Ultramafic-hosted Hydrothermal Systems Research Articles

Fossil hydrothermal oceanic systems through in-situ B isotopes in ophicarbonates (N. Apennines, Italy)

In submarine-hydrothermal systems, fluid-rock interactions play a pivotal role in fostering life on rocky planets. Carbonated-ultramafic rocks (i.e., ophicarbonates) represent an important witness of such environments and their study may provide new insights into hydrothermal processes. Here, we report in-situ trace element concentrations and the first in-situ boron isotope analyses (δ11B) of serpentines from the Ligurian N. Apennine (Italy) ophicarbonates, which represent non-subducted remnants of Jurassic ultramafic-hosted hydrothermal system. Based on micro-Raman analyses, lizardite is the dominant stable serpentine polymorph in the studied samples, thus constraining the temperature (T) of serpentinization below ca. 320 °C. By means of UPb LA-ICP-MS calcite geochronology, the age of the carbonation event is constrained at 137 ± 3 Ma (2σ, n = 52). The increasing inventory of several fluid-mobile elements (e.g., B, Li, As, Sb, Sr, U) associated with the REE budget variability in serpentines from ophicarbonates compared to those in pure serpentinites suggest that physico-chemical changes during the evolution of the hydrothermal system exert a relevant influence on the geochemistry of serpentines. Pure serpentinites, which are considered the protoliths of the ophicarbonates, show positive δ11B signatures from +15.8 to +35.0‰ (n = 24), thus falling in the range of present-day oceanic and forearc serpentinites and ophiolite-derived serpentinites. The δ11B imprint of serpentines in ophicarbonates clusters at +10.2 ± 2.2‰ (2SD, n = 57) and − 5.7 ± 1.5‰ (2SD, n = 36). Remarkably, this is the first report of oceanic serpentines showing negative B isotope compositions. The positive δ11B data likely reflect inheritance from the precursor serpentinite, while the negative δ11B values are here related to the hydrothermal process(es). We attempt to model how the variation in pH and different δ11B composition of the hydrothermal vent fluids (+25 and + 8‰) at different T (100 and 150 °C) can affect the δ11B imprint of serpentines. Our results indicate that either pH condition or δ11B of the hydrothermal vent fluids can shift the δ11B of serpentines from positive to negative values. Our new trace element and δ11B data are integrated and discussed with those from the literature to achieve new constraints in the variations and controls on the physical-chemical conditions of fluid-rock interaction during the progressive evolution of long-lived fossil ultramafic-hosted hydrothermal system. Finally, we discuss how subduction processes can potentially modify the B geochemistry of ophicarbonates and the information that we could achieve by studying B isotopes in such high-P lithologies to unravel the B- and C-cycles into the Earth's mantle since the onset of modern plate tectonics.

Characterization of Geochemistry in Hydrothermal Sediments From the Newly Discovered Onnuri Vent Field in the Middle Region of the Central Indian Ridge

The recently discovered Onnuri hydrothermal vent field (OVF) is a typical off-axis ultramafic-hosted vent system, located on the summit of the dome-like ocean core complex (OCC) at a distance of ∼12 km from the ridge axis along the middle region of the Central Indian Ridge (CIR). The plume chemistry with high methane anomaly was consistent with the precursor of hydrothermal activity; however, the fundamental characteristic of the OVF system, such as the hydrothermal circulation process and source of heat, remains poorly understood. Here, we focus on the geochemical features of surface sediments and minerals collected at and around the OVF region in order to better understand this venting system. The results reveal that the OVF sediments are typified by remarkably high concentrations of Fe, Si, Ba, Cu, and Zn, derived from hydrothermal fluid and S and Mg from seawater; depleted C-S isotope compositions; and abundant hydrothermally precipitated minerals (i.e., Fe–Mn hydroxides, sulfide and sulfate minerals, and opal silica). Notably, the occurrence of pure talc and barite bears witness to strong hydrothermal activity in the OVF, and their sulfur and strontium isotope geochemistry agree with extensive mixing of the unmodified seawater with high-temperature fluid derived from the gabbroic rock within the ultramafic-dominated ridge segment. The findings reveal that the OVF is a representative example of an off-axis, high-temperature hydrothermal circulation system, possibly driven by the exothermic serpentinization of exposed peridotites. Given the widespread distribution of OCC with detachment faults, furthermore, the OVF may be the most common type of hydrothermal activity in the CIR, although the paucity of data precludes generalizing this result. This study provides important information contributing to our understanding of the ultramafic-hosted hydrothermal vent system with a non-magmatic heat source along mid-ocean ridges.

