Characterization of magmatic sulfur in the Aegean island arc by means of the δ34S values of fumarolic H2S, elemental S, and hydrothermal gypsum from Nisyros and Milos islands

A delta(34)S value of +6.3 +/- 1.5% was estimated for the rhyodacitic degassing magma present underneath the hydrothermal system of Nisyros, based on the S isotope ratios of H2S in fumarolic vapors. This value was estimated by modeling the irreversible water-rock mass transfers occurring during the generation of the hydrothermal liquid which separates these fumarolic vapors. The S isotope ratio of the rhyodacitic degassing magma of Nisyros is consistent with fractional crystallization of a parent basaltic magma with an initial delta(34)S value of +4% (+/-at least 1.5%). This positive value could be explained by mantle contamination due to by either transference of fluids derived from subducted materials or involvement of altered oceanic crust, whereas contribution of biogenic sulfides from sediments seems to be negligible or nil. This conclusion agrees with the lack of N-2 and CO2 from thermal decomposition of organic matter contained in subducted sediments, which is a characteristic of the whole Aegean arc system. Since hydrothermal S at Milos and Santorini has isotope ratios similar to those determined at Nisyros, it seems likely that common controlling processes are active throughout the Aegean island arc. (C) 2002 Elsevier, Science B.V. All rights reserved.

Evidence of growth and sector zoning in hydrothermal quartz from Alpine veins

Several quartz crystals from three different Alpine vein localities and of known petrologic setting and evolution have been examined for possible elemental sector zoning in order to help to constrain the mechanisms of such trace element incorporation. Using different in situ techniques (EMPA, LA-ICPMS, SIMS, FTIR-spectroscopy), it was established that Al and Li concentrations can exceed several hundreds of ppma for distinct growth zones within crystals formed at temperatures of about 300 degrees C or less and that also display patterns of cyclic growth when examined with cathodoluminescence. In contrast, crystals formed at temperatures closer to 400 degrees C and without visible cyclic growth have low concentrations of Al and Li as well as other trace elements. Al and Li contents are correlated along profiles measured within the crystals and in general their proportion does not change along the profiles. No relationships were found between Al, Na, and K, and germanium has a qualitative relationship with Al. FTIR spectra also show OH(-) absorption bands within the quartz, with higher amplitudes in zones rich in Al and Li. Sector zoning is present. It is most pronounced between prismatic and rhombohedral faces of the same growth zone, but also between the rhombohedral faces of r and z, which contain different amounts of trace elements. The sector zoning is also expressed by changes in the Li/Al ratio, with higher ratios in 17 compared to r faces. It is concluded that the incorporation of trace elements into hydrothermal quartz from Alpine veins is influenced by growth mechanisms and surface-structures of the growing quartz crystals, the influence of which may change as a function of temperature, pH, as well as the chemical composition of the fluid.

Natural evidence for rapid abiogenic hydrothermal generation of CH4

Although recent hydrothermal experiments imply that abiogenic methane (CH4) generation from hydrothermal reduction of CO2 can occur, evidence from natural systems was still lacking. Based on the chemical and isotopic equilibrium signatures of low-temperature fumarolic gas discharges, we are able to provide hard evidence for its natural occurrence, namely in three subduction-related bi-phase hydrothermal systems of the Mediterranean, whose temperatures range from 260 to 470 degrees C. The attainment of equilibrium and the time spans of recent volcanic dormancy allowed us to calculate minimum rates for chemical and isotopic equilibration. These are significantly higher than those previously reported and might be due to the presence of a saturated water vapor phase in the investigated systems. The fact that nature provides conditions enabling relatively fast production of hydrocarbons from CO2 strongly supports the concerns that were recently raised from laboratory experiments. These address the use of the carbon isotope composition of reduced carbon in Archean sediments as a tracer of early life and the occurrence of CH4 on extraterrestrial planets as a bioindicator. In view of the potential role of abiogenic CH4 as a precursor of life, we also present an estimate of abiogenic hydrothermal CH4 fluxes throughout the Archean. It is not expected that these fluxes exceeded 80 Mt/yr during the past 4.0 Ga. This, however, would have been enough to facilitate HCN production on the prebiotic Earth. (C) 2007 Elsevier Ltd. All rights reserved.

