Trace element mobility during hydrothermal alteration of oceanic basalts

Trace element analyses have been carried out on hydrothermally altered pillow basalts of greenschist facies dredged from the median valley of the Mid-Atlantic Ridge. Sr is leached from the rock, and its behavior is apparently controlled by the same reactions as Ca. Cu is also leached from the basalt, but often shows local precipitation in veins as sulfides. Fe, B, Li, Ba, Mn, Ni and Co show sufficient variations in concentration and location within the altered basalts to indicate that some mobilisation occurs, but there may be subsequent uptake or precipitation into the secondary mineral assemblages. V, Y, Zr and Cr do not appear to be affected by hydrothermal alteration.The production of a metal-enriched solution by hydrothermal alteration and subsequent precipitation of metal salts to form metalliferous sediments is indicated, as is precipitation of metal sulfides in the basaltic basement.     

Geochemistry of hydrothermal Mn-oxide deposits from the S.W. Pacific island arc

Hydrothermal Mn-oxide crusts have been removed from the Tonga-Kermadec Ridge, the first such hydrothermal deposits to be reported in the S.W. Pacific island arc. In several respects the deposits are similar to hydrothermal Mn-crusts from oceanic spreading centre settings. They are limited in areal extent, comprise well-crystalline birnessite and generally display extreme fractionation of Mn from Fe. They are strongly depleted in many elements compared to hydrogenous Mn deposits but are comparatively enriched in Li, Zn, Mo and Cd. The Group IA and Group IIA metals show strong intercorrelations and the behaviour of Mg in the purest samples may indicate the extent to which normal seawater has influenced the composition of the deposits.Certain aspects of the deposits are not typical of hydrothermal Mn deposits. In particular at least some of the crusts have developed on a sediment or unconsolidated talus substrate. Some crusts, or specific layers within some crusts, display a chemical composition which suggests a significant input from normal seawater.     

Geochemistry of Some Marine Fe–Mn Nodules and Crusts with Respect to Pt Contents

Bulk chemical analyses for Pt and Pd in marine Fe–Mn nodules and crusts from different provenances are presented, together with a wide range of elements. Platinum contents vary from 70–328 ppb, whereas Pd contents extend from 0.6–4.7 ppb only. Bromine and Pb show strong positive correlations with Pt. Lead is remarkably enriched in Fe–Mn precipitates over seawater, but Br is a conservative‐type element in seawater and shows no enrichment in Fe–Mn precipitates. Hence, the Pt–Br–Pb element association combines two elements, Br and Pb, of extremely contrasting enrichment factors in Fe–Mn precipitates.     

Extreme positive Ce-anomalies in a 3.0 Ga submarine volcanic sequence,Murchison Province: Oxygenated marine bottom waters

Systematic positive anomalies of Ce, where Ce/Ce* spans 2.1 to 11.4, are present in basalts and rhyolites of a 2.96 Ga submarine volcanic sequence of the Murchison Province, Western Australia. This volcanic sequence is host to a stratabound Cu–Zn deposit that formed on the seafloor from a seawater hydrothermal system. These are true Ce anomalies as Pr/Pr* < 1. In modern oxygenated marine water Ce is sequestered by Mn-oxides and hydroxides, which coprecipitate with Fe-oxides and hydroxides as nodules and crusts on the ocean floor, as well as Fe–Mn chemical sediments from hydrothermal systems at ocean spreading centers. Fe–Mn sediments have positive Ce anomalies and marine water complementary negative anomalies. Such Ce anomalies have not formerly been reported for Archean hydrothermally altered volcanic rocks. These extreme anomalies are attributed to Mn-transport in shallow-circulating oxygenated marine bottom waters peripheral to the deeper, hotter, hydrothermal system from which the Cu–Zn deposit formed, and record an oxygenated marine environment ~ 500 Ma before the so-called great oxidation event at ~ 2.4 Ga. Results for positive Ce anomalies in the Golden Grove volcanic sequence are complementary to negative anomalies in Archean BIF, collectively stemming from particulate scavenging of Ce^+ 3 in an oxic water column.     