Gold and tin mineralisation in the ultramafic-hosted Cheoeum vent field, Central Indian Ridge

The Cheoeum vent field (CVF) is the first example of an inactive ultramafic-hosted seafloor massive sulphide (SMS) deposit identified in the middle part of the Central Indian Ridge. Here, we report on the detailed mineralogy and geochemistry of ultramafic-hosted sulphide sample atop a chimney, together with a few small fragments. Hydrothermal chimneys are characterised by high concentrations of Au (up to 17.8 ppm) and Sn (up to 1720 ppm). The sulphide mineralisation in the CVF shows (1) early precipitation of anhedral sphalerite and pyrite–marcasite aggregates under relatively low-temperature (< 250 °C) fluid conditions; (2) intensive deposition of subhedral pyrrhotite, isocubanite, chalcopyrite, Fe-rich sphalerite (Sp-III), and electrum from high-temperature (250–365 °C) and reduced fluids in the main mineralisation stage; and (3) a seawater alteration stage distinguished by the mineral assemblage of marcasite pseudomorphs, altered isocubanite phase, covellite, amorphous silica, and Fe-oxyhydroxides. Electrum (< 2 μm in size) is the principal form of Au mineralisation and is mainly associated with the main mineralisation stage. The consistently high fineness of electrum (801 to 909‰) is indicative of the selective saturation of Au over Ag in the fluid during high-temperature mineralisation, which differs from the Au mineralisation associated with typical basaltic-hosted hydrothermal systems on mid-ocean ridges. Tin is mainly substituted in structures of sphalerite, isocubanite, and chalcopyrite as a solid solution, and not as mineral inclusions. The continuously ascending hydrothermal fluids enable the early formed Sn-bearing sulphide to be dissolved and reprecipitated, producing significantly Sn-enriched replacement boundaries between isocubanite and Sp-III. This study suggests that Au–Sn mineralisation could be facilitated by the low redox potential of ultramafic-hosted hydrothermal systems such as in the CVF, which may be a common occurrence along slow-spreading mid-ocean ridges.

Precipitation of Calcite Veins in Serpentinized Harzburgite at Tianxiu Hydrothermal Field on Carlsberg Ridge (3.67°N), Northwest Indian Ocean: Implications for Fluid Circulation

Serpentinization and calcite precipitation of mantle peridotites exhumed along detachment faults at the slow- to ultraslow-spreading centers can provide important clues to the hydrothermal alteration processes. The Tianxiu hydrothermal field is a new-found active and ultramafichosted hydrothermal vent site along the Carlsberg Ridge, Northwest Indian Ocean. Two types of calcite veins are recognized in serpentinized harzburgite samples collected from the seafloor at the water depth of 3 500 m (3.67°N/63.83°E) and 400 m north of Tianxiu hydrothermal field. Calcite veins I occur in the fractures that cut through mesh texture in the highly serpentinized harzburgite, while calcite veins II precipitate within the mesh texture in the relatively weaker serpentinized harzburgite. Both veins show similar δ13CPDB (+0.54‰ and +0.58‰) but different δ18OPDB(−16.67‰ and +4.46‰) values, suggesting that they were derived from the same carbon source but precipitated at different temperatures. Taking the deep seawater temperature of 2 °C as the precipitation temperature of the calcite veins I, the equilibrium δ18OV-SMOW of calcite-precipitating fluid was calculated to be 1.78‰, which is close to the average δ18OV-SMOW value (1.74‰) of vent fluid samples from the ultramafic-hosted hydrothermal systems worldwide. The formation temperature of calcite veins II is inferred to be approximately 134 °C, based on the calculated δ18OV-SMOW above. The temperature differences of calcite precipitation probably resulted from the fluid cooling conductively and mixing with seawater along the presumed fractures during slow upflow. The low-temperature calcite postdates the mesh texture, while the high-temperature calcite may precipitate under relatively low water/rock ratios, alkaline and reduced conditions among the mesh texture, which is revealed by the geochemical models. Therefore, it is suggested that they both have been influenced by hydrothermal fluids and the sampling site is near the discharge zone of hydrothermal circulation.

Rare earth element uptake during olivine/water hydrothermal interaction

Ultramafic-hosted hydrothermal vent systems link the hydrosphere with the peridotitic mantle via serpentinization. Here, the fractionation and mobility of selected trace (Nd, Sm, Gd, Dy, Yb, Sr and Ba) and major cations (Si, Ca, Mg, Fe, Ni) during seawater-peridotite interaction was investigated through a series of experiments where natural olivine grains were reacted with an artificial seawater solution at a range of temperatures (15–90 °C) and grain size distributions. No evidence for any significant olivine dissolution or precipitation of carbonate and, Fe-oxy-hydroxide phases was observed in these experiments. Experimental data show a strong decoupling of REE (Nd, Sm, Gd, Dy, and Yb) from Sr and Ba under all experimental conditions, with Sr and Ba remaining quantitatively in solution. The REE were removed from the solution and were adsorbed onto olivine surface with kinetic rate constants (i.e. uptake over time) that increase with increasing temperature and increasing surface area (i.e. decreasing particle size). Dysprosium and Yb (heavy REE; HREE) were removed from solution with a faster rate than Nd and Sm (light REE; LREE). Gadolinium is decoupled from this trend, with a slower kinetic rate constant than Sm. The activation energies (Ea) of REE adsorption on olivine were higher for Nd and Sm than Dy and Yb. This suggests that the adsorbance of LREE is generally more dependent on temperature than the HREE. The Ea correlates well with the summed 1st, 2nd and 3rd ionization energies of REE suggesting a link between kinetic rates of element adsorption and electron configuration of the 4f-orbitals. Gadolinium has higher Ea than the other analyzed REE, consistent with the electron configuration of Gd3+ where all 4f-orbitals are filled with one electron each. These experimental data suggest that REE are adsorbed on the surface of olivine via inner sphere complexes under low-temperature hydrothermal conditions, when alteration processes are limited or extremely slow. Scavenging and fractionation of REE may occur within the recharge zone of peridotite-hosted hydrothermal systems at relatively low temperatures (<100 °C), leading to fluids with progressively higher LREE/HREE which could impose seawater-derived LREE enrichments in serpentinized peridotites during high temperature, high pressure water/rock interaction deeper in the oceanic lithosphere.

