Stable isotope evidence for multiple fluid regimes during carbonate cementation of the Upper Tertiary Hazeva Formation, Dead Sea Graben, southern Israel

Stable carbon- and oxygen-isotope compositions of calcite and dolomite cements have been used to understand porewater evolution in the Upper Tertiary Hazeva Formation within the Dead Sea Graben, southern Israel. Sandstone samples were obtained from four boreholes in three tectonic blocks of the graben over depths of 253–6448 m, a variation that largely reflects differential subsidence of individual fault-bounded blocks. Early carbonate cements dominate diagenesis. Calcite occurs at <1600 m, but was replaced by dolomite at greater depths. Dolomite at 1600–2700 m is Fe-poor (<0.8 mol% FeCO₃), and at 4700–6200 m, Fe-rich (0.5–7.2 mol% FeCO₃). Magnesite, anhydrite and halite are the final diagenetic phases. Calcite has positively correlated δ¹⁸O (+21‰ to +25‰) and δ¹³C (−6‰ to −2‰) values that generally decrease with depth. Dolomite has a wider variation in δ¹⁸O (+18‰ to +30‰) and δ¹³C (−8‰ to −1‰) values, which also generally are lower with increasing depth. However, the δ¹³C and δ¹⁸O values of dolomite from the uppermost 400 m of the Hazeva Formation in the Sedom Deep-1 borehole are anomalous in spanning the entire range of stable carbon and oxygen isotopic compositions over this relatively small interval.The decreasing dolomite δ¹³C values likely indicate an increased contribution of carbon from organic sources with increasing depth. Except for the uppermost 400 m, Hazeva Formation dolomite in the Sedom Deep-1 borehole has stable carbon-isotope compositions that imply initial dolomitization at much shallower levels, prior to the preferential subsidence of this tectonic block. The oxygen isotopic compositions of the calcite cement are best explained by equilibration at present burial temperatures (≤55 °C) with porewater of meteoric origin. Its δ¹⁸O values increased from −5‰ at the shallowest depths to 0‰ at 1600 m. The dolomite oxygen isotopic compositions also reflect equilibration at present burial temperatures with porewaters ranging from 0‰ at 1600 m to +7‰ at 3600 m (100 °C). In the deepest fault block (Sedom Deep-1 borehole), however, increasingly Fe-rich dolomite has (re)equilibrated with porewater whose δ¹⁸O values decreased from +9‰ at 4750 m (120 °C) to +1‰ to +2‰ by 6200 m (150 °C).Much of the dolomite likely formed at relatively shallow depths from saline brines derived from precursors to the Dead Sea. These infiltrated the Hazeva Formation, mixing with and largely displacing meteoric water, and dolomitizing calcite. Rock–water ratios tended to be high during these processes. However, the upper 400 m of the Hazeva Formation in the deepest fault block were likely deposited during its rapid tectonic subsidence, and largely escaped the initial style of dolomitization pervasive elsewhere in the study area. These sediments were also capped by evaporites. This relatively thin interval likely became a preferential conduit for brines that escaped underlying and overlying strata, including the Fe-rich, lower ¹⁸O fluids (evolved seawater?) present in the deepest part of the graben. These rocks present the most promising target for the passage and accumulation of hydrocarbons in the study area.     

Comparison of microbial gases from the Middle America Trench and Scripps Submarine Canyon: implications for the origin of natural gas

