Sub-seafloor Phase Separation Research Articles

Geochemical indications of hydrothermal fluid through sediments within the Geolin Mounds and Mienhua Volcano hydrothermal fields, southernmost Okinawa Trough

This study focused on the chemistry of sedimentary pore fluids to clarify hydrothermal fluid migrating within sediments at the Geolin Mounds (GLM) and Mienhua Volcano (MHV) hydrothermal fields, southernmost Okinawa Trough, where are characterized by covering of thick sediment. The significant downward decrease in Mg2+ (low to 23.3 mmol L−1) and concurrent increase in Li+ (up to 2,269 μmol L−1) in sedimentary pore fluids implied a substantial influence of hydrothermal fluid, which might be associated with high-temperature (>350 °C) rock/sediment-fluid interaction. The best fitting of the 1-D advection-diffusion equation to pore-fluid Cl−, Mg2+, and Li+ concentrations further evidenced the upward hydrothermal through sediments with rates of 0.13 ∼ 124 cm yr−1. The apparently Cl-depleted and slightly Cl-enriched pore fluids in the GLM and MHV hydrothermal fields supported the occurrence of subseafloor phase separation and classified their hydrothermal fluids into vapor-rich and brine-rich phases, respectively. The low pH values (pH = 5.67 ∼ 6.21) with downward increasing trends of pore-fluid dissolved inorganic carbon (DIC, up to 60 mmol L−1) and its heavy isotopic compositions (δ13CDIC = +2.5 ∼ +7.0 ‰) inferred in-situ liquid CO2-impregnated sedimentary circumstance in the GLM and MHV hydrothermal fields. This sedimentary environment, as demonstrated, enhanced the chemical weathering of silicate and carbonate minerals, resulting in the elevated concentrations of Ca2+ and K+ in pore fluids. It highlights the impact of acidic and in-situ CO2-saturated fluids within sediments on geochemical alterations of bulk solids/sediments and interstitial fluids.

Subcritical Phase Separation and Occurrence of Deep-Seated Brines at the NW Caldera Vent Field, Brothers Volcano: Evidence from Fluid Inclusions in Hydrothermal Precipitates

The northwestern caldera wall of Brothers volcano in the southern Kermadec arc features several clusters of hydrothermal venting in a large area that extends from near the caldera floor (~1700 mbsl) almost up to the crater rim (~1300 mbsl). Abundant black smoker-type hydrothermal chimneys and exposed stockwork mineralization in this area provide an excellent archive of hydrothermal processes that form seafloor massive sulfide deposits. Using sulfate precipitates from chimneys and stockwork recently recovered by remotely operated vehicles, we conducted fluid inclusion microthermometry and Sr isotope studies to determine the role of phase separation and mixing between vent fluid and seawater. The variability in the vast majority of fluid inclusion salinities (i.e., 0.1–5.25 wt.% NaCl eq.) and entrapment temperatures of up to 346°C are indicative of phase-separated hydrothermal fluids. Large salinity variations in samples with entrapment temperatures mostly below the boiling temperature for the sample’s depth show that the majority of fluids ascending below the NW Caldera are phase separating in the subsurface and cooling, prior to discharge. In several samples, entrapment temperatures of over 343°C suggest that phase-separating fluids have at least sporadically exited the seafloor at the NW Caldera site. Isobaric-isenthalpic mixing trends between coexisting phase-separated vapors and brines with seawater are consistent with phase-separated fluids at near-seafloor pressures of ~170 bar and suggest that the vast majority of the ascending fluids continue to phase separate to within tens to hundreds of meters below seafloor prior to mixing with seawater. A small subset of the most saline fluid inclusions (up to 18.6 wt.% NaCl eq.) is unlikely formed by near-seafloor phase separation and is considered to be produced either by supercritical phase separation or by the contribution of a magmatic brine from near the magmatic-hydrothermal interface. 87Sr/86Sr values of sulfate samples range from 0.7049 (i.e., near hydrothermal end-member) to 0.7090 (i.e., near seawater) and show that the crystals grew from vapor- and brine-derived fluids in a hydrothermally dominated mixing regime. Our work provides new insights into mineral growth conditions, mixing regimes, and in particular, the extent and character of subseafloor phase separation during the formation of hydrothermal vents and their underlying stockwork in seawater-dominated, arc-related hydrothermal systems.

