Vent Fluids Research Articles

Carbon and hydrogen isotope fractionation during aerobic oxidation of short-chain alkanes in experimental incubations of vent fluids

Aerobic oxidation of short-chain alkanes was observed in gas samples from the Lutao intertidal hydrothermal vents in Taiwan, during storage at 20 °C for up to 29 months without adding bacterial strains and replenishing substrates. The carbon isotope fractionation factors (εC) of methane (C1), ethane (C2), and propane (C3), were calculated using the Rayleigh fractionation equation to be −37.1 ± 7.5‰, −14.8 ± 4.8‰, and −4.7 ± 5.2‰, respectively. The hydrogen isotope fractionation factor (εH) of methane was determined to be −281 ± 187‰. DNA sequencing of the 16S rRNA gene in the vent fluids suggests that aerobic oxidation is dominated by methanotrophs of the genera Methylomicrobium and Methylophaga, which use the ribulose monophosphate pathway (RuMP). The degrees of isotope fractionation (εC and εH values) herein are larger than previously reported values, possibly due to the limited O2 supply and low abundance of aerobic methane-oxidizing bacteria in the experiments. Since the fractionation factor of methane is higher than those of ethane and propane, the aerobic oxidation of thermogenic or microbial alkanes could produce a carbon isotope reversal, which is frequently noted as a trait of abiotic hydrocarbons. This work demonstrates that in addition to anaerobic microbial oxidation, aerobic oxidation with a low cell density can also produce significant isotope fractionation of alkanes in geological closed/semi-closed environments and open flow reaction systems that are characterized by moderate temperatures and a limited supply of substrates and O2; these environments include cold seeps, mud volcanoes, and low-temperature hydrothermal plumes/aquifers/reservoirs.

Reaction Mechanism and Water/Rock Ratios Involved in Epidosite Alteration of the Oceanic Crust

AbstractEpidosites are a prominent type of subseafloor hydrothermal alteration of basalts in ophiolites and greenstone belts, showing an end‐member mineral assemblage of epidote + quartz + titanite + Fe‐oxide. Epidosites are known to form within crustal‐scale upflow zones and their fluids have been proposed as deep equivalents of black‐smoker seafloor vent fluids. Proposals of the mass of fluid per mass of rock (W/R ratio) needed to form epidosites are contradictory, varying from 20 (Sr isotopes) to > 1,000 (Mg mobility). To test these proposals we have conducted a petrographic, geochemical and reactive‐transport numerical simulation study of the chemical reaction that generates km3‐size epidosite zones within the lavas and sheeted dike complex of the Samail ophiolite, Oman. At 250–400°C the modeled epidosite‐forming fluid has near‐neutral pH (∼ 5.2), high fO2, low sulfur and very low Fe (10−6 mol/kg) contents. These features argue against a genetic link with black‐smoker fluids. Chemical buffering by the epidosite fluid enriches the precursor spilites in Ca and depletes them in Na and Mg. Completion of the spilite‐to‐epidosite reaction requires enormous W/R ratios of 700–∼40,000, depending on initial Mg content and temperature. Collectively, the variably altered rocks in the Samail epidosite zones record flow of ∼1015 kg of fluid through each km3 of precursor spilite rock. This fluid imposed on the epidosite an Sr‐isotope signature inherited from the previous rock‐buffered chemical evolution of the fluid through the oceanic crust, thereby explaining the apparently contradictory low W/R ratios based on Sr isotopes.

Depositional Environment and Genesis of the Nabeba Banded Iron Formation (BIF) in the Ivindo Basement Complex, Republic of the Congo: Perspective from Whole-Rock and Magnetite Geochemistry

The Nabeba high-grade iron deposit (Republic of the Congo) is hosted by banded iron formation (BIF) in the Ivindo Basement Complex, which lies in the northwestern part of the Congo Craton. The Nabeba BIF is intercalated with chlorite-sericite-quartz schist and comprises two facies (oxide and a carbonate-oxide). In this study, whole-rock and LA-ICP-MS magnetite geochemistry of the BIF was reported. Magnetite samples from both BIF facies had fairly similar trace element compositions except for the rare earth element plus yttrium (REE + Y) distribution patterns. The high V, Ni, Cr, and Mg contents of the magnetite in the Nabeba BIF could be ascribed to the involvement of external medium-high temperature hydrothermal fluids during their deposition in relatively reduced environment. The Post-Archean Australian Shale (PAAS)-normalized REY patterns of the Nabeba BIF magnetite were characterized by LREE depletion coupled with varying La and positive Eu anomalies. Processing of the information gathered from the geochemical signatures of magnetite and the whole-rock BIF suggested that the Nabeba BIF was formed by the mixing of predominantly anoxic seawater (99.9%) with 0.1% of high-temperature (>250 °C) hydrothermal vent fluids, similar to the formation mechanism of many Archean Algoma-type BIFs reported elsewhere in the world.

