Serpentinization of ultramafic rocks in the sea and on land leads to the generation of alkaline fluids rich in molecular hydrogen (H2) and methane (CH4) that favour the formation of carbonate mineralization, such as veins in the sub-seafloor, seafloor carbonate chimneys and terrestrial hyperalkaline spring deposits. Examples of this type of seawater–rock interaction and the formation of serpentinization-derived carbonates in a shallow-marine environment are scarce, and almost entirely lacking in the geological record. Here we present evidence for serpentinization-induced fluid seepage in shallow-marine sedimentary rocks from the Upper Cretaceous (upper Campanian to lower Maastrichtian) Qahlah Formation at Jebel Huwayyah, United Arab Emirates. The research object is a metre-scale structure (the Jebel Huwayyah Mound) formed of calcite-cemented sand grains, which formed a positive seafloor feature. The Jebel Huwayyah Mound contains numerous vertically orientated fluid conduits containing two main phases of calcite cement. We use C and O stable isotopes and elemental composition to reconstruct the fluids from which these cements precipitated and infer that the fluids consisted of variable mixtures of seawater and fluids derived from serpentinization of the underlying Semail Ophiolite. Based on their negative δ13C values, hardgrounds in the same section as the Jebel Huwayyah Mound may also have had a similar origin. The Jebel Huwayyah Mound shows that serpentinization of the Semail Ophiolite by seawater occurred very soon after obduction and marine transgression, a process that continued through to the Miocene, and, with interaction of meteoric water, up to the present day.

Serpentine minerals and brucite in ultramafic rocks from the South Chamorro Seamount were characterized chemically to investigate the serpentinization of the Mariana forearc mantle. Relict primary minerals of the serpentinites are olivine, enstatite and minor Cr-spinel and diopside. The secondary minerals are mostly serpentine and brucite with minor magnetite. The serpentine minerals, mostly lizardite and chrysotile, display large compositional variations. Al2O3 and Cr2O3 contents depend generally upon the nature of the primary mineral from which the serpentine was derived. Both serpentine minerals and brucite exhibit wide Mg, Fe and Mn substitution: the Mg# ranges are 95.1–77.2 and 88.9–60.8, respectively. These mineralogical and chemical features allowed us to estimate an upper temperature limit for serpentinization of ∼200–300°C, in agreement with recent thermal models which suggest that the serpentinized mantle wedge of the Izu-Bonin-Mariana subduction zone is cold. The high degree of serpentinization (40–100%, average >75%), and the serpentine + brucite paragenesis of these ultramafics imply that the Mariana forearc mantle has a significantly reduced density and strength down to ∼30 km, which provides a driving mechanism for serpentinite diapirism. Pervasive serpentinization of the forearc by fluids released from the décollement zone also explains the low seismicity of the Izu-Bonin-Mariana subduction zone.

Ilvaite is sparsely disseminated in a serpentinized plagioclase wehrlite of the Asama igneous complex that underwent the Sambagawa regional metamorphism of pumpellyite-actinolite to greenschist facies. Ilvaite in the Asama complex is monoclinic (a = 13.019(5), b = 8.808(2), c = 5.850(4) Å, β = 90.19(4)°), and its composition is similar to the ideal end-member composition (). Ilvaite occurs in mats of serpentine (chrysotile); it probably formed during serpentinization, which might have accompanied the Sambagawa metamorphism. The associated secondary minerals include salitic clinopyroxene, magnetite and andradite. The ilvaite-free mineral assemblage that formed during the serpentinization is usually serpentine-clinopyroxene-magnetite, which is widespread in the complex. The phase relations between coexisting minerals suggest that the conditions during the formation of the ilvaite-bearing assemblage were reducing when compared to those of the assemblage serpentine-clinopyroxene-magnetite. The reducing conditions during the ilvaite formation were presumably brought about by hydrogen gas that1 was generated during the serpentinization of olivine.