Extreme enrichment of Sb, Tl and other trace elements in altered MORB

We have analyzed 25 trace elements (e.g., Sb, Tl, Sn, rare earth elements (REE), Th, U, Nb, Pb, Zr, Hf, and Y) in altered mid-ocean ridge basalts (MORB) from locations near the mouth of the Gulf of California. Our results imply that the heavy REE and Y are not seriously affected by seawater alteration, in agreement with previous studies. The elements Zr, Hf, Nb, light REE and Sr are enriched up to a factor of 2 in some extremely altered samples. However, element ratios between Zr, Hf, and Nb (e.g., Zr/Hf, and Zr/Nb) are not greatly affected, presumably due to the chemical similarity of these elements during any exchange process. The enrichment of Th and Sn is even higher. Antimony, Tl, Cs, Rb, Rb, and Ba are most easily altered by water-rock interaction and are therefore the best indicators for seawater alteration. The enrichment factor of the most mobile element Sb is up to 2000.

There is a weak correlation between the concentration in seawater and the enrichment factors. On the other hand, the worldwide pelagic clay pattern matches the enrichment pattern much more closely, and the limited data available for local oceanic sediments give an even better correlation. A plausible model to explain the enrichment pattern may be an elemental exchange between basalt and seawater that had interacted earlier with overlying sediments.     

The influence of submarine weathering of basalts on their partial melting during subduction

Compositional changes beyond that of simple hydration are present in most of the analyzed examples of submarine weathering of basalt. Recalculations of 278 analyses from the literature of altered basalts to simplified basalt, amphibolite and eclogite mineral assemblages result in significant increases of the quartz contents of the rock relative to fresh basalt in most examples. The increased quartz contents result in mineral assemblages that have enhanced potentials to generate andesitic partial melts from the basalt or amphibolite forms of most altered basalts and trondhjemitic partial melts from the eclogite form of most altered basalts.     

Hydrothermal Alteration of Limestone and Mineral Exploration of Zn-Pb Skarn Deposits in the Sako-nishi Area of the Kamioka Mine, Central Japan

Abstract: Crystalline limestone of the Sako-nishi area in the Kamioka Zn-Pb mine, central Japan, is depleted in ¹⁸O and ¹³C toward the center of mineralization due to interaction with hydrothermal fluids with a dominant meteoric water component. The relationship between isotopic composition and mineral assemblage, texture, the chemical composition of the minerals, and the bulk chemical composition in the limestone was examined. A decrease in the δ¹⁸OSMOW value correlated with: (1) increase of fine-grained calcite which is enriched in Mn and exhibits a bright cathodoluminescence, (2) progressive hy-drothermal alteration of clinopyroxene in the original limestone into tremolite within the weakly-altered zone, and into chlorite and actinolite within the strongly-altered zone, (3) dominance of hydrothermal chlorite in altered limestone having δ¹⁸O values of less than 10%. This chlorite was enriched in Fe compared to mafic minerals in the unaltered limestone. The enrichment of Fe and Mn was more conspicuous in calcite and chlorite in skarn deposits. The occurrence and chemical composition of hydrothermal minerals in the limestone, skarn, and ore indicate that the ¹⁸O–depleted zones were formed in the later stage from fluids, which were responsible for mineralization and skarnization, and for Fe and Mn enrichment. The Al, Mn, and Fe contents, and the ratios of Mg/(Mg+Mn+Fe), Al/Mg, and Mn/Sr in the hydrochloric acid leachate of limestone varied with decreasing δ¹⁸O and δ¹³C values, reflecting increases in high-Mn calcite and high-Fe chlorite. These indexes were useful for the identification of hydrothermally altered limestone. Furthermore, the potential score weighted by each index was more effective and accurate means of detecting promising mineralization zones. An anomalous potential score due to the presence of hydrothermal minerals in the outcropping limestone occurred along the Atotsu–1GO fault. This structure indicates that the skarn deposits of the Sako-nishi area belong to Mozumi-type Zn–Pb skarn deposits, in which fissures and faults served as major passages for the hydrothermal fluid. High-Mn carbonate and high-Fe chlorite widely occur in base-metal vein deposits and Zn-Pb type skarn deposits. Leaching of altered rock with hydrochloric acid in addition to stable isotope composition and cathodoluminescence imaging is effective for geochemical exploration for hydrothermal deposits because it makes possible the detection of the elemental composition of hydrothermal minerals such as chlorite and carbonate and because of the rapidity and convenience of analysis.     

