Serpentinization is a hydration and metamorphic transformation of ferromagnesian minerals, such as olivine and pyroxene, in mafic and ultramafic rock to produce serpentinite. [1] Minerals formed by serpentinization include the serpentine group minerals (antigorite, lizardite, chrysotile), brucite, talc, Ni-Fe alloys, and magnetite. [1] [2] The mineral alteration is particularly important at the sea floor at tectonic plate boundaries. [3] [4]
Serpentinization is a form of low-temperature (0 to ~600 °C) [5] metamorphism of ferromagnesian minerals in mafic and ultramafic rocks, such as dunite, harzburgite, or lherzolite. These are rocks low in silica and composed mostly of olivine ((Mg2+, Fe2+)2SiO4), pyroxene (XY(Si,Al)2O6), and chromite (approximately FeCr2O4). Serpentinization is driven largely by hydration and oxidation of olivine and pyroxene to serpentine group minerals (antigorite, lizardite, and chrysotile), brucite (Mg(OH)2), talc (Mg3Si4O10(OH)2), and magnetite (Fe3O4). [2] Under the unusual chemical conditions accompanying serpentinization, water is the oxidizing agent, and is itself reduced to hydrogen, H
2. This leads to further reactions that produce rare iron group native element minerals, such as awaruite (Ni
3Fe) and native iron; methane and other hydrocarbon compounds; and hydrogen sulfide. [1] [6]
During serpentinization, large amounts of water are absorbed into the rock, increasing the volume, reducing the density and destroying the original structure. [7] The density changes from 3.3 to 2.5 g/cm3 (0.119 to 0.090 lb/cu in) with a concurrent volume increase on the order of 30-40%. [8] The reaction is highly exothermic, releasing up to 40 kilojoules (9.6 kcal) per mole of water reacting with the rock, and rock temperatures can be raised by about 260 °C (500 °F), [9] [10] providing an energy source for formation of non-volcanic hydrothermal vents. [11] The hydrogen, methane, and hydrogen sulfide produced during serpentinization are released at these vents and provide energy sources for deep sea chemotroph microorganisms. [12] [9]
Olivine is a solid solution of forsterite, the magnesium endmember of (Mg2+, Fe2+)2SiO4, and fayalite, the iron endmember, with forsterite typically making up about 90% of the olivine in ultramafic rocks. [13] Serpentine can form from olivine via several reactions:
+ + 4 H 2O → | (Reaction 1a) |
+ → + | (Reaction 1b) |
Reaction 1a tightly binds silica, lowering its chemical activity to the lowest values seen in common rocks of the Earth's crust. [14] Serpentinization then continues through the hydration of olivine to yield serpentine and brucite (Reaction 1b). [15] The mixture of brucite and serpentine formed by Reaction 1b has the lowest silica activity in the serpentinite, so that the brucite phase is very important in understanding serpentinization. [14] However, the brucite is often blended in with the serpentine such that it is difficult to identify except with X-ray diffraction, and it is easily altered under surface weathering conditions. [16]
A similar suite of reactions involves pyroxene-group minerals:
+ + H 2O → | (Reaction 2a) |
+ 3 H 2O → + | (Reaction 2b) |
Reaction 2a quickly comes to a halt as silica becomes unavailable, and Reaction 2b takes over. [17] When olivine is abundant, silica activity drops low enough that talc begins to react with olivine:
+ + → | (Reaction 3) |
This reaction requires higher temperatures than those at which brucite forms. [16]
The final mineralogy depends both on rock and fluid compositions, temperature, and pressure. Antigorite forms in reactions at temperatures that can exceed 600 °C (1,112 °F) during metamorphism, and it is the serpentine group mineral stable at the highest temperatures. Lizardite and chrysotile can form at low temperatures very near the Earth's surface. [18]
Ultramafic rocks often contain calcium-rich pyroxene (diopside), which breaks down according to the reaction:
+ 6 H+ → + 3 Ca2+ + H 2O + | (Reaction 4) |
This raises both the pH, often to very high values, and the calcium content of the fluids involved in serpentinization. These fluids are highly reactive and may transport calcium and other elements into surrounding mafic rocks. Fluid reaction with these rocks may create metasomatic reaction zones enriched in calcium and depleted in silica, called rodingites. [19]
