Hydrothermal alteration of basalt by seawater under seawater-dominated conditions

Fresh mid-ocean ridge basalt glass and diabase have been reacted with seawater at 150–300°C, 500 bar, and water/rock mass ratios of 50, 62, and 125, using experimental apparatus which allowed on-line sampling of solution to monitor reaction progress. These experiments characterize reaction under what we have called “seawater-dominated” conditions of hydrothermal alteration.In an experiment at 300°C, basalt glass undergoing alteration removed nearly all Mg²⁺ from an amount of seawater 50 times its own mass. In the process, the glass was converted entirely to mixed-layer smectite-chlorite, anhydrite, and minor hematite. Removal of Mg from seawater occurred as a Mg(OH)₂ component incorporated into the secondary clay. This produced a precipitous drop in solution pH early in the experiment, accompanied by a dramatic increase in the concentrations of Fe, Mn, and Zn in solution. As Mg removal neared completion and the glass was hydrolyzed, pH rose again and heavy metal concentrations dropped.At water/rock ratios of 62 and 125 and 150–300°C, the mineral assemblage produced was similar to that at a water/rock ratio of 50. Solution chemistry, however, contrasted with the earlier experiment in that Mg concentrations in solution were greater and pH lower. This caused significant leaching of heavy metals. At 300°C nearly all of the Na, Ca, Cu, Zn, and CO₂ and most of the K, Ba, Sr, and Mn were leached from the silicates. H₂S, Al, Si, and possibly Co were also significantly mobilized, whereas V, Cr, and Ni were not. Little or no seawater sulfate was reduced.Although submarine hot spring solutions sampled to date along mid-ocean ridges clearly come from rock-dominated hydrothermal systems, evidence from ocean floor metabasalts and from heat flow studies indicates that seawater-dominated conditions of alteration prevail at least locally both in axial hightemperature systems and in ridge flank systems at lower temperatures.     

Low temperature basalt alteration by sea water: an experimental study at 70°C and 150°C

Basaltic glass and diabase were reacted with seawater at 70°C at 1 bar and 150°C at 500 bars to determine fluid composition and alteration mineralogy. All experiments were performed at a water/ rock mass ratio of 10.The changes in seawater chemistry depended on temperature and crystallinity of the basalt. The experiment at 70°C produced a slight but continuous loss of Mg, Na and K and enrichment of Ca and SiO₂ in the seawater while pH decreased slowly. At 150°C, in contrast, Mg and SO₄ were quickly and quantitatively removed while Ca, SiO₂, Na, K, Fe, Mn and Ba were added to the seawater. pH rose to values between 5.5 and 6.5 after an initial drop to lower values. Basalt glass reacted more extensively at 150°C than diabase.Smectite was the major alteration product (iron-rich saponite) at 150°C for both the glass and diabase experiments. Smectite from the diabase experiment was well crystallized while that from the glass experiment was poorly crystallized. The smectites are similar to smectites found in altered oceanic ophiolitic basalts.     

Sulfide remobilization during low temperature alteration of seafloor basalt

The behavior of sulfide minerals during the physical and chemical changes accompanying seafloor alteration was studied in three basalt flows from the bottom of D.S.D.P. Hole 418A, Leg 53. The rocks are mildly altered, and contain primary, authigenic, and vein sulfide minerals. Sulfide habit, mineralogy, and trace element content are inter-related and are correlated with the extent and type of silicate and oxide alteration. Incipient alteration at > 90°–100°C was accompanied by low temperature reequilibration of pyrrhotite, and locally, by the oxidation of pyrrhotite to pyrite plus magnetite. The dominant stage of alteration, at ≤90°C, is characterized by dissolution and local redistribution of pyrite and chalcopyrite, whose precipitation appears to be controlled by the water/rock ratio and the extent to which the water has been modified by reaction with the basalt. Chalcopyrite was concentrated relative to pyrite by slight changes in fluid composition caused by reaction with other minerals. Concurrent precipitation of smectite causes a net increase in rock volume, tending to restrict seawater access. Calculations of rock cooling rate through time suggest that the most prolonged hydrothermal circulation occurs at low temperatures, giving rise to pervasive low temperature alteration assemblages.     