Trace Metal Distribution in Sulfide Minerals from Ultramafic-Hosted Hydrothermal Systems: Examples from the Kairei Vent Field, Central Indian Ridge

The ultramafic-hosted Kairei vent field is located at 25°19′ S, 70°02′ E, towards the Northern end of segment 1 of the Central Indian Ridge (CIR-S1) at a water depth of ~2450 m. This study aims to investigate the distribution of trace elements among sulfide minerals of differing textures and to examine the possible factors controlling the trace element distribution in those minerals using LA-ICP-MS spot and line scan analyses. Our results show that there are distinct systematic differences in trace element distributions throughout the different minerals, as follows: (1) pyrite is divided into three types at Kairei, including early-stage euhedral pyrite (py-I), sub-euhedral pyrite (py-II), and colloform pyrite (py-III). Pyrite is generally enriched with Mo, Au, As, Tl, Mn, and U. Pyrite-I has high contents of Se, Te, Bi, and Ni when compared to the other types; py-II is enriched in Au relative to py-I and py-III, but poor in Ni; py-III is enriched in Mo, Pb, and U but is poor in Se, Te, Bi, and Au relative to py-I and py-II. Variations in the concentrations of Se, Te, and Bi in pyrite are most likely governed by the strong temperature gradient. There is generally a lower concentration of nickel than Co in pyrite, indicating that our samples precipitated at high temperatures, whereas the extreme Co enrichment is likely from a magmatic heat source combined with an influence of serpentinization reactions. (2) Chalcopyrite is characterized by high concentrations of Co, Se, and Te. The abundance of Se and Te in chalcopyrite over the other minerals is interpreted to have been caused by the high solubilities of Se and Te in the chalcopyrite lattice at high temperatures. The concentrations of Sb, As, and Au are relatively low in chalcopyrite from the Kairei vent field. (3) Sphalerite from Zn-rich chimneys is characterized by high concentrations of Sn, Co, Ga, Ge, Ag, Pb, Sb, As, and Cd, but is depleted in Se, Te, Bi, Mo, Au, Ni, Tl, Mn, Ba, V, and U in comparison with the other minerals. The high concentrations of Cd and Co are likely caused by the substitution of Cd2+ and Co2+ for Zn2+ in sphalerite. A high concentration of Pb accompanied by a high Ag concentration in sphalerite indicates that Ag occurs as Pb–Ag sulfosalts. Gold is generally low in sphalerite and strongly correlates with Pb, suggesting its presence in microinclusions of galena. The strong correlation of As with Ge in sphalerite from Kairei suggests that they might precipitate at medium temperatures and under moderately reduced conditions. (4) Bornite–digenite has very low concentrations of most trace elements, except for Co, Se, and Bi. Serpentinization in ultramafic-hosted hydrothermal systems might play an important role in Au enrichment in pyrite with low As contents. Compared to felsic-hosted seafloor massive sulfide deposits, sulfide minerals from ultramafic-hosted deposits show higher concentrations of Se and Te, but lower As, Sb, and Au concentrations, the latter often attributed to the contribution of magmatic volatiles. As with typical ultramafic-hosted seafloor massive sulfide deposits, Se enrichment in chalcopyrite from Kairei indicates that the primary factor that controls the Se enrichment is temperature-controlled mobility in vent fluids.

Normal faulting and evolution of fluid discharge in a Jurassic seafloor ultramafic-hosted hydrothermal system