In most crustal rock, the chemical activity of oxygen is prevented from dropping to very low values by the fayalite-magnetite-quartz (FMQ) buffer. [20] The very low chemical activity of silica during serpentinization eliminates this buffer, allowing serpentinization to produce highly reducing conditions. [14] Under these conditions, water is capable of oxidizing ferrous (Fe2+
) ions in fayalite. The process is of interest because it generates hydrogen gas: [1] [21] [22]
+ → + + | (Reaction 5) |
However, studies of serpentinites suggest that iron minerals are first converted to ferroan brucite, that is, brucite containing Fe(OH)2, [23] which then undergoes the Schikorr reaction in the anaerobic conditions of serpentinization: [24] [25]
→ + + | (Reaction 6) |
Maximum reducing conditions, and the maximum rate of production of hydrogen, occur when the temperature of serpentinization is between 200 and 315 °C (392 and 599 °F) [26] and when fluids are carbonate undersaturated. [1] If the original ultramafic rock (the protolith ) is peridotite, which is rich in olivine, considerable magnetite and hydrogen are produced. When the protolith is pyroxenite, which contains more pyroxene than olivine, iron-rich talc is produced with no magnetite and only modest hydrogen production. Infiltration of silica-bearing fluids during serpentinization can suppress both the formation of brucite and the subsequent production of hydrogen. [27]
Chromite present in the protolith will be altered to chromium-rich magnetite at lower serpentinization temperatures. At higher temperatures, it will be altered to iron-rich chromite (ferrit-chromite). [28] During serpentinization, the rock is enriched in chlorine, boron, fluorine, and sulfur. Sulfur will be reduced to hydrogen sulfide and sulfide minerals, though significant quantities are incorporated into serpentine minerals, and some may later be reoxidized to sulfate minerals such as anhydrite. [29] The sulfides produced include nickel-rich sulfides, such as mackinawite. [30]
Laboratory experiments have confirmed that at a temperature of 300 °C (572 °F) and pressure of 500 bars, olivine serpentinizes with release of hydrogen gas. In addition, methane and complex hydrocarbons are formed through reduction of carbon dioxide. The process may be catalyzed by magnetite formed during serpentinization. [6] One reaction pathway is: [24]
+ + 26 H 2O + CO 2 → + + | (Reaction 7) |
Lizardite and chrysotile are stable at low temperatures and pressures, while antigorite is stable at higher temperatures and pressure. [31] Its presence in a serpentinite indicates either that serpentinization took place at unusually high pressure and temperature or that the rock experienced higher grade metamorphism after serpentinization was complete. [2]
Infiltration of CO2-bearing fluids into serpentinite causes distinctive talc-carbonate alteration . [32] Brucite rapidly converts to magnesite and serpentine minerals (other than antigorite) are converted to talc. The presence of pseudomorphs of the original serpentinite minerals shows that this alteration takes place after serpentinization. [2]
Serpentinite may contain chlorite (a phyllosilicate mineral), tremolite (Ca2(Mg5.0-4.5Fe2+0.0-0.5)Si8O22(OH)2), and metamorphic olivine and diopside (calcium-rich pyroxene). This indicates that the serpentinite has been subject to more intense metamorphism, reaching the upper greenschist or amphibolite metamorphic facies. [2]
Above about 450 °C (842 °F), antigorite begins to break down. Thus serpentinite does not exist at higher metamorphic facies. [12]
The presence of traces of methane in the atmosphere of Mars has been hypothesized to be a possible evidence for life on Mars if methane was produced by bacterial activity. Serpentinization has been proposed as an alternative non-biological source for the observed methane traces. [33] [34] In 2022 it was reported that microscopic examination of the ALH 84001 meteorite, which came from Mars, shows that indeed the organic matter it contains was formed by serpentinization, not by life processes. [35] [36]
Using data from the Cassini probe flybys obtained in 2010–12, scientists were able to confirm that Saturn's moon Enceladus likely has a liquid water ocean beneath its frozen surface. A model suggests that the ocean on Enceladus has an alkaline pH of 11–12. [37] The high pH is interpreted to be a key consequence of serpentinization of chondritic rock, that leads to the generation of H