Mineralogical and geochemical characteristics and ore-forming mechanism of hydrothermal sediments in the middle and southern Okinawa Trough

In this study, analysis of mineralogy and geochemistry of fifteen surface sediment samples from four hydrothermal fields in the middle and southern Okinawa Trough is presented. Sediment samples can be divided into two types: (1) Metalliferous group (MS group) containing large amounts of sulfides and sulfate are enriched in Pb, Zn, Cu, Fe, Au, Ag, Ba, As, Hg, Se, Sb, Mo, slightly enriched in U, V, and have rare earth elements (REE) patterns similar to those of hydrothermal vent fluids and sulfides, indicating formation by a complex combination of wasting and erosion primary massive sulfide deposits and plume fallout of sulfides and sulfate. The occurrence of sphalerite with high contents of Fe and of co-existing pyrrhotite as major Fe-sulfide indicate that these minerals are formed at high temperature with low-sulfur fugacity in the Clam and Jade hydrothermal sites. The enrichment of Pb, Zn, Cu, Au, Ag, Ba, As, Hg, Se, Sb, and Mo is related to the presence of galena, sphalerite, Cu-sulfides, stibnite, and realgar in the sediments. (2) Non-metalliferous group (non-MS group) containing small amounts of pyrite are slightly enriched in Pb, Zn, Cu, Au, Ag, As, Hg, Se, Sb, and Mo relative to the East China Sea (ECS) continental shelf sediments, with REE exhibiting a “shale-like flat” patterns and close to Taiwan sediments in a REE discrimination plot, indicating formation by a large amount of terrigenous materials originated from Taiwan Island and a small amount of particles of sulfides in the hydrothermal nonbuoyant plume. The slight enrichment of Pb, Zn, Cu, Au, Ag, As, Hg, Se, Sb, and Mo maybe caused by co-precipitation with the fine-grained sulfides settling from the nonbuoyant plume. The positive relationships between the HREE fractionation index (Gd/Yb)N, heavy mineral proportion, and δEu suggest that (Gd/Yb)N can be used as a sensitive indicator for reflecting the effect of hydrothermal activity on the sediments.

Iron, copper, and zinc isotopic fractionation in seafloor basalts and hydrothermal sulfides

Studies of the Fe, Cu, and Zn isotopic compositions of volcanic rocks and sulfides provide an important tool for understanding magmatic, hydrothermal, and alteration processes, thereby enabling the determination of both transition metal sources and the quantification of the petrologic environmental impacts of hydrothermal activities. In this study, the δ56Fe and δ57Fe values of the mid-ocean ridge basalts (MORBs) are higher than those of the seafloor hydrothermal fluids, while the reverse is true for the δ66Zn and δ68Zn values, suggesting that basalt-fluid interactions preferentially incorporate isotopically light Fe and heavy Zn into the fluids, resulting in the relative enrichment of heavier Fe and lighter Zn isotopes in altered basaltic rocks. Most of the δ56Fe values (−1.96 to +0.11‰) of the sulfide minerals are within the range of the vent fluids, but they are significantly lower than those of the MORBs and back-arc basin basalts (BABBs), suggesting that the Fe in the sulfides was mainly derived from the fluids. However, the majority of the chalcopyrite δ56Fe and δ57Fe values are higher than those of the sphalerite and pyrite. This suggests that high-temperature sulfide minerals are enriched in 56Fe and 57Fe, whereas medium- and low-temperature sulfides are depleted in 56Fe and 57Fe. Moreover, the δ65Cu (−0.88 to −0.16‰) and δ66Zn (−0.39 to −0.03‰) values of the sulfide minerals are significantly lower than those of the MORBs, BABBs, and fluids, suggesting that 63Cu and 64Zn were preferentially removed from the fluids and incorporated into the chalcopyrite and sphalerite, respectively. Consequently, vent fluid injection and deposition can cause the heavier Cu and Zn isotopic compositions of hydrothermal plumes, seawater, and sediments.

Seafloor Incubation Experiment with Deep-Sea Hydrothermal Vent Fluid Reveals Effect of Pressure and Lag Time on Autotrophic Microbial Communities.

