Strontium and oxygen isotope decoupling in the Hercynian Trois Seigneurs Massif,Pyrenees: evidence for fluid circulation in a brittle regime

Systematic shifts of oxygen isotopic compositions in the higher grade parts of the high temperature-low pressure Hercynian metamorphic sequence, exposed in the Trois Seigneurs Massif, have previously been explained as a result of an influx of surface-derived water during the prograde part of the metamorphic cycle. It has been suggested that this caused a regional lowering of ⁸⁷Sr/⁸⁶Sr in the metamorphic sequence. Mapping of strontium isotopic compositions across a 15 m meta-carbonate horizon in the higher grade pelite-psammite sequence shows that strontium isotopic compositions were homogenised over length scales of metres or less during the Hercynian metamorphism, which brought the carbonate and pelite-psammite to oxygen isotopic equilibrium with a common fluid. Comparison of model pre-Hercynian ⁸⁷Sr/⁸⁶Sr profiles across the carbonate (based on a depositional/diagenetic age of 450 Ma and initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7086 given by 10 m length scale averaging) with the post-Hercynian ⁸⁷Sr/⁸⁶Sr profile (calculated from analysed ⁸⁷Sr/⁸⁶Sr and Rb/Sr compositions) implies strontium isotopic diffusion distances of ca. 0.4 m in the carbonate and ca. 7 m in the pelite-psammite. The limited Sr-isotopic diffusion distance of 0.4–0.7 m within the carbonate is compatible with pervasive oxygen-isotopic exchange over distances restricted to 4–15 m if fluid strontium concentrations were between 4 and 50 ppm. The strontium isotopic transport distances are not compatible with pervasive oxygen isotopic alteration over the observed 5 km regional scale. Either the flow was perfectly layer-parallel or, more probably, the regional-scale alteration of oxygen took place by fluid circulation in the brittle regime early in, or prior to, the Hercynian metamorphic event. Flow along cracks with incomplete diffusive exchange between fluid and wall rock would allow greater decoupling of oxygen and strontium isotopic transport than pervasive advective transport with local fluid-solid equilibrium.     

Isotopic-geochemical characteristics of the lost city hydrothermal field

The isotopic (δD, δ¹⁸O, δ¹³C, and ⁸⁷Sr/⁸⁶Sr) and geochemical characteristics of hydrothermal solutions from the Mid-Atlantic Ridge and the material of brucite-carbonate chimneys at the Lost City hydrothermal field at 30°N, MAR, were examined to assay the role of the major factors controlling the genesis of the fluid and hydrothermal chimneys of the Lost City field. The values of δD and δ¹⁸O in fluid samples indicates that solutions at the Lost City field were produced during the serpentinization of basement ultramafic rocks at temperatures higher than 200°C and at relatively low fluid/rock ratios (<1). The active role of serpentinization processes in the genesis of the Lost City fluid also follows from the results of the electron-microscopic studying of the material of hydrothermal chimneys at this field. The isotopic (δ¹⁸O, δ¹³C, and ⁸⁷Sr/⁸⁶Sr) and geochemical (Sr/Ca and REE) signatures indicate that, before its submarine discharging at the Lost City field, the fluid filtered through already cold altered outer zones of the Atlantis Massif and cooled via conductive heat loss. During this stage, the fluid could partly dissolve previously deposited carbonates in veins cutting serpentinite at the upper levels of the Atlantis Massif and the carbonate cement of sedimentary breccias underlying the hydrothermal chimneys. Because of this, the age of modern hydrothermal activity at the Lost City field can be much younger than 25 ka.     

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

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

Fluid flow through the sedimentary cover in northern Switzerland recorded by calcite–celestite veins (Oftringen borehole,Olten)