Platinum-group elements, S, Se and Cu in highly depleted abyssal peridotites from the Mid-Atlantic Ocean Ridge (ODP Hole 1274A): Influence of hydrothermal and magmatic processes

Highly depleted harzburgites and dunites were recovered from ODP Hole 1274A, near the intersection between the Mid-Atlantic Ocean Ridge and the 15°20′N Fracture Zone. In addition to high degrees of partial melting, these peridotites underwent multiple episodes of melt–rock reaction and intense serpentinization and seawater alteration close to the seafloor. Low concentrations of Se, Cu and platinum-group elements (PGE) in harzburgites drilled at around 35–85 m below seafloor are consistent with the consumption of mantle sulfides after high degrees (>15–20 %) of partial melting and redistribution of chalcophile and siderophile elements into PGE-rich residual microphases. Higher concentrations of Cu, Se, Ru, Rh and Pd in harzburgites from the uppermost and lowest cores testify to late reaction with a sulfide melt. Dunites were formed by percolation of silica- and sulfur-undersaturated melts into low-Se harzburgites. Platinum-group and chalcophile elements were not mobilized during dunite formation and mostly preserve the signature of precursor harzburgites, except for higher Ru and lower Pt contents caused by precipitation and removal of platinum-group minerals. During serpentinization at low temperature (<250 °C) and reducing conditions, mantle sulfides experienced desulfurization to S-poor sulfides (mainly heazlewoodite) and awaruite. Contrary to Se and Cu, sulfur does not record the magmatic evolution of peridotites but was mostly added in hydrothermal sulfides and sulfate from seawater. Platinum-group elements were unaffected by post-magmatic low-temperature processes, except Pt and Pd that may have been slightly remobilized during oxidative seawater alteration.     

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: Interaction of seawater with fayalite and magnetite at 200–350°C

Sulfate reduction during seawater reaction with fayalite and with magnetite was rapid at 350°C, producing equilibrium assemblages of talc-pyrite-hematite-magnetite at low water/rock ratios and talc-pyrite-hematite-anhydrite at higher water/rock ratios. At 250°C, seawater reacting with fayalite produced detectable amounts of dissolved H₂S, but extent of reaction of solid phases was minor after 150 days. At 200°C, dissolved H₂S was not detected, even after 219 days, but mass balance calculations suggest a small amount of pyrite may have formed. Reaction stoichiometry indicates that sulfate reduction requires large amounts of H⁺, which, in subseafloor hydrothermal systems is provided by Mg metasomatism. Seawater contains sufficient Mg to supply all the H⁺ necessary for quantitative reduction of seawater sulfate.Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H₂S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.     

An experimental investigation of high-temperature interactions between seawater and rhyolite,andesite, basalt and peridotite

Natural seawater was allowed to react with rhyolite, andesite, basalt, and peridotite at 200°–500° C, and 1,000 bars at water/rock mass ratios of 5 and 50 in order to investigate the effects of rock type, water/rock ratio, and temperature on solution chemistry and alteration mineralogy. The results indicate that interactions of seawater with various igneous rocks are similar in the production of a hydrous Mg-silicate and anhydrite as major alteration products. Fluids involved in the interactions lose Mg to alteration phases while leaching Fe, Mn, and Si from the rocks. The pH of the solutions is primarily controlled by Mg-OH-silicate formation and therefore varies with Mg and Si concentration of the system. Other reactions which involve Mg (such as Mg-Ca exchange) or which produce free H⁺, cause major differences in fluid chemistry between different seawater/ rock systems. High water/rock ratio systems (50/1) are generally more acidic and more efficient in leaching than low ratio systems (5/1), due to relatively more seawater Mg available for Mgsilicate production. The experiments show that large-scale seawater/rock interaction could exert considerable control on the chemistry of seawater, as well as producing large bodies of altered rock with associated ore-deposits.Active plate margins of convergence or divergence are suitable environments for hydrothermal systems due to the concurrence of igneous activity, tectonism, and a nearby water reservoir (seawater or connate water). The experimental data indicate that seawater interactions with igneous host rocks could generate many of the features of ore-deposits such as the Kuroko deposits of Japan, the Raul Mine of Peru, the Bleida deposit of Morocco, and deposits associated with ophiolites. Serpentinization of peridotite and alteration of igneous complexes associated with plate margins can also be explained by seawater interaction with the cooling rock. Geothermal energy production could benefit from experimental investigations of hot water/rock systems by development of chemical, temperature, and pressure control systems to maximize the lifetime of hydrothermal flow.     