Chemical and isotopic compositions have been measured on 62 microbial gases from Tertiary hemipelagic sediments in the Middle America Trench off Guatemala and from decaying kelp and surf grass currently accumulating in Scripps Submarine Canyon off southern California. Gases from the Middle America Trench have been generated primarily by the reduction of carbon dioxide; methane δ¹³C varies from −84‰ to −39‰, methane δD varies from −208‰ to −145‰, and carbon dioxide δ¹³ C varies from −27‰ to +28‰. Gases from Scripps Submarine Canyon have been generated primarily by acetate dissimilation; methane δ¹³ C varies from −63‰ to −43‰, methane δD varies from −331‰ to −280‰, and carbon dioxide δ¹³C varies from −17‰ to +3‰.Methane δ¹³C values as heavy as −40‰ appear to be uncommon for gases produced by carbon dioxide reduction and, in the Middle America Trench, are associated with unusually positive carbon dioxide δ¹³C values. However, based on the 25‰ intramolecular fractionation between acetate car☐yl carbon and methyl carbon estimated from the Scripps Submarine Canyon data, methane produced by acetate dissimilation may commonly have heavy δ¹³C values. The δD of methane derived from acetate is more negative than natural methanes from other origins. Microbial methane δD values appear to be controlled primarily by interstitial water δD and by the relative proportions of methane derived from carbon dioxide and acetate.The chemical and isotopic compositions of microbial gas and thermogenic gas overlap, making it difficult to determine the origins of many commercial natural gases from methane δ¹³C and C₂₊ hydrocarbon concentrations alone. Measurements of methane δD and carbon dioxide δ¹³C can provide useful additional information, and together with ethane δ¹³C data, help identify gases with mixed microbial and thermogenic origins.     

Carbon and oxygen isotopes of Maastrichtian–Danian shallow marine carbonates: Yacoraite Formation, northwestern Argentina

The Maastrichtian–Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ¹³C, +2‰ δ¹⁸O). The top of the member reveals an isotopic shift of δ¹³C (−5‰) and δ¹⁸O (−10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (−2‰ δ¹³C, −1‰ δ¹⁸O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si–Mn–Fe–Na, low Ca–Mg–Sr). These isotopic and lithological changes relate to the Cretaceous–Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.     

The origin of dolomite associated with salt diapirs in central Tunisia: Preliminary investigations of field relationships and geochemistry

Black and white dolomite crystals (mm to cm width) of different isotopic composition are associated with Triassic diapirism in central Tunisia, as well as with evaporite minerals and clays. The white dolomites occur mostly in the Jabal Hadifa diapir near the contact with Cretaceous limestones, whereas the smaller black dolomites occur in the Jabal Hamra diapir. The former dolomite has a narrow range of δ¹⁸O and δ¹³C values (− 3.83‰ to − 6.60‰ VPDB for δ¹⁸O; − 2.11‰ to − 2.83‰ VPDB for δ¹³C), whereas the latter dolomite has a wider range and more depleted values (− 4.92‰ to − 9.97‰ for δ¹⁸O; − 0.55‰ to − 6.08‰ for δ¹³C). However, the ⁸⁷Sr / ⁸⁶Sr ratios of most of the samples are near Triassic seawater values. Dolomite formation is due to at least two different fluids. The main fluid originated from deeper hydrothermal or basinal sources related to the Triassic saliferous rocks and ascended through faults during the diapiric intrusion. The second, less important fluid source is related to meteoric water originating from Cretaceous rocks.     

Isotopic and molecular composition of coal-bed gas in the Amasra region (Zonguldak basin—western Black Sea)

Previous studies on the coal-bed methane potential of the Zonguldak basin have indicated that the gases are thermogenic and sourced by the coal-bearing Carboniferous units. In this earlier work, the origin of coal-bed gas was only defined according to the molecular composition of gases and to organic geochemical properties of the respective source rocks, since data on isotopic composition of gases were not available. Furthermore, in the western Black Sea region there also exist other source rocks, which may have contributed to the coal-bed gas accumulations. The aim of this study is to determine the origin of coal-bed gas and to try a gas-source rock correlation. For this purpose, the molecular and isotopic compositions of 13 headspace gases from coals and adjacent sediments of two wells in the Amasra region have been analyzed. Total organic carbon (TOC) measurements and Rock-Eval pyrolysis were performed in order to characterize the respective source rocks. Coals and sediments are bearing humic type organic matter, which have hydrogen indices (HI) of up to 300 mgHC/gTOC, indicating a certain content of liptinitic material. The stable carbon isotope ratios (δ¹³C) of the kerogen vary from −23.1 to −27.7‰. Air-free calculated gases contain hydrocarbons up to C₅, carbon dioxide (<1%) and a considerable amount of nitrogen (up to 38%). The gaseous hydrocarbons are dominated by methane (>98%). The stable carbon isotope ratios of methane, ethane and propane are defined as δ¹³C₁: −51.1 to −48.3‰, δ¹³C₂: −37.9 to −25.3‰, δ¹³C₃: −26.0 to −19.2 ‰, respectively. The δD₁ values of methane range from −190 to −178‰. According to its isotopic composition, methane is a mixture, partly generated bacterially, partly thermogenic. Molecular and isotopic composition of the gases and organic geochemical properties of possible source rocks indicate that the thermogenic gas generation took place in coals and organic rich shales of the Westphalian-A Kozlu formation. The bacterial input can be related to a primary bacterial methane generation during Carboniferous and/or to a recent secondary bacterial methane generation. However, some peculiarities of respective isotope values of headspace gases can also be related to the desorption process, which took place by sampling.     

