Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

An experimental comparison of gas generation from three oil fractions: Implications for the chemical and stable carbon isotopic signatures of oil cracking gas

Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in ¹³C than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 °C/h, the dryness index of the gases (defined as the volume percentage of C₁ in C_1–5) from the cracking of saturates ranges from 26.2–90.6% with the methane carbon isotope change ranging from −54.8‰ to −35.5‰, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from −39.9‰ to −32.2‰. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C₂/C₃) vs. δ¹³C₂–δ¹³C₃ and δ¹³C₁ vs. δ¹³C₂–δ¹³C₃, indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation.The kinetic parameters for the bulk generation of C_1–5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 °C/Ma and an initial temperature of 50 °C show that the temperatures of C_1–5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C_1–5 gases from the aromatics is modeled to be initiated about 122 °C whereas the initiation temperature for the saturates sample is 176 °C. Below 189 °C (EasyRo = 1.8%), the yields of C_1–5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of ¹³C enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

Geochronology and geochemistry of Mesozoic mafic–ultramafic complexes in the southern Liaoning and southern Jilin provinces,NE China: Constraints on the spatial extent of destruction of the North China Craton

LA–ICP–MS zircon U–Pb ages, geochemical and Sr–Nd–Pb isotope data are presented for mafic–ultramafic complexes from the southern Liaoning–southern Jilin area with the aim of determining the nature of the Mesozoic lithospheric mantle and to further constrain the spatial extent of destruction of the North China Craton (NCC). The complexes consist of olivine-websterite, gabbro, dolerite, and gabbro-diorite. Zircons from the complexes show typical zoning absorption, are euhedral–subhedral in shape, and yield high Th/U ratios (1.23–2.87), indicating a magmatic origin. Zircon U–Pb age data indicate that they formed in the Early Cretaceous (129–137 Ma). Geochemically, they have SiO₂ = 44.3–49.8%, MgO = 6.8–26.5%, Cr = 102–3578 ppm, and Ni = 31–1308 ppm, and are characterized by enrichment in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depletion in high field strength elements (HFSEs) and heavy rare earth elements (HREEs), as well as a wide range of Sr–Nd–Pb isotopic compositions [(⁸⁷Sr/⁸⁶Sr)i = 0.70557–0.71119; ε_Nd (t) = ?5.4 to ?20.1; (²⁰⁶Pb/²⁰⁴Pb)i = 15.13–17.85; Δ7/4 = ?11.49 to 16.00; Δ8/4 = 102.64–203.48]. Compared with the southern Liaoning mafic–ultramafic rocks, the southern Jilin mafic–ultramafic rocks have high TiO₂ and Al₂O₃ contents, high ε_Nd (t) values, low (La/Yb)_N values, low initial ⁸⁷Sr/⁸⁶Sr ratios, and low radiogenic Pb isotopic compositions. These findings indicate that the primary magmas of the southern Jilin complexes were derived from lithospheric mantle that was previously metasomatized by a melt derived from the delaminated ancient lower crust, whereas the primary magmas of the southern Liaoning complexes originated from partial melting of a lithospheric mantle source that was previously modified by melt derived from the broken-off Yangtze slab. Therefore, the lateral extent of the NCC destruction should include the southern Liaoning–southern Jilin area.     

Organic geochemistry of the Vindhyan sediments: Implications for hydrocarbons

The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S₁ (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S₂ (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the T_max (temperature at highest yield of S₂) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH₄ (C₁), C₂H₆ (C₂), C₃H₈ (C₃) and nC₄H₁₀, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ¹³C₁) and ethane (δ¹³C₂) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C₁–C₄) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.     

Sr–Nd–Hf–Pb isotope geochemistry of basaltic rocks from the Cretaceous Gyeongsang Basin,South Korea: Implications for basin formation