Isotopic and element exchange during serpentinization and metasomatism at the Atlantis Massif (MAR 30°N): Insights from B and Sr isotope data

The Lost City hydrothermal system at the southern Atlantis Massif (Mid-Atlantic Ridge, 30°N) provides a natural laboratory for studying serpentinization processes, the temporal evolution of ultramafic-hosted hydrothermal systems, and alteration conditions during formation and emplacement of an oceanic core complex. Here we present B, O, and Sr isotope data to investigate fluid/rock interaction and mass transfer during detachment faulting and exhumation of lithospheric sequences within the Atlantis Massif. Our data indicate that extensive serpentinization was a seawater-dominated process that occurred predominately at temperatures of 150-250 °C and at high integrated W/R ratios that led to a marked boron enrichment (34-91 ppm). Boron removal from seawater during serpentinization is positively correlated with changes in δ¹¹B (11-16‰) but shows no correlation with O-isotope composition. Modeling indicates that B concentrations and isotope values of the serpentinites are controlled by transient temperature-pH conditions. In contrast to prior studies, we conclude that low-temperature marine weathering processes are insignificant for boron geochemistry of the Atlantis Massif serpentinites. Talc- and amphibole-rich fault rocks formed within a zone of detachment faulting at temperatures of approximately 270-350 °C and at low W/R ratios. Talc formation in ultramafic domains in the massif was subsequent to an early stage of serpentinization and was controlled by the access of Si-rich fluids derived through seawater-gabbro interactions. Replacement of serpentine by talc resulted in boron loss and significant lowering of δ¹¹B values (9-10‰), which we model as the product of progressive extraction of boron. Our study provides new constraints on the boron geochemical cycle at oceanic spreading ridges and suggests that serpentinization associated with ultramafic-hosted hydrothermal systems may have important implications for the behavior of boron in subduction zone settings.     

Chemical exchange during hydrothermal alteration of basalt by seawater—I. Experimental results for major and minor components of seawater

Fresh mid-ocean ridge basalt of varying crystallinity has been powdered and reacted with seawater and an artificial Na-K-Ca-Cl solution at 200–500°C and 500–1000 bar in sealed gold capsules. Water/rock mass ratios of 1–3 were used and durations ranged from 2 to 20 months.These time periods were sufficient for most elements to approach a steady-state concentration in solution which was determined by equilibrium with alteration minerals (Mg, SiO₂, SO₄), by rate of formation of these minerals (Na, Ca), or by depletion from the rock (K, B, Ba). The resulting solutions closely resemble the brines from the basalt-seawater geothermal system at Reykjanes, Iceland. Mg was almost completely removed from seawater into the alteration products smectite, tremolite-actinolite, or talc. Sulfate also was removed to low concentrations, both by precipitation of anyhydrite and by reduction to sulfide. Net transfer of Na from seawater into solids occurred in most experiments by formation of sodic feldspar and possibly analcime. Sr was removed from seawater in some experiments but showed no change or a small gain in others. SiO₂, Ca, K, Ba, B and CO₂ were leached from basalt and enriched in solution. SiO₂ concentrations were controlled by saturation with quartz at 300°C and above. The principal Ca-bearing phases which formed were anhydrite, the hydrated Ca-silicate truscottite, tremolite-actinolite, and possibly wairakite. No K-rich phases formed. For some minerals the crystallinity of the starting basalt affected the amount which formed.Removal of Mg from seawater into solid alteration products occurred rapidly and was balanced largely by leaching of Ca from basalt. Net transfer of Na from seawater into solids occurred more slowly and was balanced mainly by leaching of additional Ca from basalt. Thus, reaction between seawater and basalt at low water/rock ratios can be considered to consist of two exchanges: Mg for Ca, and Na for Ca.     