Abundant veins filled by calcite, celestite and pyrite were found in the core of a 719 m deep borehole drilled in Oftringen near Olten, located in the north-western Molasse basin, close to the thrust of the Folded Jura. Host rocks are calcareous marl, argillaceous limestone and limestone of the Dogger and Malm. The δ¹⁸O values of vein calcite are lower than in host rock carbonate and, together with microthermometric data from fluid inclusions in vein calcite, indicate precipitation from a seawater-dominated fluid at average temperatures of 56–68°C. Such temperatures were reached at the time of maximum burial of the sedimentary pile in the late Miocene. The depth profile of δ¹³C and ⁸⁷Sr/⁸⁶Sr values and Sr content of both whole-rock carbonate and vein calcite show marked trends towards negative δ¹³C, high ⁸⁷Sr/⁸⁶Sr, and low Sr content in the uppermost 50–150 m of the Jurassic profile (upper Oxfordian). The ⁸⁷Sr/⁸⁶Sr of vein minerals is generally higher than that of host rock carbonate, up to very high values corresponding to Burdigalian seawater (Upper Marine Molasse, Miocene), which represents the last marine incursion in the region. No evidence for internally derived radiogenic Sr (clay minerals) has been found and so an external source is required. S and O isotope composition of vein celestite and pyrite can be explained by bacterial reduction of Miocene seawater sulphate. The available data set suggests the vein mineralization precipitated from descending Burdigalian seawater and not from a fluid originating in the underlying Triassic evaporites.     

Isotopic evidence (Sr/Sr, δLi) for alteration of the oceanic crust at deep-rooted mud volcanoes in the Gulf of Cadiz, NE Atlantic Ocean

The chemical and isotopic composition of pore fluids is presented for five deep-rooted mud volcanoes aligned on a transect across the Gulf of Cadiz continental margin at water depths between 350 and 3860 m. Generally decreasing interstitial Li concentrations and ⁸⁷Sr/⁸⁶Sr ratios with increasing distance from shore are attributed to systematically changing fluid sources across the continental margin. Although highest Li concentrations at the near-shore mud volcanoes coincide with high salinities derived from dissolution of halite and late-stage evaporites, clayey, terrigenous sediments are identified as the ultimate Li source to all pore fluids investigated. Light δ⁷Li values, partly close to those of hydrothermal vent fluids (δ⁷Li: +11.9‰), indicate that Li has been mobilized during high-temperature fluid/sediment or fluid/rock interactions in the deep sub-surface. Intense leaching of terrigenous clay has led to radiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.7106) in pore fluids of the near-shore mud volcanoes. In contrast, non-radiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.7075) at the distal locations are attributed to admixing of a basement-derived fluid component, carrying an isotopic signature from interaction with the basaltic crust. This inference is substantiated by temperature constraints from Li isotope equilibrium calculations suggesting exchange processes at particularly high temperatures (>200 °C) for the least radiogenic pore fluids of the most distal location.Advective pore fluids in the off-shore reaches of the Gulf of Cadiz are influenced by successive exchange processes with both oceanic crust and terrigenous, fine-grained sediments, resulting in a chemical and isotopic signature similar to that of fluids in near-shore ridge flank hydrothermal systems. This suggests that deep-rooted mud volcanoes in the Gulf of Cadiz represent a fluid pathway intermediate between mid-ocean ridge hydrothermal vent and shallow, marginal cold seep. Due to the thicker sediment coverage and slower fluid advection rates, the overall geochemical signature is shifted towards the sediment-diagenetic signal compared to ridge flank hydrothermal environments.     

Isotope Geochemistry of the Pb-Zn-Ba(-Ag-Au) Mineralization at Triades-Galana,Milos Island,Greece

The Pb-Zn-Ba(-Ag-Au) mineralization in the Triades and Galana mine areas is hosted in 2.5–1.4 Ma pyroclastic rocks, and structurally controlled mostly by NE-SW or N-S trending brittle faults. Proximal pervasive silica and distal pervasive sericite-illite alteration are the two main alteration types present at the surface. The distribution of mineralization-alteration in the district suggests at least two hydrothermal events or that hydrothermal activity lasted longer at Galana. The Sr isotope signature of sphalerite and barite (⁸⁷Sr/⁸⁶Sr = 0.709162 to 0.710214) and calculated oxygen isotope composition of a fluid in equilibrium with barite and associated quartz at temperatures of around 230°C are suggestive of a seawater hydrothermal system and fluid/rock interaction. Lead isotope ratios of galena and sphalerite (²⁰⁶Pb/²⁰⁴Pb from 18.8384 to 18.8711; ²⁰⁷Pb/²⁰⁴Pb from 15.6695 to 15.6976; ²⁰⁸Pb/²⁰⁴Pb from 38.9158 to 39.0161) are similar to those of South Aegean Arc volcanic and Aegean Miocene plutonic rocks, and compatible with Pb derived from an igneous source. Galena and sphalerite from Triades-Galana have δ³⁴S_VCDT values ranging from +1 to +3.6‰, whereas barite sulfate shows δ³⁴S_VCDT values from +22.8 to +24.4‰. The sulfur isotope signatures of these minerals are explained by seawater sulfate reduction processes. The new analytical data are consistent with a seawater-dominated hydrothermal system and interaction of the hydrothermal fluid with the country rocks, which are the source of the ore metals.     