In the southern Aosta Valley (Italian Western Alps), several massive magnetite bodies occur within serpentinized ultramafic rocks belonging to the Mesozoic meta-ophiolite nappe. The ultramafic rocks consist of lherzolite with minor dunite bodies and show a high pressure metamorphic overprint. The results of a multi-methodological study, based on optical microscopy, electron microprobe analysis and single-crystal X-ray diffraction, are reported here in order to give new insights into (1) the mineralogy and crystal chemistry of spinels and silicates and (2) the genesis of the massive magnetite bodies. Chromium-rich relict cores inside the magnetite grains suggest a derivation from primary chromite concentrations. The major-element behaviour shows the presence of two chromite types: a Cr2O3-rich (Al2O3-poor) type and a Cr2O3-poor (Al2O3-rich) type. Magnetite ore deposits probably represent the product of transformation from a chromite proto-ore which formed in ultramafic rocks pertaining to an ophiolite suite. The transformation of chromite to magnetite occurred during multiple stages: the pre- metamorphic setting of the ultramafics and the petrographic evidence suggest that metasomatism started before the onset of the alpine metamorphism and was active during the early alpine, eclogite- facies metamorphic overprint related to a subduction process under high fluid activity.

Ferritchromite is rarely reported in forearc mantle peridotites. This contribution describes ferritchromite alteration and zoned Cr-spinel in serpentinites from the Rio San Juan Complex in the Dominican Republic. These rocks originated from the forearc mantle and protruded along lithosphere-scale faults in the mid Eocene. The cores of the Cr-spinel grains have Cr# ratios [i.e.atomic Cr/(Cr + Al)] between 0.48 and 0.66; such values are relatively high and are considered to represent primary compositions. Relatively high Zn contents in the grain cores (0.46 c 0.95 wt.% ZnO) are also thought to be primary; they reflect exceptionally cool conditions in the northern Caribbean forearc mantle. A progressive change in the zoning of Cr-spinel is recorded in the samples. Weakly zoned grains of Cr-spinel have rims with lower Mg# ratios [i.e.atomic Mg/(Mg + Fe2+)] and slightly higher Cr# ratios than the cores. More strongly zoned grains of Cr-spinel, in addition to low Mg# and high Cr# in their rims, have a marked increase in Fe3+# [i.e.Fe3+/(Fe3+ + Al + Cr)] of up to 0.35 in their rims and are partially coated by Mg-rich chlorite. All grains show core-to-rim decreases in their Zn content and increases in Ti, Mn and V. The association with Mg-rich chlorite and the compositional zoning are reminiscent of those reported for ferritchromite. Ferritchromite (with Fe3+# >0.5) is common in ultramafic rocks in amphibolite-grade terranes; however, the serpentinite samples described herein show little evidence of high-grade metamorphism. The lowtemperature serpentine-group mineral lizardite is dominant and high-temperature antigorite is either very rare or absent; other high-temperature minerals, such as talc, tremolite and cummingtonite, are trace constituents. The observed zoning in the Cr-spinel is thought to represent 'immature' ferritchromite, probably formed in response to a short-lived thermal event. This event appears to have been on too short a timescale to produce either proper ferritchromite or significant quantities of high-temperature minerals. It may be related to the emplacement of the nearby Rio Boba Intrusion, or the upward protrusion of the serpentinites along the lithosphere-scale Septentrional fault zone from the base of the mantle wedge through its hotter interior. We suggest that such alteration is rare in forearc serpentinites because they are not commonly heated during exhumation along the plane of subduction. This work demonstrates that Cr-spinel compositions can be modified by relatively low-grade metamorphism.

Nanodiamonds can be synthesized hydrothermally in the laboratory by using a C-O-H fluid in the graphite stability field, in which the graphite/nanodiamond transition depends on the crystal size as a function of temperature. In nature, the hydrothermal circulation of seawater in serpentinites plays an important role in the carbon speciation in the oceanic crust and exposed mantle, in which hydrocarbons (mainly CH4) of abiogenic origin (via Fischer-Tropsch-type reaction) and occasionally graphite particles are detected. Can nanodiamonds nucleate and grow in serpentinite-hosted hydrothermal systems? To answer this question, a theoretical modelling study which compares the physico-chemical conditions in hydrothermal synthesis with those observed in modern and fossil serpentinite-hosted hydrothermal systems is proposed. Nanodiamonds are predicted to precipitate from a C-O-H fluid, consisting of CH4-CO2-H2O at 350 – 400°C and P<0.2 GPa near the FMQ buffer (Fayalite-Magnetite-Quartz), which are conditions compatible with those existing in serpentinite-hosted hydrothermal systems. In these environments, carbon-supersaturated fluids can be derived from water consumption (serpentine formation) under low water/rock ratios, which may promote the growth of nanodiamonds. This theoretical approach sheds light on the intriguing problem of carbon speciation in abyssal-type hydrothermal systems, suggesting that serpentinites may host nanodiamond deposits, even though none have been found yet.