Carbonatization of oceanic crust by the seafloor hydrothermal activity and its significance as a CO2 sink in the Early Archean

Early Archean (3.46 Ga) hydrothermally altered basaltic rocks exposed near Marble Bar, eastern Pilbara Craton, have been studied in order to reveal geological and geochemical natures of seafloor hydrothermal carbonatization and to estimate the CO₂ flux sunk into the altered oceanic crust by the carbonatization. The basaltic rocks are divided into basalt and dolerite, and the basalt is further subdivided into type I, having original igneous rock textures, and type II, lacking these textures due to strong hydrothermal alteration. Primary clinopyroxene phenocrysts are preserved in some part of the dolerite samples, and the alteration mineral assemblage of dolerite (chlorite + epidote + albite + quartz ± actinolite) indicates that the alteration condition was typical greenschist facies. In other samples, all primary minerals were completely replaced by secondary minerals, and the alteration mineral assemblage of the type I and type II basalts (chlorite + K-mica + quartz + carbonate minerals ± albite) is characterized by the presence of K-mica and carbonate minerals and the absence of Ca-Al silicate minerals such as epidote and actinolite, suggesting the alteration condition of high CO₂ fugacity. The difference of the alteration mineral assemblages between basalt and dolerite is probably attributed to the difference of water/rock ratio that, in turn, depends on their porosity.Carbonate minerals in the carbonatized basalt include calcite, ankerite, and siderite, but calcite is quite dominant. The δ¹³C values of the carbonate minerals are −0.3 ± 1.2‰ and mostly within the range of marine carbonate, indicating that the carbonate minerals were formed by seafloor hydrothermal alteration and that carbonate carbon in the altered basalt was derived from seawater. Whole-rock chemical composition of the basaltic rocks is essentially similar to that of modern mid-ocean ridge basalt (MORB) except for highly mobile elements such as K₂O, Rb, Sr, and Ba. Compared to the least altered dolerite, all altered basalt samples are enriched in K₂O, Rb, and Ba, and are depleted in Na₂O, reflecting the presence of K-mica replacing primary plagioclase. In addition, noticeable CO₂ enrichment is recognized in the basalt due to the ubiquitous presence of carbonate minerals, but there was essentially neither gain nor loss of CaO. This suggests that the CO₂ in the hydrothermal fluid (seawater) was trapped by using Ca originally contained in the basalt. The CaO/CO₂ ratios of the basalt are generally the same as that of pure calcite, indicating that Ca in the basalt was almost completely converted to calcite during the carbonatization, although Mg and Fe were mainly redistributed into noncarbonate minerals such as chlorite.The carbon flux into the Early Archean oceanic crust by the seafloor hydrothermal carbonatization is estimated to be 3.8 × 10¹³ mol/yr, based on the average carbon content of altered oceanic crust of 1.4 × 10^-3 mol/g, the alteration depth of 500 m, and the spreading rate of 1.8 × 10¹¹ cm²/yr. This flux is equivalent to or greater than the present-day total carbon flux. It is most likely that the seafloor hydrothermal carbonatization played an important role as a sink of atmospheric and oceanic CO₂ in the Early Archean.     