Supra-subduction zone magmatism of the Neyriz ophiolite,Iran: constraints from geochemistry and Sr-Nd-Pb isotopes

The Neyriz ophiolite along the northeast flank of the Zagros fold-thrust belt in southern Iran is an excellent example of a Late Cretaceous supra-subduction zone (SSZ)-related ophiolite on the north side of the Neotethys. The ophiolite comprises a mantle sequence including lherzolite, harzburgite, diabasic dikes, and cumulate to mylonitic gabbro lenses, and a crustal sequence comprising a sheeted dike complex and pillow lavas associated with pelagic limestone and radiolarite. Mantle harzburgites contain less CaO and Al₂O₃, are depleted in rare earth elements, and contain spinels that are more Cr-rich than lherzolites. Mineral compositions of peridotites are similar to those of both abyssal and SSZ- peridotites. Neyriz gabbroic rocks show boninitic (SSZ-related) affinities, while crustal rocks are similar to early arc tholeiites. Mineral compositions of gabbroic rocks resemble those of SSZ-related cumulates such as high forsterite olivine, anorthite-rich plagioclase, and high-Mg# clinopyroxene. Initial εNd(t) values range from +7.9 to +9.3 for the Neyriz magmatic rocks. Samples with radiogenic Nd overlap with least radiogenic mid-ocean ridge basalts and with Semail and other Late Cretaceous Tethyan ophiolitic rocks. Initial ⁸⁷Sr/⁸⁶Sr ranges from 0.7033 to 0.7044, suggesting modification due to seafloor alteration. Most Neyriz magmatic rocks are characterized by less radiogenic ²⁰⁷Pb/²⁰⁴Pb (near the northern hemisphere reference line), suggesting less involvement of sediments in their mantle source. Our results for Neyriz ophiolite and the similarity to other Iranian Zagros ophiolites support a subduction initiation setting for its generation.     

Isotopic evidence (Sr/Sr, δLi) for alteration of the oceanic crust at deep-rooted mud volcanoes in the Gulf of Cadiz, NE Atlantic Ocean

The chemical and isotopic composition of pore fluids is presented for five deep-rooted mud volcanoes aligned on a transect across the Gulf of Cadiz continental margin at water depths between 350 and 3860 m. Generally decreasing interstitial Li concentrations and ⁸⁷Sr/⁸⁶Sr ratios with increasing distance from shore are attributed to systematically changing fluid sources across the continental margin. Although highest Li concentrations at the near-shore mud volcanoes coincide with high salinities derived from dissolution of halite and late-stage evaporites, clayey, terrigenous sediments are identified as the ultimate Li source to all pore fluids investigated. Light δ⁷Li values, partly close to those of hydrothermal vent fluids (δ⁷Li: +11.9‰), indicate that Li has been mobilized during high-temperature fluid/sediment or fluid/rock interactions in the deep sub-surface. Intense leaching of terrigenous clay has led to radiogenic ⁸⁷Sr/⁸⁶Sr ratios (∼0.7106) in pore fluids of the near-shore mud volcanoes. In contrast, non-radiogenic ⁸⁷Sr/⁸⁶Sr ratios (∼0.7075) at the distal locations are attributed to admixing of a basement-derived fluid component, carrying an isotopic signature from interaction with the basaltic crust. This inference is substantiated by temperature constraints from Li isotope equilibrium calculations suggesting exchange processes at particularly high temperatures (>200 °C) for the least radiogenic pore fluids of the most distal location.Advective pore fluids in the off-shore reaches of the Gulf of Cadiz are influenced by successive exchange processes with both oceanic crust and terrigenous, fine-grained sediments, resulting in a chemical and isotopic signature similar to that of fluids in near-shore ridge flank hydrothermal systems. This suggests that deep-rooted mud volcanoes in the Gulf of Cadiz represent a fluid pathway intermediate between mid-ocean ridge hydrothermal vent and shallow, marginal cold seep. Due to the thicker sediment coverage and slower fluid advection rates, the overall geochemical signature is shifted towards the sediment-diagenetic signal compared to ridge flank hydrothermal environments.     