Application of major and trace elements as well as boron isotopes for tracing hydrochemical processes: the case of Trifilia coastal karst aquifer,Greece

The Trifilia karst aquifer presents a complex hydrochemical character due to the intricate geochemical processes that take place in the area. Their discernment was achieved by using the chemical analyses of major, trace elements and boron isotopes. Major ion composition indicates mixing between seawater and freshwater is occurring. Five hydrochemical zones corresponding to five respective groundwater types were distinguished, in which the chemical composition of groundwater is influenced mainly due to the different salinization grade of the aquifer. The relatively increased temperature of the aquifer indicates the presence of hydrothermal waters. Boron isotopes and trace elements indicate that the intruding seawater has been hydrothermally altered, as it is shown by the δ¹¹B depleted signature and the increased concentrations of Li and Sr. Trace elements analyses showed that the groundwater is enriched in various metallic elements, which derive from the solid hydrocarbons (bitumens), contained in the carbonate sediments of the Tripolis zone. The concentration of these trace elements depends on the redox environment. Thus, in reductive conditions As, Mn, Co and NH₄ concentrations are high, in oxidized conditions the V, Se, Mo, Tl and U concentration increases while Ni is not redox sensitive and present high concentration in both environments.     

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

1 Introduction Submarine metallic mineral resources consist mainly of polymetallic nodules and cobalt-rich ferromanganese crusts. Despite being discovered much later than the former, the latter are becoming one of the most important submarine polymetallic ore resources, because they containmany valuable metallic elements such as Co, platinum group elements (PGE), rare earth elements (REE), Ni and Cu, besides high contents of Fe and Mn (He et al., 2001). The Co-rich crusts are widely distr…     

Coupling of Redox Conditions of Mantle Melting and Copper and Sulfur Contents in Primary Magmas of the Tolbachinsky Dol (Kamchatka) and Juan de Fuca Ridge (Pacific Ocean)

The compositions of parental melts of Tolbachinsky Dol (Kamchatka) basalts were estimated from the compositions of olivine-hosted (Fo_90.5-83.1) primitive melt inclusions in the rocks of the Northern breakthrough of the Great Tolbachik Fissure Eruption (1975 A.C.) and of the late-Holocene cone “1004”. The parental melts contain 100–150 ppm Cu and 0.16–0.30 wt % S. These concentrations are much higher than those determined for the initial magmas of mid-ocean ridge basalts (MORB), for example of the Juan de Fuca ridge (Cu = 55–105 ppm, S=0.09–0.12 wt %). Modeling of mantle melting under variable redox conditions demonstrated that the high Cu and S contents in the Tolbachinsky Dol melts can be obtained by 6–12% melting of DMM-like source under oxidized conditions (ΔQFM = +1.2 ± 0.1) and do not require a significant (>30–35% for S) subduction-related influx of these elements to the mantle source. The high contents of Cu and S in the Tolbachinsky Dol melts are largely explained by the increase of sulfide solubility in a silicate melt under oxidized conditions. In contrast, relatively reduced (ΔQFM ～ 0) conditions of MORB generation result in low contents of Cu and S in their initial magmas. The estimated ΔQFM values agree well with the data obtained using the Cr-spinel–olivine oxybarometer. The high oxygen potential of Tolbachinsky Dol primary magmas is inherited by more evolved magmas, thus favouring Cu enrichment up to 270 ppm during magma fractionation, approaching maximum copper contents in the global systematics of island-arc rocks.     