Depressurization and sample processing delays may impact the outcome of shipboard microbial incubations of samples collected from the deep sea. To address this knowledge gap, we developed a remotely operated vehicle (ROV)-powered incubator instrument to carry out and compare results from in situ and shipboard RNA stable isotope probing (RNA-SIP) experiments to identify the key chemolithoautotrophic microbes and metabolisms in diffuse, low-temperature venting fluids from Axial Seamount. All the incubations showed microbial uptake of labeled bicarbonate primarily by thermophilic autotrophic Epsilonbacteraeota that oxidized hydrogen coupled with nitrate reduction. However, the in situ seafloor incubations showed higher abundances of transcripts annotated for aerobic processes, suggesting that oxygen was lost from the hydrothermal fluid samples prior to shipboard analysis. Furthermore, transcripts for thermal stress proteins such as heat shock chaperones and proteases were significantly more abundant in the shipboard incubations, suggesting that depressurization induced thermal stress in the metabolically active microbes in these incubations. Together, the results indicate that while the autotrophic microbial communities in the shipboard and seafloor experiments behaved similarly, there were distinct differences that provide new insight into the activities of natural microbial assemblages under nearly native conditions in the ocean.IMPORTANCE Diverse microbial communities drive biogeochemical cycles in Earth's ocean, yet studying these organisms and processes is often limited by technological capabilities, especially in the deep ocean. In this study, we used a novel marine microbial incubator instrument capable of in situ experimentation to investigate microbial primary producers at deep-sea hydrothermal vents. We carried out identical stable isotope probing experiments coupled to RNA sequencing both on the seafloor and on the ship to examine thermophilic, microbial autotrophs in venting fluids from an active submarine volcano. Our results indicate that microbial communities were significantly impacted by the effects of depressurization and sample processing delays, with shipboard microbial communities being more stressed than seafloor incubations. Differences in metabolism were also apparent and are likely linked to the chemistry of the fluid at the beginning of the experiment. Microbial experimentation in the natural habitat provides new insights into understanding microbial activities in the ocean.

Distribution and Genetic Divergence of Deep-Sea Hydrothermal Vent Copepods (Dirivultidae: Siphonostomatoida: Copepoda) in the Northwestern Pacific.

Copepods in the family Dirivultidae are one of the most successful meiofauna in deep-sea hydrothermal vent fields and are abundant near venting fluid. Although vents are spatially limited ocean habitats, they are distributed widely in the Atlantic, Pacific, and Indian Oceans. However, knowledge of dirivultid biogeography and phylogeography remains limited, especially in the northwestern Pacific. Here, we obtained partial mitochondrial COI gene sequences of three dirivultids from the northwestern Pacific-Stygiopontius senokuchiae and an unidentified Chasmatopontius species from vent fields in the Izu-Bonin Arc and Stygiopontius senckenbergi associated with the squat lobster Shinkaia crosnieri in the Okinawa Trough-and analyzed them in comparison with existing data. The among-species sequence diversity exceeded 80 out of 560 bp (14% or 0.166 in Kimura 2-parameter distance), whereas the within-species diversity was less than 10 bp (2% or 0.018 in Kimura 2-parameter distance), with no genetic saturation. Each species formed a monophyletic clade and the genetic region targeted is deemed reliable for identifying species and populations for these copepods. Among the three genera targeted, only Chasmatopontius formed a monophyletic cluster, while Aphotopontius and Stygiopontius did not. Species delimitation analyses suggested the existence of cryptic species in Chasmatopontius. Subdivision among local populations was observed in Aphotopontius, but not in Stygiopontius in the same distribution, implying potential differences in dispersal ability among different genera of dirivultids. Further sampling is required, to fill the spatial gaps to elucidate the biogeography and evolution of dirivultids in the global deep ocean.