Sr and Nd isotope data from the fluorspar district of Asturias, northern Spain

The origin and age of the hydrothermal fluids related to the precipitation of fluorite, barite and calcite in the Villabona, La Collada and Berbes localities (Asturias fluorspar district, N Spain) have been evaluated from Sr and Nd radiogenic isotopes. Sr isotope data (⁸⁷Sr / ⁸⁶Sr = 0.7081 to 0.7096) are compatible with mixing between seawater and a more evolved groundwater that interacted with the basement. From Nd isotopes in fluorite, an isochron age of 185 ± 29 Ma (Lower Jurassic) was obtained, consistent with other hydrothermal events in the Iberian Peninsula and Europe. These constraints are essential to proceed with a quantitative model for the genesis of the mineralization that includes fluid and heat flow together with reactive transport of solutes.     

Strontium isotope zoning in garnet: implications for metamorphic matrix equilibration,geochronology and phase equilibrium modelling

In principle, garnet growth rates may be calculated from ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr measurements in garnet subsamples and the surrounding rock matrix. Because of low Rb/Sr, garnet should passively record the matrix decay of ⁸⁷Rb to ⁸⁷Sr as a progressive increase in ⁸⁷Sr/⁸⁶Sr from core to rim. This concept was tested by collecting Rb‐Sr data for five garnet grains from four major orogenic belts: eastern Vermont (c. 380 Ma), western New Hampshire (c. 320 Ma), southern Chile (c. 75 Ma) and northwestern Italy (c. 35 Ma). Both normal Sr isotope zoning (increasing ⁸⁷Sr/⁸⁶Sr from core to rim) and inverse Sr zoning (decreasing ⁸⁷Sr/⁸⁶Sr from core to rim) were observed. Garnet and matrix isotope data commonly yielded grossly inaccurate model ages. Incomplete Rb and Sr equilibration among matrix minerals is invoked to explain the deviations between theoretical v. measured zoning patterns and the age disparities. Initially, the reactive matrix is dominated by rapidly equilibrating Rb‐rich mica, which imparts high ⁸⁷Sr/⁸⁶Sr values in garnet cores. Progressive participation of slower equilibrating Sr‐rich plagioclase buffers or even reduces ⁸⁷Sr/⁸⁶Sr, possibly leading to flat or decreasing ⁸⁷Sr/⁸⁶Sr from garnet cores to rims. Unusually high ⁸⁷Sr/⁸⁶Sr in garnet in combination with bulk matrix compositions causes erroneously young apparent ages, so metamorphic ages, growth rates, and associated heating and loading rates are likely suspect. Although Rb‐Sr may be the most susceptible because of the profound disparities between mica and feldspar, zircon reactivity might influence the Lu‐Hf system by up to a few per cent. The Sm‐Nd system seems generally immune to these effects. Pseudosection analysis and conventional garnet geochronology, which presume complete matrix equilibration during metamorphism, may require modification to account for differences between whole‐rock v. reactive matrix compositions.     

87Sr/86Sr isotope composition of bottled British mineral waters for environmental and forensic purposes

Mineral waters in Britain show a wide range of ⁸⁷Sr/⁸⁶Sr isotope compositions ranging between ⁸⁷Sr/⁸⁶Sr = 0.7059 from Carboniferous volcanic rock sources in Dunbartonshire, Scotland to ⁸⁷Sr/⁸⁶Sr = 0.7207 in the Dalradian aquifer of Aberdeenshire, Scotland. The ⁸⁷Sr/⁸⁶Sr composition of the waters shows a general correlation with the aquifer rocks, resulting in the waters from older rocks having a more radiogenic signature than those from younger rocks. This wide range of values means that the Sr isotope composition of mineral water has applications in a number of types of studies. In the modern commercial context, it provides a way of fingerprinting the various mineral waters and hence provides a method for recognising and reducing fraud. From an environmental perspective, it provides the first spatial distribution of bio-available ⁸⁷Sr/⁸⁶Sr in Britain that can be used in modern, historical and archaeological studies.     