Geochemical evidence for mixing of magmatic fluids with seawater, Nisyros hydrothermal system, Greece

The chemical and isotopic compositions (deltaD(H2O), delta(18)O(H2O), delta(18)O(CO2), delta(13)C(CO2), delta(34)S, and He/N-2 and He/Ar ratios) of fumarolic gases from Nisyros, Greece, indicate that both arc-type magmatic water and local seawater feed the hydrothermal system. Isotopic composition of the deep fluid is estimated to be +4.9+/-0.5parts per thousand for delta(18)O and -11+/-5parts per thousand for deltaD corresponding to a magmatic water fraction of 0.7. Interpretation of the stable water isotopes was based on liquid-vapor separation conditions obtained through gas geothermometry. The H-2-Ar, H-2-N-2, and H-2-H2O geothermometers suggest reservoir temperatures of 345+/-15 degreesC, in agreement with temperatures measured in deep geothermal wells, whereas a vapor/liquid separation temperature of 260+/-30 degreesC is indicated by gas equilibria in the H2O-H-2-CO2-CO-CH4 system. The largest magmatic inputs seem to occur below the Stephanos-Polybotes Micros crater, whereas the marginal fumarolic areas of Phlegeton-Polybotes Megalos craters receive a smaller contribution of magmatic gases.

Bitumens in the late Variscan hydrothermal vein-type uranium deposit of Pribram, Czech Republic: Sources, radiation-induced alteration, and relation to mineralization

The late Variscan (275-278 Ma) Pribram uranium deposit is one of the largest known accumulations of uraniferous bitumens in hydrothermal veins. The deposit extends along the northwestern boundary of the Central Bohemian pluton (345-335 Ma) with low-grade metamorphosed Late Proterozoic and unmetamorphosed Cambrian rocks. From a net uranium production of 41,742 metric tons (t), more than 6,000 t were extracted from bitumen-uraninite ores during 43 years of exploration and mining. Three morphological varieties of solid bitumen are recognized: globular, asphaltlike, and cokelike. While the globular bitumen is uranium free, the other two types are uraniferous. The amount of bitumen in ore veins gradually decreases toward the contact with the plutonic body and increases with depth. Two types of bitumen microtextures are recognized using high-resolution transmission electron microscopy: amorphous and microporous, the former being less common in uraniferous samples. A lower Raman peak area ratio (1,360/1,575 cm(-1)) in mineralized bitumens (0.9) compared with uranium-free samples (2.0) indicates a lower degree of microtextural organization in the latter The H/C and O/C atomic ratios in uranium-free bitumens (0.9-1.1 and 0.09, respectively) are higher than those in mineralized samples (H/C = 0.3-0.8, O/C = 0.03-0.09). The chloroform extractable matter yield is Very low in uranium-free bitumens (0.30-0.35% of the total organic carbon,TOC) and decreases with uranium content increase. The extracted solid uraniferous bitumen infrared spectra show depletion in aliphatic CH2 and CH3 groups compared to uranium-free samples. The concentration of oxygen-bearing functional groups relative to aromatic bonds in the IR spectra of uranium-free and mineralized bitumen, however, do not differ significantly. C-13 NMR confirmed than the aromaticity of a uraniferous sample is higher (F-ar = 0.61) than in the uranium-free bitumen (F-ar = 0.51). Pyrolysates from uraniferous and nonuraniferous bitumens do not differ significantly, being predominantly cresol, alkylphenols, alkylbenzenes, and alkylnaphthalenes. The liquid pyrolysate yield decreases significantly with increasing uranium content. The delta(13)C Values of bulk uranium-free bitumens and low-grade uraniferous, asphaltlike bitumens range from -43.6 to 52.3 per mil. High-grade, cokelike, uraniferous bitumens are more C-13 depleted (54.5 to -58.4 parts per thousand). In contrast to the very light isotopic ratios of the high-grade uraniferous cokelike bitumen bulk carbon, the individual n-alkanes and isoprenoids (pristane and phytane) extracted from the same sample are significantly C-13 enriched. The isotopic composition of the C13-24 n-alkanes extracted from the high-grade uraniferous sample (delta(13)C = -28.0 to 32.6 parts per thousand) are heavier compared with the same compounds in a uranium-free sample (delta(13)C = 31.9 to 33.8 parts per thousand). It is proposed that the bitumen source was the isotopically light (delta(13)C = 35.8 to 30.2 parts per thousand) organic matter of the Upper Proterozoic host rocks that were pyrolyzed during intrusion of the Central Bohemian pluton. The C-13- depleted pyrolysates were mobilized from the innermost part of the contact-metamorphic aureole, accumulated in structural traps in less thermally influenced parts of the sedimentary complex and were later extracted by hydrothermal fluids. Bitumens at the Pribram deposit are younger than the main part of the uranium mineralization and were formed through water-washing and radiation-induced polymerization of both the gaseous and liquid pyrolysates. Direct evidence for pyrolysate reduction of uranium in the hydrothermal system is difficult to obtain as the chemical composition of the original organic fluid phase was modified during water-washing and radiolytic alteration. However, indirect evidence-e.g., higher O/C atomic ratios in uranium-free bitumens (0.1) relative to the Upper Proterozoic source rocks (0.02-0.05), isotopically very light carbon in associated whewellite (delta(13)C = 31.7 to -28.4 parts per thousand), and the striking absence of bitumens in the pre-uranium, hematite stage of the mineralization-indicates that oxidation of organic fluids may have contributed to lowering of aO(2) and uraninite precipitation.