Organic Biogeochemistry in West Mata, NE Lau Hydrothermal Vent Fields

AbstractThe impact of submarine hydrothermal systems on organic carbon in the ocean—one of the largest fixed carbon reservoirs on Earth—could be profound. Yet, different vent sites show diverse fluid chemical compositions and the subsequent biological responses. Observations from various vent sites are to evaluate hydrothermal systems' impact on the ocean carbon cycle. A response cruise in May 2009 to an on‐going submarine eruption at West Mata Volcano, northeast Lau Basin, provided an opportunity to quantify the organic matter production in a back‐arc spreading hydrothermal system. Hydrothermal vent fluids contained elevated dissolved organic carbon, particulate organic carbon (POC), and particulate nitrogen (PN) relative to background seawater. The δ13C‐POC values for suspended particles in the diffuse vent fluids (−15.5‰ and −12.3‰) are distinct from those in background seawater (−23 ± 1‰), indicative of unique carbon synthesis pathways of the vent microbes from the seawater counterparts. The first dissolved organic nitrogen concentrations reported for diffuse vents were similar to or higher than those for background seawater. Enhanced nitrogen fixation and denitrification removed 37%–89% of the total dissolved nitrogen in the recharging background seawater in the hydrothermal vent flow paths. The hydrothermal plume samples were enriched in POC and PN, indicating enhanced biological production. The total “dark” organic carbon production within the plume matches the thermodynamic prediction based on available reducing chemical substances supplied to the plume. This research combines the measured organic carbon contents with thermodynamic modeled results and demonstrates the importance of hydrothermal activities on the water column carbon production in the deep ocean.

Geochemistry of vapor-dominated hydrothermal vent deposits in Yellowstone Lake, Wyoming

Yellowstone Lake hydrothermal vent systems have been studied using ROV assets to better understand the chemical and mineralogical evolution of the sublacustrine sediments through which the hot spring fluids discharge to the lake floor. Here we focus on the deposits/alteration and coexisting vent fluid chemistry associated with the Deep Hole on the lake floor, east of Stevenson Island. Remote in its location, at 120 m below the lake surface, this region in the northeast portion of Yellowstone Lake is associated with numerous hydrothermal vents and hot springs, providing evidence of high-temperature fluid-mineral interaction and phase separation phenomena. Vapor-dominated hydrothermal fluids issuing from Deep Hole vents attain temperatures in excess of 150 °C and are enriched in magmatically derived H2S and CO2. Upon mixing with lake water in the root zone of the hydrothermally active vents, the dissolved gases render the mixed fluid, both acidic and reducing, effectively transforming diatomaceous sediment, with detritally sourced Al and Fe components, to an alteration assemblage dominated by kaolinite, pyrite, and lesser boehmite. These alteration processes have been modeled by computer based simulations, coupling fluid flow and mineral dissolution kinetics, to provide insight on the temporal evolution of the vent system. Results predict rapid dissolution of amorphous silica. The magnitude and rate of silica loss, facilitated by the continuous influx of acidic source fluids, yields an increasingly silica poor alteration mineral sequence with time, characterized by quartz, followed by kaolinite and ultimately boehmite. These data are consistent with the observed decrease in SiO2/Al2O3 ratio of the vent deposits with increasing abundance of trace immobile elements, suggesting significant mass loss with reaction progress. Pyrite is predicted to form from sulfidation of magnetite, with noteworthy decrease in magnetic intensity, as measured for hydrothermally altered sediment in the near-field vent environment. Moreover, hydrogen isotope compositional data for kaolinite, together with δD vent fluid data, suggest temperatures in keeping with the high temperatures measured for the vent deposits and discharging fluid, while supporting the potential use of kaolinite as a geothermometer. The predicted and observed transformation of silica-rich protolith to kaolinite, boehmite, and pyrite underscores the large scale dissolution and removal of silica, with possible implications for the temporal evolution of vent deposits on the lake floor in the Stevenson Island Deep-Hole region.

In situ detection of the fine scale heterogeneity of active cold seep environment of the Formosa Ridge, the South China Sea

The active cold seep at Formosa Ridge (Site F) sustains the most flourishing ecosystem on the continental slope of the northern South China Sea. However, the physicochemical environment around the cold seep has scarcely been investigated. The knowledge about the variability of the seafloor habitat around the cold seep was poor and the key processes within the associated chemosynthetic ecosystem remain unclear. Here, we used an in situ integrated sensors detection approach combined with geochemical measurements to investigate the environmental condition around the chemosynthetic ecosystems fueled by the hydrocarbon seepage. Methane, hydrogen sulfide, dissolved oxygen and other biogenic elements in the bottom water were detected on a fine scale. The mixed gas composition and carbon isotope value of methane from the vent fluids suggested its origin was predominantly biogenic with slight thermogenic incorporation. Both horizontal and vertical variations in methane and oxygen concentrations were observed, which showed contrasting trends in fields from the center of flourishing communities to the margin of sediments. The concentration of methane decreased from 31,200 ppm at the flourishing center to 381 ppm at the margin on a horizontal gradient. The low concentration of hydrogen sulfide indicated that sulfide could be an energy-limiting factor for chemoautotrophic symbionts. The in situ oxygen levels were variable near the flourishing community but homogeneous at the margins. The results suggested that the availability of oxygen and methane played a substantial role in structuring the seep communities. Overall, from the flourishing center to the periphery, the chemical gradients drive the spatial distribution of chemosynthetic community at site F. The observations of the fine scale survey highlight the heterogeneity of microenvironments and provide novel information on the environmental dynamics within site F for the first time. • In situ detection of the fine scale environment in the cold seep were conducted. • Variations of methane and oxygen were observed from the center to the periphery. • The low sulfide level could be a limiting factor for the chemosynthetic community.