Nd-Sr isotopic and trace element study of rocks and fluids from the continental deep drilling Project (KTB), Germany

Geochemical analyses were interpreted on the dominant lithological units and on a deep crustal fluid from the Continental Deep Drilling Project (KTB) Pilot Hole, situated at the western margin of the Variscan Bohemian Massif. The biotite gneiss (from 384 m depth) shows a rare earth element pattern very similar to the European shale composite with Nd model ages of 940 Ma (CHUR) and 1.4 Ga (DM). The lamprophyre dike in the upper profile (1549 m), a nepheline and olivine normative basalt, is geochemically and isotopically similar to rocks from the Tertiary Central European Volcanic Province. The lower metabasite sequence (3575–4000 m), with an intrusion age of approximately 500 Ma, is made up primarily of highly metamorphosed subalkalic olivine basalts. The geochemical characteristics of the metabasites are a (La/Yb)_N of 5–10, an La concentration of 20–50 times chondrite as well as (⁸⁷Sr/⁸⁶Sr)_i of 0.7035–0.7038 and _Nd(T) of 4–6. These values suggest a depleted mantle source for the igneous precursors, evolving by assimilation-fractional crystallization processes with up to 25% of upper crust into the ultramafic, basaltic, and intermediate rock types of the metabasite sequence. The strong geochemical and chronological similarities between the KTB metabasites and rocks from the Münchberg Massif suggest that these units belong to the same lithological complex. The high salinity as well as the radiogenic ⁸⁷Sr/⁸⁶Sr ratio of 0.709413 in the KTB fluid from 4000 m depth might be the result of migrating fluids reacting with the regional Permo-Mesozoic evaporite deposits, followed by extensive Sr isotopic exchange with the upper crust.     

Petrology and geochemistry of the Salma dike, Raniganj coalfield (Lower Gondwana), eastern India: linkage with Rajmahal or Deccan volcanic activity?

The Gondwana (Early Permian to Early Cretaceous) basins of eastern India have been intruded by ultramafic–ultrapotassic (minette, lamproite and orangeite) and mafic (dolerite) rocks. The Salma dike is the most prominent among mafic intrusives in the Raniganj basin. This dike is tholeiitic in composition; MgO varies from 5.4 to 6.3% and the mg number from 54 to 59. In general, the major and trace element abundances are uniform both along and across the strike. There is geochemical and mineralogical evidence for fractional crystallization. The chondrite normalized REE pattern of the Salma dike (La/Yb_n=3.5) is similar to that of Deccan dikes of the Son–Narmada rift zone, western India. ⁸⁷Sr/⁸⁶Sr varies from 0.70552 to 0.70671 suggesting assimilation of crustal material. Some trace element abundances (e.g. Ti, Zr, Y) of the Salma dike are comparable to Group I Rajmahal basalts. The ⁴⁰Ar–³⁹Ar whole rock age of 65 Ma for the Salma dike is less than the ca. 114 Ma age for the Rajmahal basalt, but is similar to the generally accepted age for Deccan volcanic rocks. Despite geographical proximity with the Rajmahal basalt, the Salma dike is believed to be related to late phase of Deccan volcanic activity.     

Comparison of the Sr isotopic signatures in brines of the Canadian and Fennoscandian shields

A synthesis of Sr isotope data from shallow and deep groundwaters, and brines from the Fennoscandian and Canadian Shields is presented. A salinity gradient is evident in the water with concentrations varying from approximately 1–75 g L⁻¹ below 1500 m depth in the Fennoscandian Shield and from 10 up to 300 g L⁻¹ below 650 m depth in the Canadian Shield. Strontium isotope ratios were measured to assess the origin of the salinity and evaluate the degree of water–rock interaction in the systems. In both shields, the Sr concentrations are enriched relative to Cl, defining a positive trend parallel to the seawater dilution line and indicative of Sr addition through weathering processes. The depth distribution for Sr concentration increases strongly with increasing depth in both shields although the variation in Sr-isotope composition does not mirror that of Sr concentrations. Strontium-isotope compositions are presented for surface waters, and groundwaters in several sites in the Fennoscandian and Canadian Shields. Numerous mixing lines can be drawn reflecting water–rock interaction. A series of calculated lines links the surface end-members (surface water and shallow groundwater) and the deep brines; these mixing lines define a range of ⁸⁷Sr/⁸⁶Sr ratios for the deep brines in different selected sites. All sites show a specific ⁸⁷Sr/⁸⁶Sr signature and the occurrence of large ⁸⁷Sr/⁸⁶Sr variations is site specific in both shields. In Canadian Shield brines, the Sr isotope ratios clearly highlight large water rock interaction that increases the ⁸⁷Sr/⁸⁶Sr ratio from water that could have been of marine origin. In contrast to the Canadian Shield, groundwater does not occur in closed pockets in the Fennoscandian, and the well-constrained ⁸⁷Sr/⁸⁶Sr signatures in deep brines should correspond to a large, well-mixed and homogeneous water reservoir, whose Sr isotope signature results from water–rock interaction.     