Hydrodynamic modeling of magmatic–hydrothermal activity at submarine arc volcanoes, with implications for ore formation

Subduction-related magmas have higher volatile contents than mid-ocean ridge basalts, which affects the dynamics of associated submarine hydrothermal systems. Interaction of saline magmatic fluids with convecting seawater may enhance ore metal deposition near the seafloor, making active submarine arcs a preferred modern analogue for understanding ancient massive sulfide deposits.We have constructed a quantitative hydrological model for sub-seafloor fluid flow based on observations at Brothers volcano, southern Kermadec arc, New Zealand. Numerical simulations of multi-phase hydrosaline fluid flow were performed on a two-dimensional cross-section cutting through the NW Caldera and the Upper Cone sites, two regions of active venting at the Brothers volcanic edifice, with the former hosting sulfide mineralization. Our aim is to explore the flow paths of saline magmatic fluids released from a crystallizing magma body at depth and their interaction with seawater circulating through the crust. The model includes a 3×2 km2 sized magma chamber emplaced at ∼2.5 km beneath the seafloor connected to the permeable cone via a ∼200 m wide feeder dike. During the simulation, a magmatic fluid was temporarily injected from the top of the cooling magma chamber into the overlying convection system, assuming hydrostatic conditions and a static permeability distribution.The simulations predict a succession of hydrologic regimes in the subsurface of Brothers volcano, which can explain some of the present-day hydrothermal observations. We find that sub-seafloor phase separation, inferred from observed vent fluid salinities, and the temperatures of venting at Brothers volcano can only be achieved by input of a saline magmatic fluid at depth, consistent with chemical and isotopic data. In general, our simulations show that the transport of heat, water, and salt from magmatic and seawater sources is partly decoupled. Expulsion of magmatic heat and volatiles occurs within the first few hundred years of magma emplacement in the form of rapidly rising low-salinity vapor-rich fluids. About 95% of the magmatically derived salt is temporarily trapped in the crust, either as dense brine or as precipitated halite. This retained salt can only be expelled by later convection of seawater during the waning period of the hydrothermal system (i.e., “brine mining”).While the abundant mineralization of the NW Caldera vent field at Brothers could not be classified as an economic ore deposit, our model has important implications for submarine metal enrichment and the origin of distinct ore types known from exposed systems on land. Sulfide-complexed metals (notably Au) will preferentially ascend during early vapor-dominated fluid expulsion, potentially forming gold ± copper rich vein and replacement deposits in near-seafloor zones of submarine volcanoes. Dense magmatic brine will initially accumulate chloride-complexed base metals (such as Cu, Fe, Pb and Zn) at depth before they are mobilized by seawater convection. The resulting mixed brines can become negatively buoyant when they reach the seafloor and may flow laterally towards depressions, potentially forming layers of base metal sulphides with distinct zonation of metals.

Discovery of a new hydrothermal vent based on an underwater, high-resolution geophysical survey

A new hydrothermal vent site in the Southern Mariana Trough has been discovered using acoustic and magnetic surveys conducted by the Japan Agency for Marine-Earth Science and Technology's (JAMSTEC) autonomous underwater vehicle (AUV), Urashima. The high-resolution magnetic survey, part of a near-bottom geophysical mapping around a previously known hydrothermal vent site, the Pika site, during the YK09-08 cruise in June–July 2009, found that a clear magnetization low extends ∼500m north from the Pika site. Acoustic signals, suggesting hydrothermal plumes, and 10m-scale chimney-like topographic highs were detected within this low magnetization zone by a 120kHz side-scan sonar and a 400kHz multibeam echo sounder. In order to confirm the seafloor sources of the geophysical signals, seafloor observations were carried out using the deep-sea manned submersible Shinkai 6500 during the YK 10-10 cruise in August 2010. This discovered a new hydrothermal vent site (12°55.30′N, 143°38.89′E; at a depth of 2922m), which we have named the Urashima site. This hydrothermal vent site covers an area of approximately 300m×300m and consists of black and clear smoker chimneys, brownish-colored shimmering chimneys, and inactive chimneys. All of the fluids sampled from the Urashima and Pika sites have chlorinity greater than local ambient seawater, suggesting subseafloor phase separation or leaching from rocks in the hydrothermal reaction zone. End-member compositions of the Urashima and Pika fluids suggest that fluids from two different sources feed the two sites, even though they are located on the same knoll and separated by only ∼500m. We demonstrate that investigations on hydrothermal vent sites located in close proximity to one another can provide important insights into subseafloor hydrothermal fluid flow, and also that, while such hydrothermal sites are difficult to detect by conventional plume survey methods, high-resolution underwater geophysical surveys provide an effective means.