Nikubuchi peridotite body in the sanbagawa metamorphic belt; thermal history of the ‘Al-pyroxene-rich suite’ peridotite body in high pressure metamorphic terrain

Oceanic tholeiite glass has been reacted with natural seawater at 25°–500° C, 1 kbar, with both low (5) and high (50) water/rock mass ratios. Initial experiments were conducted at constant temperatures between 100° C and 500° C (100° intervals) in order to characterize the mineralogy and chemical exchange trends for both water/rock ratios. However, the primary purpose of this investigation was to study the chemical and mineralogical changes that may take place as reacted seawater cools as it traverses a temperature gradient before exiting onto the seafloor, as may happen in some submarine hydrothermal systems. Consequently, a series of cooling or temperature gradient experiments were performed in which seawater that had reacted with basalt at 500° C was cooled to 25° C in a step-wise fashion; mineralogy and fluid chemistry were determined at 100 degree intervals during cooling.For all of the experiments, the elemental exchange trends were the same. With respect to the initial sea-water, Fe, Mn, Ca, Si and H⁺ increased while Na and Mg decreased. However, the extent of the exchange depended heavily on the temperature and water/rock ratio. During cooling, fluid compositions in the temperature gradient runs generally approached those of the constant temperature experiments. Even though fluid compositions were very similar at 500° C for both water/rock ratios, the high water/rock ratio systems were more efficient in leaching transition metals from the rock and maintained substantial concentrations in solution during cooling, even to temperatures as low as 25° C. The Fe/Mn ratio in the fluid, however, was quite different for the two water/rock ratios; consequently, the effective water/rock ratio appears to be one parameter that can control the Fe/Mn ratio in exiting hydrothermal fluids and may influence the Fe/Mn ratio in metal-rich sediments.Alteration minerals produced in these seawater/ basalt experiments are very similar to those found at submarine springs on the East Pacific Rise, 21° N. Iron sulfides, pyrite and pyrrhotite, precipitated during cooling for both water/rock ratios, demonstrating the ore-forming potential of submarine hydrothermal systems.     

The formation of high temperature clay minerals from basalt alteration during hydrothermal discharge on the East Pacific Rise axis at 21°N

Aluminous, high-temperature clay minerals form from alteration of tholeiitic basaltic glass and calcic plagioclase during hydrothermal venting on the crest of the East Pacific Rise at 21°N. The clay alteration assemblages are layered crusts (up to 1 mm thick) completely replacing glass and calcic plagioclase adjacent to surfaces exposed to hydrothermal fluids. The interiors of the affected basalt samples have unaltered appearances and oxygen isotopic compositions just slightly heavier than that of MORB. The surficial alteration crusts are mixtures of beidellitic smectite (aluminous, dioctahedral), randomly interstratified mixed-layer Al-rich chlorite/smectite, minor chlorite, an x-ray amorphous aluminosilicate material, and possible minor serpentine (amesite). A δ¹⁸O value of +4.1 ± 0.2%. (SMOW) is determined for the beidellitic smectite. Assuming that this smectite equilibrated with hydrothermal fluid having an oxygen isotope value between that of seawater (0%.) and 350°C hydrothermal fluid from EPR, 21°N vents (+1.6%.), an equilibration temperature between 290°C and 360°C is calculated for the beidellitic smectite. This is substantially higher than any previously reported temperature for an oceanic smectite. The mixed-layer Al-rich chlorite/smectite has a δ¹⁸O value of +3.5%., which corresponds to equilibration at 295°–360°C. The aluminous composition of the alteration assemblage is uncommon for clay minerals produced by submarine hydrothermal basalt alteration. We suggest that this assemblage is largely the product of high-temperature interaction between basalt glass + plagioclase and Mg-poor, acidic hydrothermal fluids, with possibly some contribution of Mg from bottom seawater, and that the aluminous clays either incorporate Al³⁺ remobilized from basalt by lowpH hydrothermal fluids, or are residual phases remaining after intense alteration of basaltic glass + plagioclase.     