Oxygen isotope compositions of iron oxides from high-grade BIF-hosted iron ore deposits of the Central Hamersley Province, Western Australia: Constraints on the evolution of hydrothermal fluids

The Hamersley province of northwest Australia is one of the world's premier iron ore regions with high-grade martite-microplaty hematite iron ore deposits mostly hosted within banded iron formation (BIF) sequences of the Brockman Iron Formations of the Hamersley Group. These high-grade iron ores contain between 60 and 68 wt percent Fe, and formed by the multistage interaction of hydrothermal fluids with the host BIF formation. The oxygen isotope compositions of magnetite and hematite from BIF, hydrothermal alteration assemblages, and high-grade iron Ore were analyzed from the Mount Tom Price, Paraburdoo, and Charmar iron ore deposits. The delta(18)O values of magnetite and hematite from hydrothermal alteration assemblages and high-grade iron ore range from -9.0 to -2.9 per mil, a depletion of 5 to 15 per mil relative to the host BIF. The delta(18)O values are spatially controlled by faults within the deposits, a response to higher fluid flux and larger influence the isotopic compositions by the hydrothermal fluids. The oxygen isotope composition of hydrothermal fluids (delta(18)O(fluid)) indicates that the decrease in the (18)O content of iron oxides was due to the interaction of both basinal brines and meteoric fluids with the original BIF. Late-stage talc-bearing ore at the Mount Tom Price deposit formed in the presence of a pulse of delta(18)O-enriched basinal brine, indicating that hydrothermal fluids may have repeatedly interacted with the BIFs during the Paleoproterozoic.

Organic and inorganic geochemistry of Ljubija siderite deposits, NW Bosnia and Herzegovina

The Ljubija siderite deposits, hosted by a Carboniferous sedimentary complex within the Inner Dinarides, occur as stratabound replacement-type ore bodies in limestone blocks and as siderite-sulfides veins in shale. Three principal types of ore textures have been recognized including massive dark siderite and ankerite, siderite with zebra texture, and siderite veins. The ore and host rocks have been investigated by a combination of inorganic (major, trace, and rare earth element concentrations), organic (characterization of hydrocarbons including biomarkers), and stable isotope geochemical methods (isotope ratios of carbonates, sulfides, sulfates, kerogen, and individual hydrocarbons). New results indicate a marine origin of the host carbonates and a hydrothermal-metasomatic origin of the Fe mineralization. The differences in ore textures (e.g., massive siderite, zebra siderite) are attributed to physicochemical variations (e.g., changes in acidity, temperature, and/or salinity) of the mineralizing fluids and to the succession and intensity of replacement of host limestone. Vein siderite was formed by precipitation from hydrothermal fluids in the late stage of mineralization. The equilibrium fractionation of stable isotopes reveals higher formation temperatures for zebra siderites (around 245A degrees C) then for siderite vein (around 185A degrees C). Sulfur isotope ratios suggest Permian seawater or Permian evaporites as the main sulfur source. Fluid inclusion composition confirms a contribution of the Permian seawater to the mineralizing fluids and accord with a Permian mineralization age. Organic geochemistry data reflect mixing of hydrocarbons at the ore site and support the hydrothermal-metasomatic origin of the Ljubija iron deposits.