Comparison of microbial communities associated with phase-separation-induced hydrothermal fluids at the Yonaguni Knoll IV hydrothermal field, the Southern Okinawa Trough

Microbial communities associated with a variety of hydrothermal emissions at the Yonaguni Knoll IV hydrothermal field, the southernmost Okinawa Trough, were analyzed by culture-dependent and -independent techniques. In this hydrothermal field, dozens of vent sites hosting physically and chemically distinct hydrothermal fluids were observed. Variability in the gas content and formation in the hydrothermal fluids was observed and could be controlled by the potential subseafloor phase-separation and -partition processes. The hydrogen concentration in the hydrothermal fluids was also variable (0.8-3.6 mmol kg(-1)) among the chimney sites, but was unusually high as compared with those in other Okinawa Trough hydrothermal fields. Despite the physical and chemical variabilities of the hydrothermal fluids, the microbial communities were relatively similar among the habitats. Based on both culture-dependent and -independent analyses of the microbial community structures, members of Thermococcales, Methanococcales and Desulfurococcales likely represent the predominant archaeal components, while members of Nautiliaceae and Thioreductoraceae are considered to dominate the bacterial population. Most of the abundant microbial components appear to be chemolithotrophs sustained by hydrogen oxidation. The relatively consistent microbial communities found in this study could have been because of the sufficient input of hydrogen from the hydrothermal fluids rather than other chemical properties.

Diverse Range of Mineralization Induced by Phase Separation of Hydrothermal Fluid: Case Study of the Yonaguni Knoll IV Hydrothermal Field in the Okinawa Trough Back‐Arc Basin

AbstractThe Yonaguni Knoll IV hydrothermal vent field (24°51′N, 122°42′E) is located at water depths of 1370–1385 m near the western edge of the southern Okinawa Trough. During the YK03–05 and YK04–05 expeditions using the submersible Shinkai 6500, both hydrothermal precipitates (sulfide/sulfate/carbonate) and high temperature fluids (Tmax = 328°C) presently venting from chimney‐mound structures were extensively sampled. The collected venting fluids had a wide range of chemistry (Cl concentration 376–635 mmol kg−1), which is considered as evidence for sub‐seafloor phase separation. While the Cl‐enriched smoky black fluids were venting from two adjacent chimney‐mound structures in the hydrothermal center, the clear transparent fluids sometimes containing CO2 droplet were found in the peripheral area of the field. This distribution pattern could be explained by migration of the vapor‐rich hydrothermal fluid within a porous sediment layer after the sub‐seafloor phase separation. The collected hydrothermal precipitates demonstrated a diverse range of mineralization, which can be classified into five groups: (i) anhydrite‐rich chimneys, immature precipitates including sulfide disseminations in anhydrite; (ii) massive Zn‐Pb‐Cu sulfides, consisting of sphalerite, wurtzite, galena, chalcopyrite, pyrite, and marcasite; (iii) Ba‐As chimneys, composed of barite with sulfide disseminations, sometimes associated with realgar and orpiment overgrowth; (iv) Mn‐rich chimneys, consisting of carbonates (calcite and magnesite) and sulfides (sphalerite, galena, chalcopyrite, alabandite, and minor amount of tennantite and enargite); and (v) pavement, silicified sediment including abundant native sulfur or barite. Sulfide/sulfate mineralization (groups i–iii) was found in the chimney–mound structure associated with vapor‐loss (Cl‐enriched) fluid venting. In contrast, the sulfide/carbonate mineralization (group iv) was specifically found in the chimneys where vapor‐rich (Cl‐depleted) fluid venting is expected, and the pavement (group v) was associated with diffusive venting from the seafloor sediment. This correspondence strongly suggests that the subseafloor phase separation plays an important role in the diverse range of mineralization in the Yonaguni IV field. The observed sulfide mineral assemblage was consistent with the sulfur fugacity calculated from the FeS content in sphalerite/wurtzite and the fluid temperature for each site, which suggests that the shift of the sulfur fugacity due to participation of volatile species during phase separation is an important factor to induce diverse mineralization. In contrast, carbonate mineralization is attributed to the significant mixing of vapor‐rich hydrothermal fluid and seawater. A submarine hydrothermal system within a back‐arc basin in the continental margin may be considered as developed in a geologic setting favorable to a diverse range of mineralization, where relatively shallow water depth induces sub‐seafloor phase separation of hydrothermal fluid, and sediment accumulation could enhance migration of the vapor‐rich hydrothermal fluid.