A 100-km wide slump along the upper slope of the Canadian Arctic was likely preconditioned for failure by brackish pore water flushing

Exploration of the continental slope of the Canadian Beaufort Sea has revealed a remarkable coalescence of slide scars with headwalls between 130 and 1100 m water depth (mwd). With increased depth, the scars widen and merge into one gigantic regional slide scar that is more than 100 km wide below ~1100 mwd. To understand the development of these features, five sites were investigated with an Autonomous Underwater Vehicle, which provided 1-m bathymetric grids and Chirp profiles, and surveyed with a Remotely Operated Vehicle. The morphologies are consistent with retrograde failures that occurred on failure planes located between 30 and 75 m below the modern seafloor. At issue is whether the continental slope in this area is preconditioned for failure. While rapid sedimentation during glacial periods, and the presence of shallow gas cannot be ruled out, given the geological environment, it is unclear that they are primary preconditioning factors. Evidence of widespread flushing of the slope with brackish waters, and observed flows of brackish water within slide scars, suggest fluid venting and overpressure may play a role in the development of the extensive slope failures seen along this margin. The impact of pore water salinity changes at the depth of the failure plane on slope stability has not been considered in marine settings previously.

The longevity of pockmarks – A case study from a shallow water body in northern Denmark

Pockmarks or crater-like depressions formed due to fluid venting, is a well-known geological phenomenon. On a global scale, pockmarks expel a significant amount of fluids and greenhouse gasses to the marine environment and the atmosphere. Despite pockmarks being well-studied, the longevity and history of activity are rarely addressed. In this study, we analyse more than twenty nearshore seafloor depressions of varying morphology and size in the shallow waters of the western Limfjord in northern Denmark. By using high-resolution seismo-acoustic and sediment core data, we characterize the morphology and sediments of the pockmarks. We further use 14C-dating and pore water analyses to address the timing and activity of the depressions. Our results show that the depressions coincide with submarine groundwater discharge areas and hence represent freshwater pockmarks. The pockmarks most likely formed initially due to two eruptive events of thermogenic light oil/gas ca. 2000 and 900 yrs. BP, both triggered by relative sea-level fall. Freshwater seepage continues to sustain and develop the pockmark morphology and we show that pockmarks grow by collapse of pockmark walls and amalgamation of discrete erosive seepage sites at the bottom. The episodic expulsions of thermogenic fluids and the continuous seepage of freshwater probably prolonged the longevity of the studied pockmarks and further demonstrates the complex nature of pockmark formation and activity. While thermogenic and biogenic gas escape to the surface, on the global scale, is relevant for the greenhouse gas budget, the outflow of groundwater which may or may not be polluted is relevant with respect to the geochemistry, biota and productivity of the receiving marine environment especially in shallow water settings.

Apatite nanoparticles in 3.46–2.46 Ga iron formations: Evidence for phosphorus-rich hydrothermal plumes on early Earth

AbstractPhosphorus is an essential nutrient that is thought to have regulated primary productivity in global oceans after the advent of oxygenic photosynthesis. The prime source of seawater phosphorus is regarded to be continental weathering of phosphate minerals. Ancient seawater phosphorus concentrations have been constrained using the phosphorus content of iron-rich chemical sediments—banded iron formations (BIFs); however, the removal processes and depositional phases remain unclear. Here we report that nanometer-sized apatite crystals (<500 nm) are ubiquitous in 3.46–2.46 Ga BIFs and cherts from the Kaapvaal (South Africa) and Yilgarn, and Pilbara (Western Australia) cratons. The apatite is uniformly dispersed in a chemical sediment comprising greenalite nanoparticles, which were encased in very early diagenetic silica cement that limited compaction and chemical reactions. The lack of organic carbon (below detection; <0.3 wt%) and absence of primary iron oxides implies that the phosphorus was not derived from the degradation of organic matter or seawater scavenging by oxide particles. Instead, the occurrence of apatite in sediments derived from hydrothermally sourced Fe2+ and SiO2(aq) suggests that phosphorus too was derived from vent plumes. Today, seawater P is rapidly removed from vent fluids due to scavenging by oxidized Fe2+. However, prior to the Great Oxidation Event (2.45–2.32 Ga), dissolved phosphorus released during anoxic alteration of seafloor basalts escaped the iron-oxidation trap. Our results point to the existence of a submarine hydrothermal flux of dissolved phosphorus that supplied nutrients to the early anoxic oceans. High amounts of seawater P may help to explain why phosphorus is ubiquitous in cell biology—it was not limiting during the origin and early evolution of life.