Fluid–Sediment Interaction in a Marine Shallow-Water Hydrothermal System in the Wakamiko Submarine Crater, South Kyushu, Japan

The Wakamiko submarine crater is a small depression located in Kagoshima Bay, southwest Japan. Marine shallow‐water hydrothermal activity associated with fumarolic gas emissions at the crater sea floor (water depth 200 m) is considered to be related with magmatic activity of the Aira Caldera. During the NT05‐13 dive expedition conducted in August 2005 using remotely operated vehicle Hyper‐Dolphine (Japan Agency for Marine‐Earth Science and Technology), an active shimmering site was discovered (tentatively named the North site) at approximately 1 km from the previously known site (tentatively named the South site). Surface sediment (up to 30 cm) was cored from six localities including these active sites, and the alteration minerals and pore fluid chemistry were studied. The pore fluids of these sites showed a drastic change in chemical profile from that of seawater, even at 30 cm below the surface, which is attributed to mixing of the ascending hydrothermal component and seawater. The hydrothermal component of the North site is estimated to be derived from a hydrothermal aquifer at 230°C based on the hydrothermal end‐member composition. Occurrence of illite/smectite interstratified minerals in the North site sediment is attributed to in situ fluid–sediment interaction at a temperature around 150°C, which is in accordance with the pore fluid chemistry. In contrast, montmorillonite was identified as the dominant alteration mineral in the South site sediment. Together with the significant low potassium concentration of the hydrothermal end‐member, the abundant occurrence of low‐temperature alteration mineral suggests that the hydrothermal aquifer in the South site is not as high as 200°C. Moreover, the montmorillonite is likely to be unstable with the present pore fluid chemistry at the measured temperature (117°C). This disagreement implies unstable hydrothermal activity at the South site, in contrast to the equilibrium between the pore fluid and alteration minerals in the North site sediment. This difference may reflect the thermal and/or hydrological structure of the Wakamiko Crater hydrothermal system.     

Hydrothermal processes along mid-ocean ridges: An experimental investigation

An experimental investigation of high-temperature seawater/basalt interactions has been conducted in order to better evaluate the geochemical and economic implications of hydrothermal circulation of seawater in the oceanic crust along active mid-ocean ridges. The results indicate that, as seawater reacts with basalt between 200 ° C and 500 ° C at 500–800 bars, the fluid tends to change from an oxygenated, slightly alkaline, Na⁺, Mg⁺⁺, SO₄ ⁼, Cl^? solution to a reducing, acidic, Na⁺, Ca⁺⁺, Cl^?, solution with Fe, Mn and Cu concentrations up to 1500, 190 and 0.3 ppm respectively. Silica concentrations in the fluid reach concentrations of 200–600 ppm; however, Al abundances remain very low (～0.5 ppm). Gray and green smectites, anhydrite, albite, tremolite-actinolite, chalcopyrite, pyrrhotite and hematite were the dominant alteration products formed. These data imply that large-scale circulation of seawater in the oceanic crust could account for the Al-deficient metalliferous sediments associated with mid-ocean ridges and could be important in the genesis of certain Fe-Cu sulfide ore deposists. The process could also affect the geochemical budgets of certain elements and exert substantial control of the steady-state composition of seawater by removing excess Na and Mg and adding Ca, Si, and H to the oceans.     

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 H₂S 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.     

Hydrothermal alteration of hemi-pelagic sediments: experimental evaluation of geochemical processes in shallow subduction zones