Petrology, isotope geochemistry and chemical budgets of oceanic gabbros-seawater interactions in the Equatorial Atlantic

 Petrological and chemical variations, as well as oxygen and strontium isotopic data are presented for metagabbros from the Romanche and Vema fracture zones. These rocks were affected by several types and degrees of alterations ranging from slight hydrothermal alteration to complete amphibolitization. Five major kinds of alteration processes ranging from late-magmatic deuteric alteration (stage I) to low temperature (<150 °C) alteration (stage V) were identified. Water-rock interactions between 300 and 650 °C are the most dominant interactions resulting in the most prevailing secondary mineralogical assemblages which characterize the amphibolite and/or greenschist facies (amphibole ± plagioclase ± epidote ± titanite ± chlorite ± prehnite). Hydrothermal alteration of these gabbroic rocks results in isotopic exchanges between rocks and seawater-derived fluids. These exchanges lead to decrease of gabbroic δ¹⁸O toward values as low as +3.9‰, and larger Sr isotopic variations than other oceanic gabbroic rocks (⁸⁷Sr/⁸⁶Sr ratios shift to 0.7029–0.7051). Calculation of a chemical budget indicates that metagabbros are hydrated and enriched in Fe and probably in Mg and Cl, while Si, Ca and Ti are released to the hydrothermal fluids. In addition to metamorphic recrystallization and geochemical transformation, hydrothermal alteration of oceanic gabbros contributes to the control of the global ocean geochemistry. Received: 8 March 1999 / Accepted: 12 July 1999     

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.     

Influence of localised igneous activity on cleat dawsonite formation in Late Permian coal measures, Upper Hunter Valley, Australia

Stable (δ¹³C and δ¹⁸O) and radiogenic ⁸⁷Sr/⁸⁶Sr isotopic data have been used to investigate the origin of cleat dawsonite (NaAlCO₃(OH)₂) in the Late Permian Wittingham Coal Measures of the Upper Hunter region in the Sydney Basin, New South Wales. The δ¹³C_PDB values have a narrow range (− 1.7‰ to + 2.4‰), with an average of + 0.3‰, suggesting a magmatic source for the carbon. In contrast, δ¹⁸O_SMOW values have a wide range (+ 13.6‰ to + 19.8‰), and decrease systematically with decreasing distance from a major intrusion. This systematic variation reflects establishment of localised hydrothermal cells. Water–rock interaction between fluids associated with these hydrothermal cells, and Rb-poor volcaniclastic detritus in the coal measures, produced mantle-like ⁸⁷Sr/⁸⁶Sr (0.705032 to 0.706464) in the dawsonite.     

酒泉盆地青西凹陷下沟组湖相热水沉积岩锶同位素地球化学特征

以地质背景、物质组分和岩石组构分析为基础,对酒泉盆地青西凹陷下沟组湖相热水沉积钠长石—铁白云石岩进行了Sr同位素地球化学研究。结果表明,热水沉积岩87Sr／86Sr比值变化范围为0.712 25～0.717 81,平均值0.715 61,远高于同期海水和下沟组玄武岩,略高于代表早白垩世湖水锶同位素组成的藻灰岩,但低于基底壳源硅铝质岩,反映热流体不可能为单纯的湖水或幔源岩浆水;其中直接化学结晶沉淀的纹层状泥微晶热水沉积岩锶同位素比值变化范围较小,可代表均一化的热卤水池流体锶同位素组成特征;指示不同喷流口位置的“水爆角砾岩”锶同位素组成变化较大,但同一位置的热水角砾与胶结物锶同位素组成基本一致,说明两者应属于具相同成因意义的同期热水喷流沉积产物;综合青西凹陷下沟组湖相热水沉积岩锶同位素地球化学特征,初步推测早白垩世湖底热流体可能为富集硅铝质基底岩石高放射成因Sr的深循环下渗湖水与少量上升幔源岩浆水构成的混合热流体,可为青西凹陷早白垩世湖底热流体性质的确定以及热流体循环动力学模型和热水沉积模式的建立奠定基础。     