Research Article| April 16, 2018 Normal faulting and evolution of fluid discharge in a Jurassic seafloor ultramafic-hosted hydrothermal system Jeff Alt; Jeff Alt 1Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, Michigan 48109, USA Search for other works by this author on: GSW Google Scholar Laura Crispini; Laura Crispini 2Dipartimento di Scienze della Terra dell’Ambiente e della Vita (DISTAV), Università degli Studi di Genova, Corso Europa 26, 16132 Genoa, Italy Search for other works by this author on: GSW Google Scholar Laura Gaggero; Laura Gaggero 2Dipartimento di Scienze della Terra dell’Ambiente e della Vita (DISTAV), Università degli Studi di Genova, Corso Europa 26, 16132 Genoa, Italy Search for other works by this author on: GSW Google Scholar David Levine; David Levine 1Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, Michigan 48109, USA Search for other works by this author on: GSW Google Scholar Giorgia Lavagnino; Giorgia Lavagnino 2Dipartimento di Scienze della Terra dell’Ambiente e della Vita (DISTAV), Università degli Studi di Genova, Corso Europa 26, 16132 Genoa, Italy Search for other works by this author on: GSW Google Scholar Pat Shanks; Pat Shanks 3U.S. Geological Survey, 973 Denver Federal Center, Denver, Colorado 80225, USA Search for other works by this author on: GSW Google Scholar Cayce Gulbransen Cayce Gulbransen 3U.S. Geological Survey, 973 Denver Federal Center, Denver, Colorado 80225, USA Search for other works by this author on: GSW Google Scholar Geology (2018) 46 (6): 523–526. https://doi.org/10.1130/G40287.1 Article history received: 05 Oct 2017 rev-recd: 23 Mar 2018 accepted: 23 Mar 2018 first online: 16 Apr 2018 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn Email Tools Icon Tools Get Permissions Search Site Citation Jeff Alt, Laura Crispini, Laura Gaggero, David Levine, Giorgia Lavagnino, Pat Shanks, Cayce Gulbransen; Normal faulting and evolution of fluid discharge in a Jurassic seafloor ultramafic-hosted hydrothermal system. Geology 2018;; 46 (6): 523–526. doi: https://doi.org/10.1130/G40287.1 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search nav search search input Search input auto suggest search filter All ContentBy SocietyGeology Search Advanced Search Abstract We document a normal fault that lies at a high angle to an oceanic detachment that exposed peridotite on the Jurassic seafloor. Faults such as this are inferred to be discharge zones for ultramafic-hosted hydrothermal systems, but have not yet been sampled from the modern seafloor. The fault comprises 0.5–2-m-thick zones of sheared talc + sulfide within serpentinite, and ends upward in carbonated serpentinite, massive sulfide, and pillow basalts. Talc alteration and enrichment in metals, light rare earth elements, and 34S of the fault rocks provide evidence of a conduit for discharge of high-temperature hydrothermal fluids related to fluid circulation and mineralization. At the seafloor, the fault rocks have been replaced by later Fe-dolomite + minor quartz, chlorite, and sulfides at temperatures of 90–120 °C during waning hydrothermal activity. This is the first view of the subsurface discharge zone of a seafloor ultramafic-hosted hydrothermal system, showing that normal faults provide pathways to focus fluid flow and reaction. An important new result is field and geochemical evidence that high-temperature hydrothermal systems with black smoker–type venting, sulfide mineralization, and talc alteration can evolve to lower-temperature Lost City–type venting and carbonate mineralization. You do not currently have access to this article.

Unraveling multiple phases of sulfur cycling during the alteration of ancient ultramafic oceanic lithosphere

Ultramafic-hosted hydrothermal systems – characterized by ongoing serpentinization reactions – exert an important influence on the global sulfur cycle. Extensive water-rock interaction causes elemental exchange between seawater and the oceanic lithosphere, effectively removing sulfate from seawater through both abiogenic and biogenic processes. Here, we use bulk rock multiple sulfur isotope signatures (32S, 33S, 34S) and in situ sulfide analyses together with petrographic observations to track the sulfur cycling processes and the hydrothermal evolution of ancient peridotite-hosted hydrothermal systems. We investigate serpentinized peridotites from the Northern Apennine ophiolite in Italy and the Santa Elena ophiolite in Costa Rica and compare those with the Iberian Margin (Ocean Drilling Program (ODP) Leg 149 and 173) and the 15°20′N Fracture Zone along the Mid-Atlantic Ridge (ODP Leg 209).In situ measurements of sulfides in the Northern Apennine serpentinites preserve a large range in δ34Ssulfide of −33.8 to +13.3‰ with significant heterogeneities within single sulfide grains and depending on mineralogy. Detailed mineralogical investigation and comparison with bulk rock Δ33Ssulfide and in situ δ34Ssulfide data implies a thermal evolution of the system from high temperatures (∼350 °C) that allowed thermochemical sulfate reduction and input of hydrothermal sulfide to lower temperatures (<120 °C) that permitted microbial activity. The change in temperature regime is locally preserved in individual samples and correlates with the progressive uplift and exposure of mantle rock associated with detachment faulting along a mid-ocean ridge spreading center. The Santa Elena peridotites preserve distinct signatures for fluid circulation at high temperatures with both closed system thermochemical sulfate reduction and input of mafic-derived sulfur. In addition, the peridotites provide strong evidence that low Ca2+ concentrations in peridotite-hosted systems can limit sulfate removal during anhydrite precipitation at temperatures above 150 °C. This may play a central role for the availability of sulfate to microbial communities within these systems. Overall, the combined application of in situ and bulk rock multiple sulfur isotope measurements with petrographic observations allows us to resolve the different episodes of sulfur cycling during alteration of the oceanic lithosphere and the temporal changes between abiogenic and biogenic processes that control the sulfur cycling in these systems.

