low-temperature condition.


See also

*
Metasomatism Metasomatism (from the Greek μετά ''metá'' "change" and σῶμα ''sôma'' "body") is the chemical alteration of a rock by hydrothermal and other fluids. It is traditionally defined as metamorphism which involves a change in the chemical com ...
*
Permineralization Permineralization is a process of fossilization of bones and tissues in which mineral deposits form internal Casting, casts of organisms. Carried by water, these minerals fill the spaces within organic tissue. Because of the nature of the casts, p ...
* Pseudomorph * Silica cycle


References

{{Reflist Sedimentary rocks Geochemical processes Silicate minerals