Mineralogical and geochemical characteristics of hydrothermal alteration of basalt in the Kuroko mine area, Japan: implications for the evolution of a Back Arc Basin hydrothermal system

Basalt in the Furutobe District of the Kuroko mine area in Japan is characterized by abundant chlorite and epidote. Fluid inclusion studies indicate that chlorite is formed at lower temperatures (230–250°C) than epidote (250–280°C). The seawater/basalt mass ratio for the early chlorite-rich alteration was high (max. 40), but that for the later alteration was low (0.1–1.8). The CaO, Na₂O and SiO₂ of the bulk rock correlate negatively with MgO, while FeO and Σ Fe correlate positively with MgO. These changes in the characteristic features of hydrothermal alteration from early to late are generally similar to those for a mid-ocean ridge geothermal system accompanying basalt alteration.The MgO/FeO ratios of chlorite and actinolite and the Fe₂O₃ concentration of epidote from the basalt are greater than those of mid-ocean ridge basalt probably owing to the differences in the Fe₂O₃/FeO and MgO/FeO ratios of the parent rocks. The lower CaO concentration and the higher Na₂O concentration of the bulk rock compared with altered mid-ocean ridge basalt can be interpreted in terms of the difference in original bulk rock compositions.The Furutobe basalt, as well as other submarine back arc basalts, contains more vesicles filled with hydrothermal minerals (epidote, calcite, quartz, chlorite, pyrite) than do the mid-ocean ridge basalts. The abundance of vesicles plays an important role in controlling the secondary mineralogy and geochemistry of hydrothermally altered submarine back arc basin basalts.     

Geology and geochemistry of the Huilvshan gold deposit,Xinjiang, China: Implications for mechanism of gold precipitation

The Huilvshan gold deposit in the west Junggar (Xinjiang, China) is hosted in chloritized basalts, chlorite–siderite-altered basalts, and quartz–siderite rocks. Our study demonstrated that all these rocks were derived by alteration of basalts in a shear zone. The orebodies, consisting of quartz-sulfide veins and disseminated sulfides, formed in five stages: quartz–muscovite (I), disseminated sulfides (II), quartz–ankerite-sulfide (III), quartz–calcite-sulfide (IV), and quartz–calcite (V). Auriferous minerals are native gold in stage III and electrum in stage IV. During alteration of basalts in the shear zone, ore-forming elements were released from basalts to ore-forming fluid. Compared with fresh basalts, sulfide-bearing chloritized basalts contain much higher Sr, Ba, P, La, Ce, U, Mn, Ni, Zn, As, Ag, and Au contents. Phase analysis of the As–Cu–Fe–S–O system with the SUPCRT92 software package indicates that a decrease of the a_H2S value, caused by the fluid–rock reactions and crystallization of sulfides, induced gold precipitation.     

Pillow lavas of the Sierra Leone test site,Mid-Atlantic Ridge, 5°–7°N: Sr-Nd isotope systematics,geochemistry, and petrology

Based on detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial MAR rift zone between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in the basalts and their glasses. It was shown that some samples show significant nonsystematic differences in the ⁸⁷Sr/⁸⁶Sr ratio between the basalts and their chilled glasses and less significant difference in ?_Nd; higher Sr ratios can be observed both in the glasses and basalts of the same lava fragments. No significant correlation is observed between the isotope characteristics of the samples and their geochemistry; it was also shown that seawater did not affect the Sr and Nd isotope composition of the chilled glasses of the studied pillow lavas. It is suggested that such differences in isotope ratios are related to a small-scale heterogeneity of the melts owing to incomplete homogenization during their rapid ascent to the surface. The heterogeneity of the basaltic melts is explained by their partial contamination by the older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the ocean floor surface. The wider scatter of the Sr isotopic ratios relative to Nd is related to the presence of xenocrysts of calcic plagioclase; correspondingly, the absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all of the studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. The causes of this phenomenon remain unclear.     