Seismic imaging of magma sills beneath an ultramafic-hosted hydrothermal system

Hydrothermal circulation at mid-ocean ridge volcanic segments extracts heat from crustal magma bodies. However, the heat source driving hydrothermal circulation in ultramafic outcrops, where mantle rocks are exhumed in low-magma-supply environments, has remained enigmatic. Here we use a three-dimensional P -wave velocity model derived from active-source wide-angle refraction-reflection ocean bottom seismometer data and pre-stack depth-migrated images derived from multichannel seismic reflection data to investigate the internal structure of the Rainbow ultramafic massif, which is located in a non-transform discontinuity of the Mid-Atlantic Ridge. Seismic imaging reveals that the ultramafic rocks composing the Rainbow massif have been intruded by a large number of magmatic sills, distributed throughout the massif at depths of ∼2–10 km. These sills, which appear to be at varying stages of crystallization, can supply the heat needed to drive high-temperature hydrothermal circulation, and thus provide an explanation for the hydrothermal discharge observed in this ultramafic setting. Our results demonstrate that high-temperature hydrothermal systems can be driven by heat from deep-sourced magma even in exhumed ultramafic lithosphere with very low magma supply.

Magnetic exploration of a low-temperature ultramafic-hosted hydrothermal site (Lost City, 30°N, MAR)

A 2003 high-resolution magnetic survey conducted by the Autonomous Underwater Vehicle ABE over the low-temperature, ultramafic-hosted hydrothermal field Lost City reveals a weak positive magnetic anomaly. This observation is in direct contrast to recent observations of strong positive magnetic anomalies documented over the high-temperature ultramafic-hosted hydrothermal vents fields Rainbow and Ashadze, which indicates that temperature may control the production of magnetization at these sites. The Lost City survey provides a unique opportunity to study a field that is, to date, one of a kind, and is an end member of ultramafic-hosted hydrothermal systems. Our results highlight the key contribution of temperature on magnetite production resulting from serpentinization reactions. Whereas high temperature promotes significant production and partitioning of iron into magnetite, low temperature favors iron partitioning into various alteration phases, resulting in a magnetite-poor rock. Moreover, the distribution of magnetic anomalies confirms results of a previous geological survey indicating the progressive migration of hydrothermal activity upslope. These discoveries contribute to the results of 25 yrs of magnetic exploration of a wide range of hydrothermal sites, from low- to high-temperature and from basalt- to ultramafic-hosted, and thereby validate using high-resolution magnetics as a crucial parameter for locating and characterizing hydrothermal sites hosting unique chemosynthetic-based ecosystems and potentially mineral-rich deposits.

Experimental study of carbonate formation in oceanic peridotite

Interactions of CO2-rich aqueous fluids with mantle peridotite have major implications for geochemical budgets and microbial life in the shallow oceanic lithosphere through the formation of carbonate minerals and reduced carbon species. However, the underlying mechanisms controlling the transformation of CO2 to carbonates in ultramafic-hosted hydrothermal systems remain incompletely understood. A long-term laboratory experiment was conducted at 300°C and 35MPa to investigate serpentinization and carbonate formation pathways during hydrothermal alteration of peridotite. Powdered harzburgite was initially reacted with a Ca-rich aqueous fluid for 14,592h (608days) and changes in fluid composition were monitored with time. Once the system reached a steady state, a CO2(aq)-rich fluid was injected and allowed to react with the system for 5907h (246days). Fluid speciation and mineral analyses suggest that serpentinization of harzburgite in the CO2-poor system led to the precipitation of serpentine, brucite, magnetite, and minor calcite, in addition to other minor phases including chlorite and sulfur-poor Ni sulfides. The addition of the CO2(aq)-rich fluid caused dolomite, Ca-rich dolomite, and high-Mg calcite to form at the expense of olivine, calcite, and brucite, while serpentine remained unreactive. Replacement textures and mineral assemblages mimic those documented in carbonate-altered seafloor serpentinites, particularly those from the Mid-Atlantic Ridge and the Iberia Margin. In contrast to thermodynamic predictions, magnesite did not form in the experiment because the dissolution of clinopyroxene, in combination with the lack of serpentine reactivity, maintained low Mg/Ca ratios in solution. Clinopyroxene dissolution and unreactive serpentine may similarly maintain low Mg/Ca ratios in submarine serpentinization systems and limit magnesite formation in subseafloor environments. Results of this study suggest that the formation of Ca–Mg carbonates by mineral carbonation is favorable in subseafloor serpentinization systems and likely represents a significant, but poorly quantified, carbon sink in hydrothermally altered oceanic lithosphere at slow-spreading mid-ocean ridges.