Evolution of a Submarine Magmatic-Hydrothermal System: Brothers Volcano, Southern Kermadec Arc, New Zealand

Brothers volcano, which is part of the active Kermadec arc, northeast of New Zealand, forms an elongate edifice 13 km long by 8 km across that strikes northwest-southeast. The volcano has a caldera with a basal diameter of ~3 km and a floor at 1,850 m below sea level, surrounded by 290- to 530-m-high walls. A volcanic cone of dacite rises 350 m from the caldera floor and partially coalesces with the southern caldera wall. Three hydrothermal sites have been located: on the northwest caldera wall, on the southeast caldera wall, and on the dacite cone. Multiple hydrothermal plumes rise ~750 m through the water column upward from the caldera floor, originating from the northwest caldera walls and atop the cone, itself host to three separate vent fields (summit, upper flank, northeast flank). In 1999, the cone site had plumes with relatively high concentrations of gas with a ΔpH of −0.27 relative to seawater (proxy for CO2 + S gases), dissolved H2S up to 4,250 nM, high concentrations of particulate Cu (up to 3.4 nM), total dissolvable Fe (up to 4,720 nM), total dissolvable Mn (up to 260 nM) and Fe/Mn values of 4.4 to 18.2. By 2002, plumes from the summit vent field had much lower particulate Cu (0.3 nM), total dissolvable Fe (175 nM), and Fe/Mn values of 0.8 but similar ΔpH (−0.22) and higher H2S (7,000 nM). The 1999 plume results are consistent with a magmatic fluid component with the concentration of Fe suggesting direct exsolution of a liquid brine, whereas the much lower concentrations of metals but higher overall gas contents in the 2002 plumes likely reflect subsea-floor phase separation. Plumes above the northwest caldera site are chemically distinct, and their compositions have not changed over the same 3-year interval. They have less CO2 (ΔpH of −0.09), no detectable H2S, total dissolved Fe of 955 nM, total dissolved Mn of 150 nM, and Fe/Mn of 6.4. An overall increase in 3He/4He values in the plumes from R/RA = 6.1 in 1999 to 7.2 in 2002 is further consistent with a magmatic pulse perturbing the system. The northwest caldera site is host to at least two large areas (~600 m by at least 50 m) of chimneys and sub-cropping massive sulfide. One deposit is partially buried by sediment near the caldera rim at ~1,450 m, whereas the other crops out along narrow, fault-bounded ledges between ~1,600 and 1,650 m. Camera tows imaged active 1- to 2-m-high black smoker chimneys in the deeper zone together with numerous 1- to 5-m-high inactive spires, abundant sulfide talus, partially buried massive sulfides, and hydrothermally altered volcanic rocks. 210Pb/226Ra dating of one chimney gives an age of 27 ± 6 years; 226Ra/Ba dating of other mineralization indicates ages up to 1,200 years. Formation temperatures derived from Δ34Ssulfate-sulfide mineral pairs are 245° to 295° for the northwest caldera site, 225° to 260°C for the southeast caldera and ~260° to 305°C for the cone. Fluid inclusion gas data suggest subsea-floor phase separation occurred at the northwest caldera site. Alteration minerals identified include silicates, silica polymorphs, sulfates, sulfides, Fe and Mn oxide and/or oxyhydroxides, and native sulfur, which are consistent with precipitation at a range of temperatures from fluids of different compositions. An advanced argillic assemblage of illite + amorphous silica + natroalunite + pyrite + native S at the cone site, the occurrence of chalcocite + covellite + bornite + iss + chalcopyrite + pyrite in sulfide samples from the southeast caldera site, and veins of enargite in a rhyodacitic sample from the northwest caldera site are indicative of high-sulfidation conditions similar to those of subaerial magmatic-hydrothermal systems. The northwest caldera vent site is a long-lived hydrothermal system that is today dominated by evolved sea-water but has had episodic injections of magmatic fluid. The southeast caldera site represents the main upflow of a relatively well established magmatic-hydrothermal system on the sea floor where sulfide-rich chimneys are extant. The cone site is a nascent magmatic-hydrothermal system where crack zones localize upwelling acidic waters. Each of these different vent sites represents diverse parts of an evolving hydrothermal system, any one of which may be typical of submarine volcanic arcs.