安徽沙坪沟斑岩钼矿床赋矿岩体钾质交代作用及其微量元素和Sr-Nd同位素响应

以沙坪沟钼矿主要的赋矿岩石——石英正长岩和花岗斑岩为对象,通过对比不同蚀变强度岩石的岩相学、岩石地球化学和同位素特征,研究该矿床的钾质交代作用-矿化特征,探讨不同热液蚀变的元素组合、蚀变过程中的元素迁移和Sr-Nd同位素的变化及其成因、不同蚀变的物理化学条件差异及其与矿化的关系,进而揭示蚀变-成矿热液流体的特征和起源。研究表明,石英正长岩和花岗斑岩的地球化学特征总体相似,显示其属同源岩浆演化产物,二者均受到钾质蚀变,但蚀变强度相差较大。钾质蚀变岩石的化学成分表现为高K_2O、Rb和低Na_2O、CaO、Sr、Ba,不同蚀变强度的岩石Rb/Sr和Sr同位素组成差别较大,花岗斑岩样品数据更显离散,甚至出现异常低的锶同位素初始值,表明热液蚀变强烈改造了Rb-Sr同位素体系,而Sm-Nd体系基本保持稳定。这一现象在东秦岭-大别钼矿带中典型的斑岩钼矿床也有出现,显示该成矿带具有相似的蚀变类型、热液起源和演化特征。而且钾长石化后期至黄铁云(绢)英岩化阶段也是最主要的钼成矿期,表明这期间流体系统pH值的降低致使Mo元素从流体中沉淀成矿。对比斑岩铜、铜-钼矿床和钼矿床的蚀变特征及其过程中元素和同位素的变化可以发现,这3种矿床均发育碱质交代作用,但蚀变强度、热液的Rb-Sr分异程度及其对原岩的改造程度存在较大差异,这暗示了各自特有的成岩、成矿物质和流体来源及大地构造背景。     

Lithospheric petrology of the eastern Arabian Plate: Constraints from Al-Ashkhara (Oman) xenoliths

Mafic granulite and spinel lherzolite xenoliths from Cenozoic alkaline basalts near Al-Ashkhara, eastern Oman, have been selected for a systematic mineralogical, geochemical and Sr–Nd–Pb isotopic study. This is the only place in E Arabia where samples of both lower crust and upper mantle can be examined. Lower crustal xenoliths consist of two mineralogically and chemically distinct groups: gabbronorite (subequal abundances of ortho- and clino-pyroxene and plagioclase) and plagioclase pyroxenite (dominant pyroxene and subordinate plagioclase). Temperature estimates for lower crustal xenoliths using the two pyroxene geothermometer (T-Wells) yield 810–865 °C. The mineral assemblage (spinel–pyroxene–plagioclase) and Al content in pyroxene indicate that plagioclase-bearing xenoliths equilibrated at 5–8 kbar (13 and 30 km depth) in the lower crust. εNd and ⁸⁷Sr/⁸⁶Sr calculated at 700 Ma for Al-Ashkhara lower crustal xenoliths (+ 6.4 to + 6.6; ⁸⁷Sr/⁸⁶Sr = 0.7028 to 0.7039) are consistent with the interpretation that juvenile, mafic melts were added to the lower crust during Neoproterozoic time and that there was no discernible contribution from pre-Neoproterozoic crust. Upper mantle xenoliths consist of both dry and hydrous (phlogopite-bearing) lherzolites. These peridotites are more Fe-rich than expected for primitive mantle or melt residues and probably formed by pervasive circulation of melts that have refertilized pre-existing mantle peridotites. Mineral equilibration temperatures range from 990 to 1070 °C. Isotopic compositions calculated at 700 Ma are εNd = + 6.8 to + 7.8 and ⁸⁷Sr/⁸⁶Sr = 0.7016 to 0.7025, indicating depleted upper mantle. Pb isotopic compositions indicate that the metasomatism was relatively recent, perhaps related to Paleogene tectonics and basanite igneous activity. Nd model ages for the spinel peridotite xenoliths range between 0.59 and 0.65 Ga. The xenolith data suggest that eastern Arabian lower crust is of hotspot origin, in contrast to western Arabian lower crust, which mostly formed at a convergent plate margin. Geochemical and isotopic differences between lower crust and upper mantle indicate that these are unrelated, possibly because delamination replaced the E Arabian mantle root in Neoproterozoic time.