Distinct sedimentary processes reflected in the isotopic signatures of dolomitic concretions in the Miocene Pohang Basin (southwestern East Sea)

Dolomitic concretions in diatomaceous hemipelagic sediments of the Miocene Pohang Basin in the southwestern East Sea (Sea of Japan) preserve distinct signals of two independent sedimentary processes, which controlled the extents of isotopic compositions. Variable δ¹⁸O (−9.1‰ to +0.7‰) and high δ¹³C (+3.1‰ to +17.9‰) values suggest that the concretions formed in the methanogenic zone with alteration of the residual mid-Miocene seawater by volcanogenic sediments. Remarkable δ¹⁸O and δ¹³C values show a strong linear relationship, indicating that distinctly independent depositional processes operated during the formation of the concretions. The degree of methanogenesis was enhanced during rapid hemipelagic sedimentation of organic-rich particles, resulting in higher δ¹³C values, and the effect of volcaniclastics was diluted, maintaining the original properties of ambient mid-Miocene seawater. In contrast, lower δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values characterize the effect of volcaniclastic sediments that were transported by intermittent gravity flows and interacted with mid-Miocene seawater. The input of volcaniclastic sediment probably degraded the role of methanogenesis by lowering the contents of organic matter and thereby decreased the δ¹³C values within the concretions. Isotopic signals recorded within the concretions highlight understanding of the depositional environment and evolution of the pore-water chemistry.     

Variations of stable isotopes with depth in regolith calcite cements in the Broken Hill region, Australia: Palaeoclimate evolution signal?

Twenty two samples of calcretes from seven depth-profiles in the Menindee catchment, Broken Hill region, Australia were analysed for their inorganic and organic carbon contents and inorganic carbon and oxygen isotopes. The organic carbon content is very low (from 0.06 to 0.31 wt.%) while inorganic carbon (carbonate) is up to 3.9 wt.%. Both δ¹³C and δ¹⁸O become more positive closer to the surface. Carbon isotopes vary from − 8.5‰ to −5.5‰ PDB. Oxygen isotopes vary from − 6‰ to − 1.8‰ V-PDB. Depth-related δ¹³C and δ¹⁸O variations correlate over at least 15 km and show no significant variation along the flow path. δ¹³C values increase by 3‰ and δ¹⁸O values increase by 4‰ with decreasing depth in a 1.40 m thick soil profile. The variation is interpreted to indicate an increasingly elevated air temperature, greater water stress and subsequently an aridification of the area through time. The Broken Hill calcrete data confirm that climatic evolution can be deduced from isotopic series and be applied successfully to the Broken Hill region.     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.     

Petrology and isotopic geochemistry of dawsonite-bearing sandstones in Hailaer basin, northeastern China

The CO₂ gas reservoir sandstones in the Hailaer Basin contain abundant dawsonite and provide an ideal laboratory to study whether any genetic relationship exists between dawsonite and the modern gas phase of CO₂. The origins of dawsonite and CO₂ in these sandstones were studied by petrographic and isotopic analysis. According to the paragenetic sequence of the sandstones, dawsonite grew later than CO₂ charging at 110–85 Ma. The dawsonite δ¹⁸O value is 7.4‰ (SMOW), and the calculated δ¹⁸O values of the water present during dawsonite growth are from −11.4‰ to −9.2‰ (SMOW). This, combined with the NaHCO₃-dominated water linked to dawsonite growth, suggests meteoric water being responsible for dawsonite growth. The δ¹³C values of gas phase CO₂ and the ratios of ³He/⁴He of the associated He suggest a mantle magmatic origin of CO₂-rich natural gas in Hailaer basin. Dawsonite δ¹³C values are −5.3‰ to −1.5‰ (average −3.4‰), and the calculated δ¹³C values of CO₂ gas in isotopic equilibrium with dawsonite are −11.4‰ to −7.3‰. These C isotopic values are ambiguous for the dawsonite C source. From the geological context, the timing of events, together with formation water conditions for dawsonite growth, dawsonite possibly grew in meteoric-derived water, atmospherically-derived CO₂ maybe, or at least the dominant, C source for dawsonite. It seems that there are few relationships between dawsonite and the modern gas phase of CO₂ in the Hailaer basin.     