Ortho- and clinopyroxenes within partially-hydrated harzburgites from Elba and Val di Cecina (Italy) show lamellar exsolution textures and variable replacement by biopyriboles, talc-chlorite-serpentine mixed layers and serpentine. Chemical and geothermometric data suggest that the pyroxenes crystallized at 1240–1051°C, followed by subsolidus exsolution at slightly lower T (1145–1025°C for clinopyroxene lamellae + orthopyroxene matrix pairs and a 1033–982°C range for orthopyroxene lamellae + clinopyroxene matrix pairs).

Investigation by transmission electron microscopy of exsolved enstatite and augite reveals a multistage hydration process. The first stage (highest T, probably in the amphibole stability field) leads to the formation of biopyribole lamellae within exsolved augite, leaving the enstatite matrix unaffected. The second stage (~500–300°C) corresponds to the topotactic replacement of enstatite by layer silicates (talc + chlorite + serpentine, with (001)layer silicates parallel to (100)enstatite). Enstatite is also replaced by randomly oriented, poorly crystalline serpentine. The last hydration stage (<300°C) corresponds to the disappearence of augite and recrystallization of serpentine, leading to completely hydrated bastites with random lizardite lamellae, polygonal serpentine and minor chrysotile.

The ‘Shinkai Seep Field’ is a serpentinite-hosted chemosynthetic ecosystem in the Southern Mariana Forearc. In June 2015 the site was revisited and a number of rissoiform gastropods were collected. Taxonomic investigations revealed that these specimens represent a hitherto undescribed species of Provanna (Gastropoda: Abyssochrysoidea), described herein as Provanna cingulata n. sp. This new species is characterized by numerous spiral keels, lack of significant axial sculpture, rounded and inflated whorls, and large size for the genus. With the shell height exceeding 16.5 mm (may reach 20 mm), it is the largest Provanna species known thus far. Phylogenetic analysis using 411 bp of the cytochrome oxidase c subunit I (COI) gene confirmed its systematic placement within the genus Provanna. This is the only gastropod from a family endemic to chemosynthetic ecosystems thus far known from the ‘Shinkai Seep Field’. Furthermore, with a collection depth of 5687 m, it represents the deepest known bathymetric range for the superfamily Abyssochrysoidea as a whole.

If life occurs elsewhere in the Solar System, there is a strong likelihood that it occurs in a deep biosphere beneath the planetary surface. The evidence for methane in the martian atmosphere has drawn attention to the possible role of serpentinites in fuelling a deep biosphere through the generation of hydrogen and/or methane. Serpentinites represent a good target for the search for biosignatures in a range of reaction products. Isotopic measurements in each of methane, sulphide and carbonate in serpentinites can help determine evidence of biological activity. We show that ancient terrestrial serpentinites retain methane that could be subject to the measurement of carbon and hydrogen isotopes. There is, therefore, potential to sample serpentinites on Mars and test for evidence of life in the deep geological record of Mars.

Heat produced in the mantle and core of the Earth by the decay of radioactive elements and mineral fusion results in large-scale mantle convection. The outer shell of the Earth that floats on the convective mantle is divided into rigid lithospheric plates. Subduction of dense cold plates into the mantle leads to plate tectonics. At divergent plate margins, heat is dissipated through hydrothermal convection cells. As ocean water is entrained into hydrothermal cells it interacts with fresh magmatic rocks and liberates ferrous iron. This iron reduces the ocean water to such an extent that it decomposes and forms hydrogen. Molecular hydrogen, as the most reduced component in the system, forms a basal component to a deep dark biosphere powered by metastable redox gradients. In this paper we review the driving force behind a hydrogen-driven deep biosphere. We present abundant observations of hydrogen produced at natural hydrothermal settings as well as in laboratory experiments. The key mineral reactions responsible for the bulk of this hydrogen production are then presented. A division of the reaction progression into an oxidized state and a reduced state is suggested. The amount of hydrogen produced is insignificant in the oxidized state whereas it becomes proportional to the amount of ferrous iron oxidized in the reduced state. The bulk of basalt-hosted aquifers are expected to reside in the oxidized state because of the low content of ferrous minerals, whereas abundant olivine in ultramafic-hosted systems is responsible for large-scale hydrogen production. Today the majority of the seafloor is basaltic. The Archean seafloor on the other hand consisted of fewer ultramafic exposures, but was dominated by ultramafic magnesium-rich lavas with a higher potential for hydrogen production than the present seafloor.