2, a geochemical source of energy that can support both abiotic and biological synthesis of organic molecules. [37] [38]
Serpentinization occurs at mid-ocean ridges, in the forearc mantle of subduction zones, in ophiolite packages, and in ultramafic intrusions. [3] [4]
Conditions are highly favorable for serpentinization at slow to ultraslow spreading mid-ocean ridges. [8] Here the rate of crustal extension is high compared with the volume of magmatism, bringing ultramafic mantle rock very close to the surface where fracturing allows seawater to infiltrate the rock. [11]
Serpentinization at slow spreading mid-ocean ridges can cause the seismic Moho discontinuity to be placed at the serpentinization front, rather than the base of the crust as defined by normal petrological criteria. [39] [8] The Lanzo Massif of the Italian Alps shows a sharp serpentinization front that may be a relict seismic Moho. [40]
Serpentinization is an important phenomenon in subduction zones that has a strong control on the water cycle and geodynamics of a subduction zone. [41] Here mantle rock is cooled by the subducting slab to temperatures at which serpentinite is stable, and fluids are released from the subducting slab in great quantities into the ultramafic mantle rock. [41] Direct evidence that serpentinization is taking place in the Mariana Islands island arc is provided by the activity of serpentinite mud volcanoes. Xenoliths of harzburgite and (less commonly) dunite are occasionally erupted by the mud volcanoes, giving clues to the nature of the protolith. [42]
Because serpentinization lowers the density of the original rock, serpentinization may lead to uplift or exhumation of serpentinites to the surface, as has taken place with the serpentinite exposed at the Presidio of San Francisco following cessation of subduction. [43]
Serpentinized ultramafic rock is found in many ophiolites. Ophiolites are fragments of oceanic lithosphere that has been thrust onto continents, a process called obduction . [44] They typically consist of a layer of serpentinized harzburgite (sometimes called alpine peridotite in older writings), a layer of hydrothermally altered diabases and pillow basalts, and a layer of deep water sediments containing radiolarian ribbon chert. [45]
Seismic wave studies can detect the presence of large bodies of serpentinite in the crust and upper mantle, since serpentinization has a huge impact on shear wave velocity. A higher degree of serpentinization will lead to lower shear wave velocity and higher Poisson's ratio. [46] Seismic measurements confirm that serpentinization is pervasive in forearc mantle. [47] The serpentinization can produce an inverted Moho discontinuity, in which seismic velocity abruptly decreases across the crust-mantle boundary, which is the opposite of the usual behavior. The serpentinite is highly deformable, creating an aseismic zone in the forearc, at which serpentinites slide at stable plate velocity. The presence of serpentinite may limit the maximum depth of megathrust earthquakes as they impede rupture into the forearc mantle. [46]
Dunite, also known as olivinite, is an intrusive igneous rock of ultramafic composition and with phaneritic (coarse-grained) texture. The mineral assemblage is greater than 90% olivine, with minor amounts of other minerals such as pyroxene, chromite, magnetite, and pyrope. Dunite is the olivine-rich endmember of the peridotite group of mantle-derived rocks.
Serpentine subgroup are greenish, brownish, or spotted minerals commonly found in serpentinite. They are used as a source of magnesium and asbestos, and as decorative stone. The name comes from the greenish color and smooth or scaly appearance from the Latin serpentinus, meaning "snake-like".
The abiogenic petroleum origin hypothesis proposes that most of earth's petroleum and natural gas deposits were formed inorganically, commonly known as abiotic oil. Scientific evidence overwhelmingly supports a biogenic origin for most of the world's petroleum deposits. Mainstream theories about the formation of hydrocarbons on earth point to an origin from the decomposition of long-dead organisms, though the existence of hydrocarbons on extraterrestrial bodies like Saturn's moon Titan indicates that hydrocarbons are sometimes naturally produced by inorganic means. A historical overview of theories of the abiogenic origins of hydrocarbons has been published.