Variability in microbial community and venting chemistry in a sediment-hosted backarc hydrothermal system: Impacts of subseafloor phase-separation

Phase-separation and -segregation (boiling/distillation of subseafloor hydrothermal fluids) represent the primary mechanisms causing intra-field variations in vent fluid compositions. To determine whether this geochemical process affects the formation of microbial communities, we examined the microbial communities at three different vent sites located within a few tens meters of one another. In addition to chimney structures, colonization devices capturing subseafloor communities entrained by the vent fluids were studied, using culture-dependent and -independent methods. Microbiological analyses demonstrated the occurrence of distinctive microbial communities in each of the hydrothermal niches. Within a chimney structure, there was a transition from a mixed community of mesophiles and thermophiles in the exterior parts to thermophiles in the interior. Beside the transition within a chimney structure, intra-field variations in microbial communities in vent fluids were apparent. Geochemical analysis demonstrated that different vent fluids have distinctive end-member compositions as a consequence of subseafloor phase-separation and -segregation, which were designated gas-depleted, normal and gas-enriched fluids. In comparison to gas-depleted and normal fluids, gas-enriched fluids harbored more abundant chemolithoautotrophs with gaseous component-dependent energy metabolism, such as hydrogenotrophic methanogenesis. Subseafloor phase-separation and -segregation may play a key role in supplying energy and carbon sources to vent-associated chemolithoautotrophs and subvent microbial communities.

Hydrothermal fluids associated with seafloor mineralization at two southern Kermadec arc volcanoes, offshore New Zealand

Massive sulfide samples have been recovered from Brothers and Rumble II West volcanoes of the southern Kermadec frontal arc, northeast of New Zealand. Both are caldera-forming volcanoes with Brothers largely dacitic and Rumble II West basaltic to basaltic-andesite in composition. The sulfide samples are considered to be pieces of chimneys from near the base of the caldera walls and are dominated by Cu–Fe–Ba ± Pb (chalcopyrite–pyrite–barite ± galena) and to a lesser extent, Zn–Fe–Ba ± Pb (sphalerite–pyrite–barite ± galena) mineralization. Gold is present in the samples up to 6.1 ppm. Paragenetic relationships suggest that the two hydrothermal systems have heated up and later cooled down. Oxidation of the sulfides is common and suggests that parts of the deposits are relatively old. Fluid inclusion microthermometric data show salinities fall predominantly in the range 3.0 to 3.4 wt% NaCl equivalent, similar to seawater values (3.2 wt%). About 15% of the Brothers salinity data range to both lower (2.2 wt%) and higher (3.9 wt%) than seawater values. Homogenization temperatures for type I inclusions in barite range between 175 and 322 °C for the Brothers samples, and between 205 and 268 °C for one Rumble II West sample. A dramatic decrease in temperature and/or change in the oxidation state of the hydrothermal fluid are considered the main mechanisms responsible for gold deposition at the Kermadec vent sites. This was achieved by mixing the hydrothermal fluid with ambient seawater within what are inferred to have been <300 °C "white smoker" chimneys, consistent with S isotope results. Fluid inclusion volatiles are dominated by H2O (99.81–99.98 mol%) followed by CO2 (0.03–0.17) and lesser amounts of N2 (0.004–0.023), CH4 (0.002–0.026) and trace COS and C2–C3 hydrocarbons. Fluid inclusions hosted by barite contain noticeably lesser amounts of gas than those within sulfides, consistent with mixing. The source of the relatively high concentrations of CH4 is enigmatic, although may be related to the thermal degradation of organic-rich sediments intercalated within the volcanic pile. Addition of a pressure correction and the effect of dissolved gases show that the hydrothermal fluids did not boil at the chimney depths. However, the range of measured salinities in the Brothers field combined with slightly positive trends in fluid inclusion CO2/CH4 versus CO2/N2 plots suggest sub-seafloor phase separation may have occurred in the hydrothermal system prior to venting.