Sulfur and copper isotopic composition of seafloor massive sulfides and fluid evolution in the 26°S hydrothermal field, Southern Mid-Atlantic Ridge

In-situ sulfur isotopic compositions of morphologically different pyrites from the SMAR (southern Mid-Atlantic Ridge) 26°S hydrothermal field, integrated with δ34S and δ65Cu values in associated chalcopyrite, reflect a recurring flux of magmatic-hydrothermal fluids and subsequent leaching by seawater. The δ34S values of sulfides (−1.27 to +5.25‰) indicate mixing of magmatic sulfur with seawater sulfate-derived sulfur. Compared to other Mid-Ocean Ridge (MOR) hydrothermal vent sites, a significant contribution of magmatic fluids is herein distinctive. Three concentric mineralogical zones around the conduit in an inactive black smoker sample include an inner chalcopyrite-dominated zone, an intermediate zone of idiomorphic and massive pyrite, and an outermost zone of porous and colloform pyrite with/without traces of chalcopyrite. The systematic increase in δ34S from the interior conduit (avg. −0.60‰, n = 8) through the intermediate zone (avg. +2.36‰, n = 14) to the exterior wall (avg. +3.02‰, n = 27), and contributions of seawater sulfate (0 to 10.7%, and to 18.6%, respectively) are most likely related to interaction between hydrothermal fluid and previously precipitated sulfides. A significant contribution of seawater sulfate-derived sulfur occurred likely via permeability or porosity upsurge across the chimney. Chalcopyrite with consistently positive δ65Cu values (+0.17 to +0.48‰), which are typical of mid-ocean ridge (MOR) hydrothermal vent fluids, is suggestive of reaction/mixing with hydrothermal fluids. Sulfur and Cu isotopic compositions of chalcopyrite further imitate the significant contributions of magmatic gases in the formation of metalliferous seafloor massive sulfides.

Size speciation of dissolved trace metals in hydrothermal plumes on the Southwest Indian Ridge

Determining the size speciation and chemical transformation of trace metals is of paramount in order to better assess the impact of hydrothermal activities on the ocean metal budgets. In this study, we examined the concentration and size speciation of dissolved trace metals (i.e. Mn, Fe, Cu, Ni, Mo, As, Pb, Cd) in the hydrothermal plumes of two vent fields (i.e. Longqi and Tiancheng) on the Southwest Indian Ridge. The majority of dissolved Mn (75–100%) in the buoyant and non-buoyant plumes were presented as soluble Mn (<1 kDa), while dissolved Fe in the buoyant plume contained considerable colloidal Fe (54–95%). More than 66% of hydrothermally dissolved Fe was removed in the buoyant plume within a short distance of dispersion. Except for the samples most proximal to the fluid source, concentrations of Cu, Ni and Mo in the plumes were comparable to those of the background seawater and independent of the plume dilution. Concentrations of dissolved As and Pb in the buoyant plume of the Tiancheng field were higher than those of the Longqi field, resulting from the scavenging of As in the Longqi field and the release of Pb from metal sulfide dissolution in the Tiancheng field. Concentrations of dissolved Cd in the non-buoyant plume were nearly identical to the background seawater and soluble Cd was dominant (75–92%) in the soluble phase. In contrast, 33–96% (or 0.024–0.085 μg/kg) of dissolved Cd was removed in the buoyant plume and the remaining dissolved Cd was mainly in colloidal phase (up to 96%), suggesting that hydrothermal plume was likely an important sink of oceanic Cd and colloidal ligands played an important role in the stabilization of hydrothermal Cd. Our study has demonstrated the very dynamic nature of trace metal speciation in hydrothermal vent fluids.