Comparative petrology, geochemistry, and petrogenesis of evolved, low-Ti lunar mare basalt meteorites from the LaPaz Icefield, Antarctica

New data is presented for five evolved, low-Ti lunar mare basalt meteorites from the LaPaz Icefield, Antarctica, LAP 02205, LAP 02224, LAP 02226, LAP 02436, and LAP 03632. These basalts have nearly identical mineralogies, textures, and geochemical compositions, and are therefore considered to be paired. The LaPaz basalts contain olivine (Fo_64-2) and pyroxene (Fs₃₂Wo₈En₆₀ to Fs_84-86Wo₁₅En_2-0) crystals that record extreme chemical fractionation to Fe-enrichment at the rims, and evidence for silicate liquid immiscibility and incompatible element enrichment in the mesostasis. The basalts also contain FeNi metals with unusually high Co and Ni contents, similar to some Apollo 12 basalts, and a single-phase network of melt veins and fusion crusts. The fusion crust has similar chemical characteristics to the whole rock for the LaPaz basalts, whereas the melt veins represent localized melting of the basalt and have an endogenous origin. The crystallization conditions and evolved nature of the LaPaz basalts are consistent with fractionation of olivine and chromite from a parental liquid similar in composition to some olivine-phyric Apollo 12 and Apollo 15 basalts or lunar low-Ti pyroclastic glasses. However, the young reported ages for the LaPaz mare basalts (∼2.9 Ga) and their relative incompatible element enrichment compared to Apollo mare basalts and pyroclastic glasses indicate they cannot be directly related. Instead, the LaPaz mare basalts may represent fractionated melts from a magmatic system fed by similar degrees of partial melting of a mantle source similar to that of the low-Ti Apollo mare basalts or pyroclastic glasses, but which possessed greater incompatible element enrichment. Despite textural differences, the LaPaz basalts and mare basalt meteorite NWA 032 have similar ages and compositions and may originate from the same magmatic system on the Moon.     

Sulfur isotope systematics in icelandic geothermal systems and influence of seawater circulation at Reykjanes

Pyrite from altered basalts from Nàmafjall and Krafla high-temperature fields and deep zones at Reykir, Leira and other low-temperature fields, and aqueous sulfides from Nàmafjall, have δ³⁴S values of 0 to 2.6%. These values are close to those for postglacial basaltic lavas from the Reykjanes Peninsula. The major source of sulfur in these meteoric hydrothermal systems is the upper-mantle or basalt. At the low-temperature fields, however, the δ³⁴S values of sulfide decrease with decreasing depth, suggesting the presence of a light sulfur source in the shallower aquifers.In contrast, in the Reykjanes and Svartsengi geothermal fields, where seawater contributes to the hydrothermal systems, sulfide sulfur is distinctly enriched in ³⁴S at all depths except for one Reykjanes pyrite from 84 m depth. The enrichment is about 8%. at the deepest core (1734 m) of Reykjanes and decreases with decreasing depth. These enrichments are most likely due to seawater sulfate being involved in the hydrothermal systems. However, in the Reykjanes fluid, dissolved heavy sulfates are not in isotopic equilibrium with sulfide. Disequilibrium between sulfate and sulfide is also demonstrated in all other Icelandic geothermal systems studied.     

Depositional Age of a Fossil Whale Bone from São Paulo Ridge,South Atlantic Ocean,Based on Os Isotope Stratigraphy of a Ferromanganese Crust

Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (¹⁸⁷Os/¹⁸⁸Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. ¹⁸⁷Os/¹⁸⁸Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.     

Petrogenesis of highly depleted peridotites and gabbroic rocks from the Mayarí-Baracoa Ophiolitic Belt (eastern Cuba)