The magmatic to hydrothermal evolution of the intrusive Mont Saint-Hilaire Complex: Insights into the late-stage evolution of peralkaline rocks

The Cretaceous Mont Saint-Hilaire complex (Quebec, Canada) comprises three major rock units that were emplaced in the following sequence: (I) gabbros; (II) diorites; (III) diverse partly agpaitic foid syenites. The major element compositions of the rock-forming minerals, age-corrected Nd and oxygen isotope data for mineral separates and trace element data of Fe-Mg silicates from the various lithologies imply a common source for all units. The distribution of the rare earth elements in clinopyroxene from the gabbros indicates an ocean island basalt type composition for the parental magma. Gabbros record temperatures of 1200 to 800 degrees C, variable silica activities between 0 center dot 7 and 0 center dot 3, and f(O2) values between -0 center dot 5 and +0 center dot 7 (log delta FMQ, where FMQ is fayalite-magnetite-quartz). The diorites crystallized under uniform a(SiO2) (a(SiO2) = 0 center dot 4-0 center dot 5) and more reduced f(O2) conditions (log delta FMQ similar to-1) between similar to 1100 and similar to 800 degrees C. Phase equilibria in various foid syenites indicate that silica activities decrease from 0 center dot 6-0 center dot 3 at similar to 1000 degrees C to < 0 center dot 3 at similar to 550 degrees C. Release of an aqueous fluid during the transition to the hydrothermal stage caused a(SiO2) to drop to very low values, which results from reduced SiO(2) solubilities in aqueous fluids compared with silicate melts. During the hydrothermal stage, high water activities stabilized zeolite-group minerals. Fluid inclusions record a complex post-magmatic history, which includes trapping of an aqueous fluid that unmixed from the restitic foid syenitic magma. Cogenetic aqueous and carbonic fluid inclusions reflect heterogeneous trapping of coexisting immiscible external fluids in the latest evolutionary stage. The O and C isotope characteristics of fluid-inclusion hosted CO(2) and late-stage carbonates imply that the surrounding limestones were the source of the external fluids. The mineral-rich syenitic rocks at Mont Saint-Hilaire evolved as follows: first, alkalis, high field strength and large ion lithophile elements were pre-enriched in the (late) magmatic and subsequent hydrothermal stages; second, percolation of external fluids in equilibrium with the carbonate host-rocks and mixing processes with internal fluids as well as fluid-rock interaction governed dissolution of pre-existing minerals, element transport and precipitation of mineral assemblages determined by locally variable parameters. It is this hydrothermal interplay between internal and external fluids that is responsible for the mineral wealth found at Mont Saint-Hilaire.

Carbon and oxygen isotope study of hydrothermal carbonates in the zinc-lead deposits of the San Vicente district, central Peru: A quantitative modeling on mixing processes and CO2 degassing