Hydrology of a spring complex, studied by geochemical time-series data, Acquarossa, Switzerland

A case study of three springs in Switzerland is used to demonstrate the value of geochemical time-series data as a powerful tool to study the dynamics of groundwater systems. Values of repeatedly measured parameters revealed intermixings of two water types: (a) a 29°C water, circulating to a depth of 1100 m and containing approximately 700 mg/l Ca, 2000 mg/l SO₄, 700 mg/l HCO₃, 20 mg/l of Na and Cl, 6 mg/l Fe, at least 47 mg/l SiO₂, and with an isotopic composition of δD = − 73.0‰ and δ¹⁸ O = −10.9‰, and (b) a 12°C or colder water, shallow, and of a post-1953 age, containing 420 mg/l TDI or less, very low in Na and Cl (4 mg/l or less), isotopic values of δD = −71.0‰ and δ¹⁸ O = −10.5‰ and tritium as in recent (post-bomb) precipitation.     

Stable isotope and geochemical evidence of formation pore fluid evolution during diagenesis of Tertiary sandstones and mudrocks of the Niger Delta

Petrological data provide evidence that framboidal pyrite, Fe-carbonates and kaolinite are the major diagenetic minerals developed during burial diagenesis in the Tertiary Niger Delta sandstones and associated mudrocks. The pyrite sulphur, carbonate carbon and oxygen and kaolinite oxygen and hydrogen isotope compositions have been determined. These data (pyrite, δ³⁴S = −24.8 to 21.0‰; “siderite”, δ¹³C(PDB) = −14.7 to +5.0‰, δ¹⁸O(PDB) = −19.1 to −0.6‰; Fe-calcite, δ¹³C(PDB) = +17.5 to 17.9‰, δ¹⁸O(PDB) = −8.3 to −8.0‰; kaolinite, δ¹⁸O(SMOW) = +14.7 to 17.5‰, δD (SMOW) = −86 to −43‰) have been used to interpret the isotopic compositions of the precipitating pore fluids and/or the temperatures of mineral formation. The interpretation of these results indicate that in the deltaic depositional setting the syndepositional pore waters had a significant but variable marine influence that favoured the early formation of pyrite. Subsequently the subsurface influence of meteoric waters, showing varying degrees of modification involving organic and/or water-rock reactions, played an increasingly significant role in the development of later diagenetic cements in the sediments when abundant authigenic carbonates and kaolinites were formed.     

Carbon isotopes of Middle–Lower Jurassic coal-derived alkane gases from the major basins of northwestern China

Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ¹³C values are found in the Tarim and Qaidam basins (δ¹³C₁: − 19.0 to − 29.9‰; δ¹³C₂: − 18.8 to − 27.1‰), and those with lowest δ¹³C values occur in the Turpan-Harmi and Junggar basins (δ¹³C₁: − 40.1 to − 44.0‰; δ¹³C₂: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C_5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ¹³C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.     

Molecular and carbon isotopic analysis of individual biological markers: evidence for sources of organic matter and paleoenvironmental conditions in the Upper Ordovician Maquoketa Group, Illinois Basin, U.S.A.

Variations in the carbon isotopic composition (δ¹³C) of pristane, phytane, n-heptadecane (n-C₁₇), C₂₉ ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ¹³C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C₁₇ (−32‰) and C₂₉ ααα 20R sterane (−31‰) are enriched in ¹³C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of ¹³C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ¹³C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.     