The Moa-Baracoa and Mayarí-Cristal massifs (eastern Cuba) are two ophiolitic complexes mainly constituted by harzburgite tectonites and minor dunites, cut by gabbroic dykes. The Moa-Baracoa massif exhibits a well developed Moho transition zone and an incomplete crustal section made up of layered gabbros and tectonically emplaced pillow basalts. A plutonic crustal section is absent in the Mayarí-Cristal massif and mantle tectonites are in tectonic contact with arc-related volcanic rocks. Mantle peridotites are very refractory in terms of modal composition, whole rock major element and HREE contents implying that Moa-Baracoa and Mayarí-Cristal harzburgites are residues after high degrees (20–30%) of partial melting. The relative enrichment of Th, Nb, Ta and LREE in peridotites is due to re-equilibration of melting residues with percolating melts. Peridotites lost on average 6 wt% of relative MgO by intense seafloor weathering. REE contents and Mg# of melts in equilibrium with cumulate gabbros from the Moho transition zone and crustal section of the Moa-Baracoa massif coincide with those of the spatially-related pillow basalts. On the other hand, no geochemical relation has been inferred between melt in equilibrium with Mayarí-Cristal segregate and the spatially-related arc volcanics. Our results indicate that the Mayarí-Baracoa Ophiolitic Belt formed at an original back-arc spreading centre. The Moa-Baracoa massif represents a portion of MORB-like lithosphere located nearby a back-arc mid-ocean spreading ridge, and the Mayarí-Cristal massif represents a piece of transitional (MORB to IAT) mantle located closer to the paleo-volcanic arc than Moa-Baracoa.     

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.     

Hydrothermal Fe-Si-Mn oxide deposits from the Central and South Valu Fa Ridge, Lau Basin

A series of samples from the Hine Hina hydrothermal field (HHF) and the Mariner hydrothermal field (MHF) in the Central and Southern Valu Fa Ridge (VFR), Lau Basin were examined to explain the source origin and formation of the hydrothermal Fe-Si-Mn oxide deposits. The mineralogy was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer spectroscopy, and energy-dispersive spectroscopy (EDS). For the Fe-Mn oxide crusts in the HHF, varying amounts of volcanic fragments and some seawater contributions were recognized, along with higher concentrations of Mn, Al, Co, Ni, Zn, Sr, Mo, elevated ∑REE and negative Ce anomalies. In contrast, the Si-rich oxide samples of the MHF were enriched in Cu, Pb and Ba, indicative of proximity to a hydrothermal jet. Moreover, conductive cooling of hydrothermal fluid evoked the Si-rich deposit formation in the MHF. The Sr, Nd and Pb isotope data provided further constraints regarding the source and formation of the Fe-Si-Mn deposits in the VFR by showing that the samples of the HHF are a mixture of three components, namely, hydrothermal fluid, seawater and volcanic materials, whereas the samples of the MHF were dominated by hydrothermal fluids. The seawater had a minor influence on the Nd isotope data, and the Pb isotope data exhibited a close association with the substrate rock and preformed volcaniclastic layers in this area. The occurrence of relatively high Mn/Fe ratios in the hydrothermal deposits of this area may be a good indicator of the propagating activities of the VFR over geological time.     

南大西洋中脊26°S热液区成矿物质来源探讨

南大西洋中脊的26°S热液区广泛发育多金属硫化物、底泥、枕状熔岩、非活动性烟囱体和活动性烟囱体。为了有效探索硫、铜等成矿物质的来源以及成矿作用过程,分别以玄武岩、烟囱体残片及块状多金属硫化物为研究对象,开展了熔融包裹体、硫同位素和铜同位素研究。结果显示：区内玄武岩新鲜未蚀变且斑晶中产出大量熔融包裹体;熔融包裹体气泡壁附着黄铜矿、黄铁矿及磁铁矿等子矿物,说明在岩浆作用过程中可从熔浆中分离出成矿所需的金属元素和硫,这些成矿元素随着岩浆去气作用进入挥发分中,并随着脱气作用迁移出来。通过对烟囱体残片及块状多金属硫化物中黄铁矿的硫同位素组成进行比对分析,发现26°S热液区内硫化物的硫同位素与大西洋各热液区硫化物的硫同位素变化范围相一致,但δ³⁴S_V-CDT值略低（3.0‰~3.9‰）。低的δ³⁴S_V-CDT值指示硫以岩浆硫源为主,海水硫酸盐还原硫占比低。黄铜矿呈现略微富铜重同位素特征且分馏程度较低,其δ⁶⁵Cu值（0.171‰~0.477‰）趋近于大洋中脊玄武岩的铜同位素值（0）。综合硫同位素及铜同位素特征,表明热液流体经历了岩浆和海水的混合过程,成矿物质主要来自于岩浆热液,成矿作用过程中可能有少量海水混入。