Carbon and oxygen isotope studies of the host and gangue carbonates of Mississippi Valley-type zinc-lead deposits in the San Vicente District hosted in the Upper Triassic to Lower Jurassic dolostones of the Pucara basin (central Peru) were used to constrain models of the ore formation. A mixing model between an incoming hot saline slightly acidic radiogenic (Pb, Sr) fluid and the native formation water explains the overall isotopic variation (delta(13)C = - 11.5 to + 2.5 parts per thousand relative to PDB and delta(18)O = + 18.0 to + 24.3 parts per thousand relative to SMOW) of the carbonate generations. The dolomites formed during the main ore stage show a narrower range (delta(13)C = - 0.1 to + 1.7 parts per thousand and delta(18)O = + 18.7 to + 23.4 parts per thousand) which is explained by exchange between the mineralizing fluids and the host carbonates combined with changes in temperature and pressure. This model of fluid-rock interaction explains the pervasive alteration of the host dolomite I and precipitation of sphalerite I. The open-space filling hydrothermal white sparry dolomite and the coexisting sphalerite II formed by prolonged fluid-host dolomite interaction and limited CO2 degassing. Late void-filling dolomite III (or calcite) and the associated sphalerite III formed as the consequence of CO2 degassing and concomitant pH increase of a slightly acidic ore fluid. Widespread brecciation is associated to CO2 outgassing. Consequently, pressure variability plays a major role in the ore precipitation during the late hydrothermal events in San Vicente. The presence of native sulfur associated with extremely carbon-light calcites replacing evaporitic sulfates (e.g., delta(13)C = - 11.5 parts per thousand), altered native organic matter and heavier hydrothermal bitumen (from - 27.0 to - 23.0 parts per thousand delta(13)C) points to thermochemical reduction of sulfate and/or thiosulfate. The delta(13)C- and delta(18)O-values of the altered host dolostone and hydrothermal carbonates, and the carbon isotope composition of the associated organic matter show a strong regional homogeneity. These results coupled with the strong mineralogical and petrographic similarities of the different MVT occurrences perhaps reflects the fact that the mineralizing processes were similar in the whole San Vicente belt, suggesting the existence of a common regional mineralizing hydrothermal system with interconnected plumbing.

Seismic reflectivity of the sediment-covered seafloor: Effects of velocity gradients and fine-scale layering

Knowledge of the reflectivity of the sediment-covered seabed is of significant importance to marine seismic data acquisition and interpretation as it governs the generation of reverberations in the water layer. In this context pertinent, but largely unresolved, questions concern the importance of the typically very prominent vertical seismic velocity gradients as well as the potential presence and magnitude of anisotropy in soft surficial seabed sediments. To address these issues, we explore the seismic properties of granulometric end-member-type clastic sedimentary seabed models consisting of sand, silt, and clay as well as scale-invariant stochastic layer sequences of these components characterized by realistic vertical gradients of the P- and S-wave velocities. Using effective media theory, we then assess the nature and magnitude of seismic anisotropy associated with these models. Our results indicate that anisotropy is rather benign for P-waves, and that the S-wave velocities in the axial directions differ only slightly. Because of the very high P- to S-wave velocity ratios in the vicinity of the seabed our models nevertheless suggest that S-wave triplications may occur at very small incidence angles. To numerically evaluate the P-wave reflection coefficient of our seabed models, we apply a frequency-slowness technique to the corresponding synthetic seismic wavefields. Comparison with analytical plane-wave reflection coefficients calculated for corresponding isotropic elastic half-space models shows that the differences tend to be most pronounced in the vicinity of the elastic equivalent of the critical angle as well as in the post-critical range. We also find that the presence of intrinsic anisotropy in the clay component of our layered models tends to dramatically reduce the overall magnitude of the P-wave reflection coefficient as well as its variation with incidence angle.

Oxygen isotope sector zoning in natural hydrothermal quartz

Oxygen isotope measurements using SIMS and laser-fluorination methods confirm the presence of concentric and sector zoning in low-temperature (200 degrees C to < 400 degrees C) hydrothermal quartz from Alpine veins. While concentric zoning is most readily explained by changes in the chemical composition of the fluid or temperature of crystallization, the reasons for sector zoning are more difficult to explain. Relative enrichment in (18)O for crystallographically different sectors of quartz corresponds to m > r > z. Sector zoning is, however, largely limited to the exterior zones of crystals and/or to crystals with large Al (> 1000 ppm) and trace element contents, probably formed at temperatures < 250 degrees C. Differences in delta(18)O between the prismatic (m) relative to the rhombohedral (r and z) growth sectors of up to 2 parts per thousand can be explained by a combination of a face-related crystallographic and/or a growth rate control. In contrast, isotopic sector zoning of up to about 1.5 parts per thousand amongst the different rhombohedral faces increases in parallel with the trace element content and is likely to represent disequilibrium growth. This is indicated by non-systematic, up to 2 parts per thousand, differences within single growth zones and the irregular, larger or smaller, delta(18)O values (of several permil) of the exterior compared to the inner zones of the same crystals. Disequilibrium growth may be related to the large trace element content incorporated into the growing quartz at lower temperatures (< 250 degrees C) and/or be related to fluid-vapour separation, allowing crystal growth from both a vapour as well as a liquid phase.