Hydrothermal Alteration in the Subsurface of an Oceanic Ultramafic-Hosted Hydrothermal System (as Preserved in Ligurian Ophiolites, Italy)

Hydrothermal Alteration in the Subsurface of an Oceanic Ultramafic-Hosted Hydrothermal System (as Preserved in Ligurian Ophiolites, Italy)

Origin of magnetic highs at ultramafic hosted hydrothermal systems: Insights from the Yokoniwa site of Central Indian Ridge

High-resolution vector magnetic measurements were performed on an inactive ultramafic-hosted hydrothermal vent field, called Yokoniwa Hydrothermal Field (YHF), using a deep-sea manned submersible Shinkai6500 and an autonomous underwater vehicle r2D4. The YHF has developed at a non-transform offset massif of the Central Indian Ridge. Dead chimneys were widely observed around the YHF along with a very weak venting of low-temperature fluids so that hydrothermal activity of the YHF was almost finished. The distribution of crustal magnetization from the magnetic anomaly revealed that the YHF is associated with enhanced magnetization, as seen at the ultramafic-hosted Rainbow and Ashadze-1 hydrothermal sites of the Mid-Atlantic Ridge. The results of rock magnetic analysis on seafloor rock samples (including basalt, dolerite, gabbro, serpentinized peridotite, and hydrothermal sulfide) showed that only highly serpentinized peridotite carries high magnetic susceptibility and that the natural remanent magnetization intensity can explain the high magnetization of Yokoniwa. These observations reflect abundant and strongly magnetized magnetite grains within the highly serpentinized peridotite. Comparisons with the Rainbow and Ashadze-1 suggest that in ultramafic-hosted hydrothermal systems, strongly magnetized magnetite and pyrrhotite form during the progression of hydrothermal alteration of peridotite. After the completion of serpentinization and production of hydrogen, pyrrhotites convert into pyrite or nonmagnetic iron sulfides, which considerably reduces their levels of magnetization. Our results revealed origins of the magnetic high and the development of subsurface chemical processes in ultramafic-hosted hydrothermal systems. Furthermore, the results highlight the use of near-seafloor magnetic field measurements as a powerful tool for detecting and characterizing seafloor hydrothermal systems.

Redox controls on Ni–Fe–PGE mineralization and Re/Os fractionation during serpentinization of abyssal peridotite

Awaruite (Ni2Fe to Ni3Fe) is often used to infer fugacity and redox gradients in hydrothermally altered peridotites. However, discrepant petrological and thermodynamic data suggest that the fO2–fS2 stability field of awaruite is not well constrained. In this study, we assess the thermodynamic properties of awaruite and re-evaluate the Fe–Ni–S systematics of hydrothermally altered peridotites. New experimental data indicate that awaruite is stable at higher fO2 than previously thought, supporting the common occurrence of awaruite in the reaction zone of modern and ancient ultramafic-hosted hydrothermal vent systems. Awaruite is known to catalyze the abiogenic synthesis of methane during active serpentinization, contributing to methanogenesis at modern oceanic hydrothermal systems and potentially on early Earth. The enhanced stability field of awaruite determined here suggests that abiogenic methanogenesis may be active at a broad range of redox conditions.Serpentinized peridotites also contain platinum-group element (PGE)–Re sulfides and metal alloys that can be derived from desulfurization of primary mantle sulfides under low fS2. Thermodynamic calculations suggest that Os will exist as metal and Re as ReS2 in the redox stability field of awaruite. Under a relatively broad range of fS2–fO2 conditions, hydrothermal alteration and desulfurization of primary mantle may produce open system behavior in the Re/Os system and variable Re–PGE ratios and contribute over time to the Os isotopic heterogeneity of the mantle, through subduction and recycling of altered oceanic lithosphere. PGE-metal alloys occur at such low abundances in peridotite that they often are nearly impossible to find. The stability of awaruite at higher fO2 suggests that it can coexist with Os–Ir–Pt metal alloys, making it an important indicator mineral for their presence in hydrothermally altered peridotites.

Uptake of carbon and sulfur during seafloor serpentinization and the effects of subduction metamorphism in Ligurian peridotites

The concentrations and isotope compositions of carbon and sulfur in Ligurian serpentinites having different metamorphic histories were analyzed in order to investigate the behavior of sulfur and carbon during seafloor serpentinization and during subduction metamorphism. Serpentinites associated with gabbros and with seafloor hydrothermal sulfide deposits in northern Apennine ophiolites that exhibit only slight effects of low-grade metamorphism have high sulfur contents (190–1440ppm total sulfur) and δ34STotal S values of up to 9.8‰ through interaction with hydrothermal fluids in high-temperature ultramafic-hosted hydrothermal systems on the seafloor. Fluid circulation was driven by mafic intrusions and the hydrothermal fluids contained a mixture of basaltic and seawater-derived sulfur. The serpentinites contain 250–480ppm total carbon having δ13CTotal C values of −9.4 to −6.0‰, reflecting mixtures of seawater carbonate (~0‰) and reduced (organic) carbon having δ13C≈−25‰ and derived from multiple sources. Entrainment of cold seawater into the subsurface beneath seafloor hydrothermal sulfide deposits maintained locally low temperatures and enabled microbial reduction of seawater sulfate. Combined with previous work documenting low-temperature serpentinization on the seafloor away from such gabbro-driven high-temperature hydrothermal activity, these results provide an integrated view of serpentinization processes in tectonically extended oceanic basement exposed in oceanic core complexes.High-P–T antigorite serpentinites in the Voltri massif (Ligurian Alps) have sulfur and carbon contents and isotope compositions similar to those of the Apennine ophiolites, indicating that the protoliths underwent similar hydrothermal processes on the seafloor. Recrystallization of chrysotile and lizardite to antigorite and minor partial dehydration to olivine during subduction metamorphism result in no significant changes in the contents or isotope compositions of sulfur or carbon in the serpentinites. We estimate that the uptake of carbon and sulfur by serpentinites in oceanic basement is comparable to or greater than that per unit volume of mafic oceanic crust. The high P–T stability of serpentine can, however, make serpentinites important for transport of carbon and sulfur to greater depths in subduction zones.