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

Petrological, geochemical, and stable isotope constraints on the genesis of the Miocene igneous rocks of Chetaibi and Cap de Fer (NE Algeria)

Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ³⁴S and δ¹⁸O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ³⁴S values (−5.4‰ to −12.2‰) and high δ¹⁸O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ³⁴S and δ¹⁸O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ³⁴S, between −33.2‰ and +25.7‰. Massive andesites with δ³⁴S between +6.8‰ and +7.6‰ preserve a ³⁴S-enriched mantle signature. The δ³⁴S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ³⁴S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ¹⁸O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ¹⁸O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ¹⁸O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ¹⁸O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].     

The Daduhe gold field at the eastern margin of the Tibetan Plateau: He, Ar, S, O, and H isotopic data and their metallogenic implications

The Daduhe gold field comprises several shear-zone-controlled Tertiary lode gold deposits distributed at the eastern margin of the Tibetan Plateau. The deposits are hosted in a Precambrian granite–greenstone terrane within the Yangtze Craton. The gold mineralization occurs mainly as auriferous quartz veins with minor sulphide minerals. Fluid inclusions in pyrite have ³He/⁴He ratios of 0.16 to 0.86 R_a, whereas their ⁴⁰Ar/³⁶Ar ratios range from 298 to 3288, indicating a mixing of fluids of mantle and crust origins. The δ³⁴S values of pyrite are of 0.7–4.2‰ (n = 12), suggesting a mantle source or leaching from the mafic country rocks. δ¹⁸O values calculated from hydrothermal quartz are between − 1.5‰ and + 6.0‰ and δD values of the fluids in the fluid inclusions in quartz are − 39‰ and − 108‰. These ranges demonstrate a mixing of magmatic/metamorphic and meteoric fluids. The noble gas isotopic data, along with the stable isotopic data suggest that the ore-forming fluids have a dominantly crustal source with a significant mantle component.     

Assessing the past thermal and chemical history of fluids in crystalline rock by combining fluid inclusion and isotopic investigations of fracture calcite

Fluid inclusion studies combined with the isotope geochemistry of several generations of fracture calcite from the Olkiluoto research site, Finland, has been used to better understand the past thermal and fluid history in the crystalline rock environment. Typically, fracture mineral investigations use O and C isotopes from calcite and an estimate of the isotopic composition of the water that precipitated the calcite to perform δ¹⁸O geothermometry calculations to estimate past temperature conditions. By combining fluid inclusion information with calcite isotopes, one can directly measure the temperature at which the calcite formed and can better determine past fluid compositions. Isotopic, petrologic and fluid inclusion studies at the Olkiluoto research site in Finland were undertaken as part of an investigation within the Finnish nuclear waste disposal program. The study revealed that four fluids were recorded by fracture calcites. From petrologic evidence, the first fluid precipitated crystalline calcite at 151–225°C with a δ¹³C signature of −21 to −13.9‰ PDB and a δ¹⁸O signature of 12.3–13.0‰ SMOW. These closed fracture fillings were found at depths greater than 500 m and were formed from a high temperature, low salinity, Na–Cl fluid of possible meteoric water altered by exchange with wallrock or dilute basinal origin. The next fluid precipitated crystalline calcite with clay at 92–210°C with a δ¹³C signature of −2.6 to +3.8‰ PDB and a δ¹⁸O signature of 19.4–20.7‰ SMOW. These closed fracture fillings were found at depths less than 500 m and were formed from a moderate to high temperature, low to moderate salinity, Na–Cl fluid, likely of magmatic origin. The last group of calcites to form, record the presence of two distinct fluid types. The platy (a) calcite formed at 95–238°C with a δ¹³C signature of −12.2 to −3.8‰ PDB and a δ¹⁸O signature of 14.9–19.6‰ SMOW, from a high temperature, low salinity, Na–Cl fluid of possible magmatic origin. The platy (b) calcite formed at 67–98°C with a δ¹³C signature of −13.0 to −6.2‰ PDB and a δ¹⁸O signature of 15.1–20.1‰ SMOW, from a low temperature, high salinity, Ca–Na–Cl fluid of possible basinal brine origin. The two calcites are related through a mixing between the two end members. The source of the fluids for the platy grey (a) calcites could be the olivine diabase dykes and sills that cut through the site. The source of fluids for the platy (b) calcites could be the Jotnian arkosic sandstone formations in the northern part of the site. At the Olkiluoto site, δ¹⁸O geothermometry does not agree with fluid inclusion data. The original source of the water that forms the calcite has the largest effect on the isotopic signature of the calcites formed. Large isotopic shifts are seen in any water by mineral precipitation during cooling under rock–water equilibrium fractionation conditions. Different calcite isotopic signatures are produced depending on whether cooling occurred in an open or closed system. Water–rock interaction, at varying W/R ratios, between a water and a host rock can explain the isotopic shifts in many of the calcites observed. In some cases it is possible to shift the δ¹⁸O of the water by +11.5‰ (SMOW) using a realistic water–rock ratio. This process still does not explain some of the very positive δ¹⁸O values calculated using fluid inclusion data. Several other processes, such as low temperature recrystallization, boiling, kinetic effects and dissolution of calcite from fluid inclusion walls can affect isotopic signatures to varying degrees. The discrepancy between fluid inclusion data and δ¹⁸O geothermometry at the Olkiluoto site was most likely due to poor constraint on the original source of the water.     