Laboratory hydrothermal experiments provide unique information regarding the fate of volatile and/or incompatibles (e.g. B, Li, and As) during oceanic crust subduction. Examination of chemical redistribution between the subducted slab, mantle wedge, arc volcanics and overlying ocean water during subduction is critical to gain further insight into arc volcanism and chemical oceanic budgets. For instance, efficient mobilization of B at shallow depths may be a key aspect of its oceanic budget, and can help to explain the systematics of B-δ¹¹B and B-¹⁰Be in arc lavas. Fluid–rock interactions at elevated temperatures and pressures in accretionary prisms were studied using a rocking autoclave hydrothermal apparatus to monitor sediment–porewater interaction over the range of 25 to 350°C, at 800 bars. Clay-rich hemi-pelagic sediments from the décollement zone of Ocean Drilling Program Site 808, Nankai Trough, were reacted with NaCl–CaCl₂ solutions at water/rock ratios of ∼3.5 to 1.5 (w/w) to mimic alteration processes in the shallow subduction zone. Fluids were extracted at 25–50°C intervals and were analyzed for major and trace chemical constituents. The fluid chemistry changed significantly during the course of these experiments, but there was generally only minor modification of the solid phase; only B, Li, As, Br, and Pb are significantly depleted. During the heating cycle, dissolved Na, Mg and SO₄ decreased sharply and NH₄, SiO₂, K, B, and Li increased at T⩾300°C. Calcium drops gradually at low temperatures, but concentrations rise sharply at T⩾300°C. Decomposition of organic matter, SO₄²⁻ depletion, and Mg-fixation dominate at low temperatures; however, albitization of calcic plagioclase leads to marked Na depletions and Ca enrichments at T⩾300°C. Dissolved SiO₂ remained below saturation with respect to quartz and amorphous silica throughout the entire experiment. B and Li mobilization with large isotopic fractionations occurred at low temperature. Exchangeable B (δ¹¹B=∼15‰) is completely leached before reaching 150°C. Substantial O₂ exchange between fluids and the solid phase occurred at T⩾200°C in the spiked experiment, where δ¹⁸O varies more than 100‰ in the fluids. During retrograde cooling, dissolved Mg, SO₄, Ca, Si, K and Sr are released as a result of carbonate or anhydrite dissolution, and marked B re-adsorption occurred at temperatures below 60°C.     

Heavy metal and sulfur transport during subcritical and supercritical hydrothermal alteration of basalt: Influence of fluid pressure and basalt composition and crystallinity

Crystalline basalt, diabase and basalt glass have been reacted with a Na-Ca-K-Cl fluid of seawater ionic strength at 350–425°C, 375–400 bars pressure and fluid/rock mass ratios of 0.5–1.0, to assess the role of temperature, basalt/diabase chemistry and texture on heavy metal and sulfur mobility during hydrothermal alteration.Alteration of basalt/diabase is characterized by cation fixation and hydrolysis reactions which show increased reaction progress with increasing temperature at constant pressure. Correspondingly, pH in a series of 400 bar experiments ranges from 4.8 to 2.7 at 350 and 425°C, respectively and is typically lower for alteration of a SiO₂-rich crystalline basalt than for other rock types, due, in part, to relatively high SiO₂ concentrations in solution. High SiO₂ concentrations stabilize hydrous Na- and Ca-rich alteration phases, causing pH to decrease according to reactions such as: 3.0 CaAl₂Si₂O₈ + 1.0 Ca⁺⁺ + 2.0 H₂O = 2.0 Ca₂Al₃Si₃O₁₂(OH) + 2.0 H⁺Phases experimentally produced include: mixed layer chlorite/smectite, Ca-rich amphibole and clinozoisite. Clinozoisite was identified as a replacement product of plagioclase from diabase-solution interaction experiments.In direct response to H⁺ production, dissolved Fe, Mn and H₂S concentrations increase dramatically. For early-stage reaction, H₂S typically exceeds Fe and Mn. However, at 425°C and after long-term reaction at 400°C, H₂S is lost from solution, apparently in response to pyrite replacement of oxide and silicate phases.Pyrrhotite formed at temperatures ≤ 375°C, whereas magnetite was identified in all run products, except from basalt glass alteration.Cu and Zn concentrations in solution are not simple functions of pH. These metals achieve greatest solubility in fluids from experiments at 375–400°C, except when basalt glass is used as a reactant. The relatively low concentrations of these species in solution during basalt glass reaction may be due to adsorption by fine grained alteration phases.     