Peridotite ( PERR-ih-doh-tyte, pə-RID-ə-) is a dense, coarse-grained igneous rock consisting mostly of the silicate minerals olivine and pyroxene. Peridotite is ultramafic, as the rock contains less than 45% silica. It is high in magnesium (Mg2+), reflecting the high proportions of magnesium-rich olivine, with appreciable iron. Peridotite is derived from Earth's mantle, either as solid blocks and fragments, or as crystals accumulated from magmas that formed in the mantle. The compositions of peridotites from these layered igneous complexes vary widely, reflecting the relative proportions of pyroxenes, chromite, plagioclase, and amphibole.
Diopside is a monoclinic pyroxene mineral with composition MgCaSi
2O
6. It forms complete solid solution series with hedenbergite and augite, and partial solid solutions with orthopyroxene and pigeonite. It forms variably colored, but typically dull green crystals in the monoclinic prismatic class. It has two distinct prismatic cleavages at 87 and 93° typical of the pyroxene series. It has a Mohs hardness of six, a Vickers hardness of 7.7 GPa at a load of 0.98 N, and a specific gravity of 3.25 to 3.55. It is transparent to translucent with indices of refraction of nα=1.663–1.699, nβ=1.671–1.705, and nγ=1.693–1.728. The optic angle is 58° to 63°.
Pyroxenite is an ultramafic igneous rock consisting essentially of minerals of the pyroxene group, such as augite, diopside, hypersthene, bronzite or enstatite. Pyroxenites are classified into clinopyroxenites, orthopyroxenites, and the websterites which contain both types of pyroxenes. Closely allied to this group are the hornblendites, consisting essentially of hornblende and other amphiboles.
Ultramafic rocks are igneous and meta-igneous rocks with a very low silica content, generally >18% MgO, high FeO, low potassium, and are usually composed of greater than 90% mafic minerals. The Earth's mantle is composed of ultramafic rocks. Ultrabasic is a more inclusive term that includes igneous rocks with low silica content that may not be extremely enriched in Fe and Mg, such as carbonatites and ultrapotassic igneous rocks.
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 to snake skin. Greek pharmacologist Dioscorides recommended eating this rock to prevent snakebite.
The Lost City Hydrothermal Field, often referred to simply as Lost City, is an area of marine alkaline hydrothermal vents located on the Atlantis Massif at the intersection between the Mid-Atlantic Ridge and the Atlantis Transform Fault, in the Atlantic Ocean. It is a long-lived site of active and inactive ultramafic-hosted serpentinization, abiotically producing many simple molecules such as methane and hydrogen which are fundamental to microbial life. As such it has generated scientific interest as a prime location for investigating the origin of life on Earth and other planets similar to it.
Anthophyllite is an orthorhombic amphibole mineral: ☐Mg2Mg5Si8O22(OH)2 (☐ is for a vacancy, a point defect in the crystal structure), magnesium iron inosilicate hydroxide. Anthophyllite is polymorphic with cummingtonite. Some forms of anthophyllite are lamellar or fibrous and are classed as asbestos. The name is derived from the Latin word anthophyllum, meaning clove, an allusion to the most common color of the mineral. The Anthophyllite crystal is characterized by its perfect cleavage along directions 126 degrees and 54 degrees.
Komatiite is a type of ultramafic mantle-derived volcanic rock defined as having crystallised from a lava of at least 18 wt% magnesium oxide (MgO). It is classified as a 'picritic rock'. Komatiites have low silicon, potassium and aluminium, and high to extremely high magnesium content. Komatiite was named for its type locality along the Komati River in South Africa, and frequently displays spinifex texture composed of large dendritic plates of olivine and pyroxene.
Talc carbonates are a suite of rock and mineral compositions found in metamorphosed ultramafic rocks.
The Merlis Serpentinites are an aligned group of small serpentinite outcrops in the northwestern French Massif Central. Their parent rocks were peridotites from the upper mantle.