Chemistry and sulfur isotopic composition of precipitation at Bologna, Italy

Individual and monthly precipitation samples from the polluted atmosphere of Bologna (Emilia-Romagna province) were collected during March 1996 to May 1997 and analyzed for major ions in solution and S isotopes in dissolved SO₄.Weighted mean enrichment factors relative to seawater are found to be 1.0 for Na, 15.2 for K, 105 for Ca, 3.3 for Mg, 17.3 for SO₄ and 663 for HCO⁻₃. Very good positive correlations are observed for the Ca²⁺–Mg²⁺–HCO⁻₃–SO²⁻₄–NO⁻₃ system, indicating that dissolution of Ca (±Mg)-carbonate particles by H₂SO₄ and HNO₃ from combustion of oil and gas is a major process controlling the chemical composition of rain and snow. Na⁺ and Cl⁻ in monthly precipitation derive essentially from sea spray, but the contribution of Na⁺ from continental sources is appreciable in a number of individual rains. NH⁺₄ appears to be on average more abundant in spring and summer precipitation, its main sources being microbial activity in soils and application of fertilizers. K⁺ is probably of continental origin from soil dust.The S isotopic composition of SO₄ is systematically positive, with mean δ³⁴S values of +3.2±1.6‰ (n=40) in individual precipitation and +2.8±1.4‰ (n=12) in monthly precipitation. These isotopic compositions are interpreted in terms of a dominant contribution of S from anthropogenic emissions and subordinate contributions from biogenic and marine sources. Pollutant SO₄ is estimated to have a δ³⁴S value in the range +2.5 to +4.5‰, whereas a distinctive δ³⁴S of −4.5‰ or lower indicates SO₄ from oxidation of biogenic gases.The isotopic and chemical compositions of SO₄ do not depend on wind direction, thus testifying to a mostly local source for pollutant S in the Bologna atmosphere.     

Geochemical relation between gas hydrates and water venting in the seismic blanking zone on the northern Cascadia continental margin offshore Vancouver Island, Canada

The isotopic composition (δD and δ¹⁸O) and chloride concentration (Cl⁻) of pore waters from the northern Cascadia continental margin offshore Vancouver Island were measured to characterize the relations between the water flow regime and the distribution, formation and dissociation of gas hydrates. The δD values of pore waters in gas hydrate-bearing sediments are slightly higher ( 1‰) than those of seawater as the result of gas hydrate dissociation during core recovery and handling. Within the seismic blanking zone, the δD values were slightly lower (− 1‰) than values measured from sites outside the blanking area (0‰). We attribute these differences to 1) distillation of D-rich water during hydrate formation in the center of the blanking zone and 2) limited migration of pore water between inside and outside of the blanking zone due to different fluid fluxes. In contrast, the δ¹⁸O values and Cl⁻ concentrations do not show significant spatial variation due to decreased isotopic fractionation of oxygen and small fraction of chloride relative to hydrogen isotope during gas hydrate formation. The δD value of pore water, therefore, appears to be a sensitive indicator of gas hydrate occurrence. We estimate that gas hydrate occupied at least 2.0 to 6.3% of sediment pore space using δD distribution in this area.