Quantitative reconstruction of pore-pressure history in sedimentary basins using fluid escape pipes

Abstract We present a novel method to reconstruct the pressure conditions responsible for the formation of fluid escape pipes in sedimentary basins. We analyzed the episodic venting of high-pressure fluids from the crests of a large anticlinal structure that formed off the coast of Lebanon in the past 1.7 m.y. In total, 21 fluid escape pipes formed at intervals of 50–100 k.y. and transected over 3 km of claystone and evaporite sealing units to reach the seabed. From fracture criteria obtained from nearby drilling, we calculated that overpressures in excess of 30 MPa were required for their formation, with pressure recharge of up to 2 MPa occurring after each pipe-forming event, resulting in a sawtooth pressure-time evolution. This pressure-time evolution is most easily explained by tectonic overpressuring due to active folding of the main source aquifer while in a confined geometry.

Characterization and origin of large Campanian depressions within the Chalk Group of the Danish Central Graben – implications for hydrocarbon exploration and development

Abstract This study re-examines large and deep U-shaped reflections (2–4 km wide and 100–200 m deep) within the Upper Cretaceous–Danian Chalk Group in the inverted Roar Basin of the Danish North Sea, previously interpreted as a moat associated with a contour-parallel current system and/or erosive channels formed by gravity-driven turbidites. Improved 3D seismic data quality and seismic interpretation techniques helped to identify overlooked reflection terminations, which suggest that rather than a linear depression, the U-shaped reflections outline several bowl-shaped depressions. In addition, vertical high-amplitude columns and vertical discontinuity zones within and below the depressions were recognized and interpreted to indicate the presence of small fluid pipes, suggesting that the formation of the depressions is more complex. Carbon isotope analysis of high acoustic impedance beds within the underlying Lower Cretaceous chalk showed negative δ 13 C values down to −20‰, and are interpreted to indicate sediments influenced by methane-derived authigenic carbonates. Permo-Triassic half-grabens seem to have been a major source of gas-bearing fluids, as evidenced by hydrocarbon leakage phenomena within Triassic–Lower Cretaceous strata. In areas where Zechstein salt is present, the leakage root lies at salt welds, causing the formation of focused seismic reflection wipe-out and dim zones. In areas where salt was absent, the leakage root comprises a much more diffuse zone across the fault boundaries of the Permo-Triassic half-graben, and gas chimneys are characterized seismically as broad vertical dim zones up to 10 km wide. Campanian inversion tectonics caused fault reactivation and several hundreds of metres of uplift in the Roar Basin, which created an instability for the trapped gas-bearing fluids. Gentle fluid venting through observed pipes caused sediment suspension and entrainment, which could be carried away by bottom-current activity, causing localized zones of non-deposition and the formation of individual depressions. This model thus does not disregard the role of bottom-current activity in the formation of the depressions, yet it includes a fluid-venting element that fits better with the architecture and overall evidence for fluid-venting features in pre-chalk strata, as well as in the Chalk Group. Importantly, it shows that prior to the thermogenic maturation of the main source rock (i.e. the Bo Member of the Farsund Formation in the Late Miocene), fluid venting had already occurred on the Late Cretaceous seafloor from deeper source rocks that are at present overmature.

Fluid Circulation Along an Oceanic Detachment Fault: Insights From Fluid Inclusions in Silicified Brecciated Fault Rocks (Mid‐Atlantic Ridge at 13°20′N)

AbstractThe MAR 13°20′N corrugated detachment fault is composed of pervasively silicified mafic cataclastic breccias, instead of ultramafics and gabbros commonly found at other detachments. These breccias record overplating of hangingwall diabases, with syntectonic silicification due to important influx of silica‐iron‐rich fluids, able to leach alkalis and calcium. Fluids trapped in quartz inclusions show important salinity variations (2.1–10 wt.% NaCl eq.) indicating supercritical phase separation. Fluid inclusions also contain minor amounts of H2 ± CO2 ± CH4 ± H2S, with high H2/CO2 and H2/H2S ratios, signatures typical of ultramafic‐hosted vent fluids. We propose that seawater infiltrated the hangingwall upper crust at the axis adjacent to the active detachment, reaching a reaction zone at the dyke complex base (∼2 km). At &gt;500°C, fluids become Si‐rich during diabase alteration (amphibolite‐facies alteration in clasts), and undergo phase separation. Brines, preferentially released in the nearby detachment fault during diabase brecciation, mix with serpentinite‐derived fluids bearing H2 and CH4. Cooling during detachment deformation and fluid upward migration triggers silica precipitation at greenschist‐facies conditions (quartz + Fe‐rich‐chlorite ± pyrite). Important variations in fluid inclusion salinity and gas composition at both sample and grain scales record heterogeneous fluid circulation at small spatial and short temporal scales. This heterogeneous fluid circulation operating at &lt;2 km depth, extending both along‐axis and over time, is inconsistent with models of fluids channeled along detachments from heat sources at the base of the crust at the fault root. Present‐day venting at detachment footwall, including Irinovskoe, is instead likely underlain by fluid circulation within the footwall, with outflow crossing the inactive detachment fault near‐surface.