Comparison of microbial communities associated with three Atlantic ultramafic hydrothermal systems

The distribution of Archaea and methanogenic, methanotrophic and sulfate-reducing communities in three Atlantic ultramafic-hosted hydrothermal systems (Rainbow, Ashadze, Lost City) was compared using 16S rRNA gene and functional gene (mcrA, pmoA and dsrA) clone libraries. The overall archaeal community was diverse and heterogeneously distributed between the hydrothermal sites and the types of samples analyzed (seawater, hydrothermal fluid, chimney and sediment). The Lost City hydrothermal field, characterized by high alkaline warm fluids (pH>11; T<95 °C), harbored a singular archaeal diversity mostly composed of unaffiliated Methanosarcinales. The archaeal communities associated with the recently discovered Ashadze 1 site, one of the deepest active hydrothermal fields known (4100 m depth), showed significant differences between the two different vents analyzed and were characterized by putative extreme halophiles. Sequences related to the rarely detected Nanoarchaeota phylum and Methanopyrales order were also retrieved from the Rainbow and Ashadze hydrothermal fluids. However, the methanogenic Methanococcales was the most widely distributed hyper/thermophilic archaeal group among the hot and acidic ultramafic-hosted hydrothermal system environments. Most of the lineages detected are linked to methane and hydrogen cycling, suggesting that in ultramafic-hosted hydrothermal systems, large methanogenic and methanotrophic communities could be fuelled by hydrothermal fluids highly enriched in methane and hydrogen.

Vent fluid chemistry of the Rainbow hydrothermal system (36°N, MAR): Phase equilibria and in situ pH controls on subseafloor alteration processes

The Rainbow hydrothermal field is located at 36°13.8′N–33°54.15′W at 2300 m depth on the western flank of a non-volcanic ridge between the South AMAR and AMAR segments of the Mid-Atlantic Ridge. The hydrothermal field consists of 10–15 active chimneys that emit high-temperature (∼365 °C) fluid. In July 2008, vent fluids were sampled during cruise KNOX18RR, providing a rich dataset that extends in time information on subseafloor chemical and physical processes controlling vent fluid chemistry at Rainbow. Data suggest that the Mg concentration of the hydrothermal end-member is not zero, but rather 1.5–2 mmol/kg. This surprising result may be caused by a combination of factors including moderately low dissolved silica, low pH, and elevated chloride of the hydrothermal fluid. Combining end-member Mg data with analogous data for dissolved Fe, Si, Al, Ca, and H 2, permits calculation of mineral saturation states for minerals thought appropriate for ultramafic-hosted hydrothermal systems at temperatures and pressures in keeping with constraints imposed by field observations. These data indicate that chlorite solid solution, talc, and magnetite achieve saturation in Rainbow vent fluid at a similar pH ( T,P ) (400 °C, 500 bar) of approximately 4.95, while higher pH values are indicated for serpentine, suggesting that serpentine may not coexist with the former assemblage at depth at Rainbow. The high Fe/Mg ratio of the Rainbow vent fluid notwithstanding, the mole fraction of clinochlore and chamosite components of chlorite solid solution at depth are predicted to be 0.78 and 0.22, respectively. In situ pH measurements made at Rainbow vents are in good agreement with pH ( T,P ) values estimated from mineral solubility calculations, when the in situ pH data are adjusted for temperature and pressure. Calculations further indicate that pH ( T,P ) and dissolved H 2 are extremely sensitive to changes in dissolved silica owing to constraints imposed by chlorite solid solution-fluid equilibria. Indeed, the predicted correlation between dissolved silica and H 2 defines a trend that is in good agreement with vent fluid data from Rainbow and other high-temperature ultramafic-hosted hydrothermal systems. We speculate that the moderate concentrations of dissolved silica in vent fluids from these systems result from hydrothermal alteration of plagioclase and olivine in the form of subsurface gabbroic intrusions, which, in turn are variably replaced by chlorite + magnetite + talc ± tremolite, with important implications for pH lowering, dissolved sulfide concentrations, and metal mobility.