Listwanite (also sometimes spelled listvenite, listvanite, or listwaenite) is a rock type that forms when the groundmass of ultramafic rocks, most commonly mantle peridotites, is partially altered to carbonate minerals and cut by ubiquitous carbonate veins containing one or more of magnesite, calcite, dolomite, ankerite, and/or siderite. Original pyroxene and olivine in the peridotite are commonly altered to Mg- or Ca-carbonate and hydrous Mg-silicates, such as serpentine and talc. Complete carbonation of peridotite means that every single atom of magnesium and calcium as well as some of the iron atoms have combined with CO2 to form secondary carbonate minerals such a magnesite, calcite, and siderite, while the remaining silica atoms, formerly found in pyroxene and olivine (prior to alteration), are found in quartz, serpentine, and talc. Thus, in terms of bulk mineralogy, listwanites consist primarily of quartz (often of a rusty red colour), carbonate, serpentine, talc, ± mariposite/fuchsite (i.e., Cr-muscovite) ± gold.
The Staten Island Serpentinite locality is a southward extension of the New England Uplands, adjacent to the Manhattan Prong. It includes Todt Hill on Staten Island, which is the highest point along the Atlantic Seaboard south of Maine, at 410 feet (120 m) above sea level. "Todt" is a Dutch word meaning "dead." This hill perhaps received its name from the Dutch settlers because the hilltops overlooking The Narrows consisted of scattered treeless rocky exposures. The chemical character of the bedrock was, in part, the reason for this. Much of Staten Island is covered by the Harbor Hill moraine, the terminal moraine of the last Wisconsin Stage glacier. However, ledges of bedrock consisting of serpentinite are exposed throughout the upland areas on Staten Island. Grymes Hill, the second highest point on Staten Island and just a few miles from Todt Hill has similar bedrock characteristics. Serpentine, the dominant mineral in serpentinite, is rich in magnesium, an element that most plants cannot tolerate in high concentrations. The enrichment of magnesium in the thin serpentine soil covering the glacier-scoured hilltops is probably responsible for the original barren exposures on Todt Hill.
Mud volcanoes in the Mariana fore-arc are a hydrothermal geologic landform that erupt slurries of mud, water, and gas. There are at least 10 mud volcanoes in the Mariana fore-arc that are actively erupting, including the recently studied Conical, Yinazao, Fantagisna, Asut Tesoro, and South Chamorro serpentinite mud volcanoes. These mud volcanoes erupt a unique serpentinite mud composition that is related to the geologic setting in which they have formed. Serpentinite mud is the product of mantle metasomatism due to subduction zone metamorphism and slab dehydration. As a result, the serpentinite mud that erupts from these mud volcanoes often contains pieces of mantle peridotite material that has not fully altered during the serpentinization process. In addition to pieces of altered mantle material, pieces of subducted seamounts have also been found within the serpentinite muds. Serpentinite mud volcanoes in the Mariana fore-arc are often located above faults in the fore-arc crust. These faults act as conduits for the hydrated mantle material to ascend towards the surface. The Mariana mud volcanoes provide a direct window into the process of mantle hydration that leads to the production of arc magmas and volcanic eruptions.
Antigorite is a lamellated, monoclinic mineral in the phyllosilicate serpentine subgroup with the ideal chemical formula of (Mg,Fe2+)3Si2O5(OH)4. It is the high-pressure polymorph of serpentine and is commonly found in metamorphosed serpentinites. Antigorite, and its serpentine polymorphs, play an important role in subduction zone dynamics due to their relative weakness and high weight percent of water (up to 13 weight % H2O). It is named after its type locality, the Geisspfad serpentinite, Valle Antigorio in the border region of Italy/Switzerland and is commonly used as a gemstone in jewelry and carvings.
Lizardite is a mineral from the serpentine subgroup with formula Mg3(Si2O5)(OH)4, and the most common type of mineral in the subgroup. It is also a member of the kaolinite-serpentine group.
Taiwan Black Jade is a type of serpentine jade, primarily composed of minerals such as antigorite and magnetite. It exhibits colors ranging from dark green to black. It is found in the Fengtian area of Hualien County, Taiwan. It was discovered during the mining of Taiwan Jade in the 1960s and 1970s but was not at that time recognized as a new variety of mineral. In the 2010s researchers conducted studies and analysis that identified it as a new type of serpentine jade.
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