Arsenian Pyrite and Cinnabar from Active Submarine Nearshore Vents, Paleochori Bay, Milos Island, Greece

Active, shallow-water (2–10 m below sea level) and low temperature (up to 115 °C) hydrothermal venting at Paleochori Bay, nearshore Milos Island, Greece, discharges CO2 and H2S rich vapors (e.g., low-Cl fluid) and high-salinity liquids, which leads to a diverse assemblage of sulfide and alteration phases in an area of approximately 1 km2. Volcaniclastic detritus recovered from the seafloor is cemented by hydrothermal pyrite and marcasite, while semi-massive to massive pyrite-marcasite constitute mounds and chimney-like edifices. Paragenetic relationships indicate deposition of two distinct mineralogical assemblages related to the venting of high-Cl and low-Cl fluids, respectively: (1) colloform As- and Hg-bearing pyrite (Py I), associated with marcasite, calcite, and apatite, as well as (2) porous and/or massive As-rich pyrite (Py II), associated with barite, alunite/jarosite, and late-stage hydrous ferric oxides. Mercury, in the form of cinnabar, occurs within the As-rich pyrite (Py I) layers, usually forming distinct cinnabar-enriched micro-layers. Arsenic in colloform pyrite I shows a negative correlation with S indicating that As1− dominates in the pyrite structure suggesting formation from a relatively reducing As-rich fluid at conditions similar to low-sulfidation epithermal systems. On the contrary, As3+ dominates in the structure of porous to massive pyrite II suggesting deposition from a sulfate-dominated fluid with lower pH and higher fO2. Bulk sulfide data of pyrite-bearing hydrothermal precipitates also show elevated As (up to 2587 ppm) together with various epithermal-type elements, such as Sb (up to 274 ppm), Tl (up to 513 ppm), and Hg (up to 34 ppm) suggesting an epithermal nature for the hydrothermal activity at Paleochori Bay. Textural relationships indicate a contemporaneous deposition of As and Hg, which is suggested to be the result of venting from both high-salinity, liquid-dominated, as well as CO2- and H2S-rich vapor-dominated fluids that formed during fluid boiling. The CO2- and H2S-rich vapor that physically separated during fluid boiling from the high-salinity liquid led to calcite formation upon condensation in seawater together with the precipitation of As- and Hg-bearing pyrite I. This also led to the formation of sulfuric acid, thereby causing leaching and dissolution of primary iron-rich minerals in the volcaniclastic sediments, finally resulting in pyrite II precipitation in association with alunite/jarosite. The Paleochori vents contain the first documented occurrence of cinnabar on the seafloor in the Mediterranean area and provide an important link between offshore hydrothermal activity and the onshore mercury and arsenic mineralizing system on Milos Island. The results of this study therefore demonstrate that metal and metalloid precipitation in shallow-water continental arc environments is controlled by epithermal processes known from their subaerial analogues.

Molecular analyses of the gill symbiosis of the bathymodiolin mussel Gigantidas platifrons.

SummaryAlthough the deep-sea bathymodiolin mussels have been intensively studied as a model of animal-bacteria symbiosis, it remains challenging to assess the host-symbiont interactions due to the complexity of the symbiotic tissue—the gill. Using cold-seep mussel Gigantidas platifrons as a model, we isolated the symbiont harboring bacteriocytes and profiled the transcriptomes of the three major parts of the symbiosis—the gill, the bacteriocyte, and the symbiont. This breakdown of the complex symbiotic tissue allowed us to characterize the host-symbiont interactions further. Our data showed that the gill's non-symbiotic parts play crucial roles in maintaining and protecting the symbiosis; the bacteriocytes supply the symbiont with metabolites, control symbiont population, and shelter the symbiont from phage infection; the symbiont dedicates to the methane oxidation and energy production. This study demonstrates that the bathymodiolin symbiosis interacts at the tissue, cellular, and molecular level, maintaining high efficiency and harmonic chemosynthetic micro niche.