Fluid elemental and stable isotope composition of the Nibelungen hydrothermal field (8°18′S, Mid-Atlantic Ridge): Constraints on fluid–rock interaction in heterogeneous lithosphere

Depending on the geological setting, the interaction of submarine hydrothermal fluids with the host rock leads to distinct energy and mass transfers between the lithosphere and the hydrosphere. The Nibelungen hydrothermal field is located at 8°18′S, about 9 km off-axis of the Mid-Atlantic Ridge (MAR). At 3000 m water depth, 372 °C hot, acidic fluids emanate directly from the bottom, without visible sulfide chimney formation. Hydrothermal fluids obtained in 2009 are characterized by low H 2S concentrations (1.1 mM), a depletion of B (192 μM) relative to seawater, lower Si (13.7 mM) and Li (391 μM) concentrations relative to basaltic-hosted hydrothermal systems and a large positive Eu anomaly, and display a distinct stable isotope signature of hydrogen (∆ 2H H2O = 7.6–8.7‰) and of oxygen (∆ 18O H2O = 2.2–2.4‰). The heavy hydrogen isotopic signature of the Nibelungen fluids is a specific feature of ultramafic-hosted hydrothermal systems and is mainly controlled by the formation of OH-bearing alteration minerals like serpentine, brucite, and tremolite during pervasive serpentinization. New isotopic data obtained for the ultramafic-hosted Logatchev I field at 14°45′N, MAR (∆ 2H H2O = 3.8–4.2‰) display a similar trend, being clearly distinguished from other, mafic-hosted hydrothermal systems at the MAR. The fluid geochemistry at Nibelungen kept stable since the first sampling campaign in 2006 and is evident for a hybrid alteration of mafic and ultramafic rocks in the subseafloor. Whereas the ultramafic-fingerprint parameters Si, Li, B, Eu anomaly and ∆ 2H H2O distinguish the Nibelungen field from other hydrothermal systems venting in basaltic settings at similar physico-chemical conditions and are related to the interaction with mantle rocks, the relatively high concentrations of trace alkali elements, Pb, and Tl can only be attributed to the alteration of melt-derived gabbroic rocks. The elemental and isotopic composition of the fluid suggest a multi-step alteration sequence: (1) low- to medium-temperature alteration of gabbroic rocks, (2) pervasive serpentinization at moderate to high temperatures, and (3) limited high-temperature interaction with basaltic rocks during final ascent of the fluid. The integrated water/rock ratio for the Nibelungen hydrothermal system is about 0.5. The fluid compositional fingerprint at Nibelungen is similar to the ultramafic-hosted Logatchev I fluids with respect to key parameters. Some compositional differences can be ascribed to different alteration temperatures and other fluid pathways involving a variety of source rocks, higher water/rock ratios, and sulfide precipitation in the sub-seafloor at Logatchev I.

Geochemical and physical structure of the hydrothermal plume at the ultramafic-hosted Logatchev hydrothermal field at 14°45′N on the Mid -Atlantic Ridge

The hydrothermal plume generated in deep waters above the Logatchev hydrothermal field (LHF) about 15°N on the Mid-Atlantic Ridge was investigated and mapped for its 3D distributions using a combination of in situ optical light scattering data, temperature and salinity data, as well as concentrations of hydrogen, methane, total dissolvable Fe, and total dissolvable Mn. Based on the results obtained for these meaningful parameters, we report the geochemical and physical characteristics of the fluids expelled from the ultramafic LHF and the chemical structure of its hydrothermal plume in the water column. The hydrothermal plume is sourced by at least seven distinct vent sites and possibly additional diffusive fluid and gas discharge. It comprises a water body characterized by strong nephelometric anomalies (expressed as ∆NTU, nephelometric turbidity units) and high concentrations of Fe and Mn (> 5 times seawater concentration), and the gas plume with several times the H 2 and CH 4 concentrations of normal seawater. Up to three plume levels with a total vertical extension of about 350 m from the seafloor were classified in the hydrothermal plume. The ∆NTU plume could be followed to approximately 2.5 km to the north and to the south from the vent site while the gas plume spread several km farther from the hydrothermal source. High concentrations of H 2 (up to 1598 nmol l − 1 ) and CH 4 (up to 323 nmol l − 1 ) accompanied by relatively low dissolvable Fe concentrations (up to 270 nmol l − 1 ) as well as low concentrations of dissolvable Mn (112 nmol l − 1 ) compared to basaltic hydrothermal systems are the characteristics of the plume. The low metal/gas ratios showed a decrease with increasing distance from the vent site. Our data demonstrate that ultramafic systems such as the LHF serve both as sources and sinks for elements, with respect to metal and gas inputs into the oceanic water column. The relevance of such systems is underlined by the discovery (and postulated frequency) of further ultramafic-hosted hydrothermal systems on slow-spreading ridges.

Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/ 86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~ 100 °C), and yet its 87Sr/ 86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine–talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/ 86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.