Oxygen Isotope Characteristics of the Footwall Alteration Zones in the Hongtoushan Volcanogenic Massive Sulfide Deposit, Liaoning Province, China and Restoration of Their Formation Temperatures

The Hongtoushan Volcanogenic Massive Sulphide Deposit (VMSD) occurs in the Hunbei granite-greenstone terrane, Liaoning Province, NE China. Rocks in the mining area have been metamorphosed around 3.0–2.8 Ga to upper amphibolite facies at temperatures between 600°C and 650°C. Cordierite-anthophyllite gneiss (CAG) in the Hongtoushan mining area, which occurs hundreds of meters below the ore horizon, corresponds to the metamorphosed semi-conformable alteration zone of the VMSD hydrothermal system, whereas the one immediately below the main ore layer represents the metamorphosed pipe-like alteration zone. Whole-rock oxygen isotope signatures were well preserved in both types of CAGs, although the mineral components have been entirely changed during regional metamorphism. Therefore, whole-rock oxygen isotopes can be used to estimate the formation temperature of both types of alteration zone. Calculations show that the semi-conformable and pipe-like alteration zones for the Hongtoushan submarine hydrothermal system were formed at 290–360°C and 285–320°C, respectively, whereas estimates for the former were slightly higher than that of the latter, indicating that the semi-conformable alteration zone represents the deep part of the Hongtoushan seafloor hydrothermal system, while the pipe-like alteration zone represents the discharge conduits for metal-rich fluids, which is closer to the seafloor.     

Sulfur in peridotites and gabbros at Lost City (30°N, MAR): Implications for hydrothermal alteration and microbial activity during serpentinization

Variations in sulfur mineralogy and chemistry of serpentinized peridotites and gabbros beneath the Lost City Hydrothermal Field at the southern face of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) were examined to better understand serpentinization and alteration processes and to study fluid fluxes, redox conditions, and the influence of microbial activity in this active, peridotite-hosted hydrothermal system. The serpentinized peridotites are characterized by low total sulfur contents and high bulk δ³⁴S values close to seawater composition. Low concentrations of ³⁴S-enriched sulfide phases and the predominance of sulfate with seawater-like δ³⁴S values indicate oxidation, loss of sulfide minerals and incorporation of seawater sulfate into the serpentinites. The predominance of pyrite in both serpentinites and gabbros indicates relatively high fO₂ conditions during progressive serpentinization and alteration, which likely result from high fluid fluxes during hydrothermal circulation and evolution of the Lost City system from temperatures of ∼250 to 150 °C. Sulfate and sulfide minerals in samples from near the base of hydrothermal carbonate towers at Lost City show δ³⁴S values that reflect the influence of microbial activity. Our study highlights the variations in sulfur chemistry of serpentinized peridotites in different marine environments and the influence of long-lived, moderate temperature peridotite-hosted hydrothermal system and high seawater fluxes on the global sulfur cycle.     

Deposition of talc — kerolite–smectite — smectite at seafloor hydrothermal vent fields: Evidence from mineralogical,geochemical and oxygen isotope studies

Talc, kerolite–smectite, smectite, chlorite–smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite–smectite to smectite-rich kerolite–smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite–smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite–smectite with lower crystalline perfection as the proportion of smectite layers in kerolite–smectite increases.Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite–smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (> 250 °C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200–250 °C) phase forming deep within the sediment (～ 0.8 m). Chlorite and chlorite–smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150–200 °C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two controls on the precipitation of this sequence are the silica activity and Mg/Al ratio (i.e. the degree of mixing of seawater with hydrothermal fluid). Higher silica activity favors the formation of talc relative to tri-octahedral smectite. Vent structures and sedimentary cover preclude complete mixing of hydrothermal fluid and ambient seawater, resulting in lower Mg/Al ratios in the interior parts of the chimneys and deeper in the sediment which leads to the precipitation of phyllosilicates with lower Mg contents. Talc and kerolite–smectite have very low trace- and rare earth element contents. Some exhibit a negative or flat Eu anomaly, which suggests Eu depletion in the original hydrothermal fluid. Such Eu depletion could be caused by precipitation of anhydrite or barite (sinks for Eu²⁺) deeper in the system. REE abundances and distribution patterns indicate that chlorite and chlorite–smectite are hydrothermal alteration products of the background turbiditic sediment.