To better understand the formative mechanism of the Cretaceous Gyeongsang Basin in South Korea, we determined the geochemical compositions of Early Cretaceous syntectonic basaltic rocks intercalated with basin sedimentary assemblages. Two distinct compositional groups appeared: tholeiitic to calc-alkaline basalts from the Yeongyang sub-basin and high-K to shoshonitic basaltic trachyandesites from the Jinju and Uiseong sub-basins. All collected samples exhibit patterns of light rare earth element enrichment and chondrite-normalized (La/Yb)_N ratios ranging from 2.4 to 23.6. In a primitive-mantle-normalized spidergram, the samples show distinctive negative anomalies in Nb, Ta, and Ti and a positive anomaly in Pb. The basalts exhibit no or a weak positive U anomaly in a spidergram, but the basaltic trachyandesites show a negative U anomaly. The basalts have highly radiogenic Sr [(⁸⁷Sr/⁸⁶Sr)_i = 0.70722–0.71145], slightly negative ε_Nd, positive ε_Hf [(ε_Nd)_i = −2.7 to 0.0; (ε_Hf)_i = +2.9 to +6.4], and radiogenic Pb isotopic compositions [(²⁰⁶Pb/²⁰⁴Pb)_i = 18.20–19.19; (²⁰⁷Pb/²⁰⁴Pb)_i = 15.60–15.77; (²⁰⁸Pb/²⁰⁴Pb)_i = 38.38–39.11]. The basaltic trachyandesites are characterized by radiogenic Sr [(⁸⁷Sr/⁸⁶Sr)_i = 0.70576–0.71119] and unradiogenic Nd, Hf, and Pb isotopic compositions [(ε_Nd)_i = −14.0 to −1.4; (ε_Hf)_i = −17.9 to +3.7; (²⁰⁶Pb/²⁰⁴Pb)_i = 17.83–18.25; (²⁰⁷Pb/²⁰⁴Pb)_i = 15.57–15.63; (²⁰⁸Pb/²⁰⁴Pb)_i = 38.20–38.70]. The “crust-like” signatures, such as negative Nb–Ta anomalies, elevated Sr isotopic compositions, and negative ε_Nd(t) and ε_Hf(t) values, of the basaltic trachyandesites resemble the geochemistry of Early Cretaceous mafic volcanic rocks from the southern portion of the eastern North China Craton. Considering the lower-crust-like low U/Pb and high Th/U ratios and the unradiogenic Pb isotopic compositions, the basaltic trachyandesites are considered to be derived from lithospheric mantle modified by interaction with melts that originated from foundered eclogite. Basaltic volcanism in the Yeongyang sub-basin is coeval with the basaltic trachyandesite magmatism, but it exhibits an elevated ⁸⁷Sr/⁸⁶Sr ratio at a given ¹⁴³Nd/¹⁴⁴Nd and highly radiogenic Pb isotopic compositions, which imply an origin from an enriched but heterogeneous lithospheric mantle source. Melts from subducted altered oceanic basalt and pelagic sediments are considered to be the most likely source for the metasomatism. An extensional tectonic regime induced by highly oblique subduction of the Izanagi Plate beneath the eastern Asian margin during the Early Cretaceous might have triggered the opening of the Gyeongsang Basin. Lithospheric thinning and the resultant thermal effect of asthenospheric upwelling could have caused melting of the metasomatized lithospheric mantle, producing the Early Cretaceous basaltic volcanism in the Gyeongsang Basin.     

Geochemical and isotopic evidence for a magmatic-hydrothermal origin of the polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen,South China

Polymetallic vein-type Zn-Pb deposits are located in the Xiangxi–Qiandong zinc-lead metallogenic belt (XQMB) of the northwestern margin of the Jiangnan Orogen, South China. Ores are mainly found in fault-bounded quartz veins hosted in the upper part of the Banxi Group that consists of low-grade metamorphic sandstone, siltstone with minor tuff interbeds. The Zn-Pb deposits primarily contain sphalerite, galena, chalcopyrite and pyrite, accompanied by quartz and minor calcite. Zinc, lead, copper, indium and gallium are enriched in these ores. Investigation of the ore fluid reveals low temperature (87–262 °C) with scattered salinity (range from 2.73 to 26.64 wt% NaCl_eqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ¹⁸O_{H2O SMOW} = 0.2‰ to 4.2‰; δD_{H2O SMOW} = −126‰ to −80‰). Carbon and oxygen isotopic composition of carbonate samples indicate the magmatic hydrothermal origin of CO₃²⁻ or CO₂ in ore-forming fluid (δ¹³C_PDB = −6.9‰ to −5.7‰, δ¹⁸O_SMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ³⁴S_VCDT = 8.8–14.2‰ and ²⁰⁶Pb/²⁰⁴Pb = 17.156–17.209, ²⁰⁷Pb/²⁰⁴Pb = 15.532–15.508, ²⁰⁸Pb/²⁰⁴Pb = 37.282–37.546) demonstrate that sulfur sources were relatively uniform, and low radiogenic lead isotopic compositions indicate that ore metals were derived from a relatively unradiogenic source, probably by mixing of mantle with crust. Therefore, polymetallic vein-type Zn-Pb mineralization in this area probably arose from a magmatic-related hydrothermal system, and the deposition of sulfides occurred in response to cooling and boiling of magmatic hydrothermal fluids (high salinity, high δ¹⁸O_H2O and δD_H2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ¹⁸O_H2O and δD_H2O). This study provides direct evidence that magmatism was involved in the ore-forming processes of the low temperature metallogenic district, South China, and it raises awareness about the presence of polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen and their potential as a source of zinc, copper, indium and gallium.     

The impact of severe biodegradation on the molecular and stable (C,H, N,S) isotopic compositions of oils in the Alberta Basin,Canada

Although the effects of biodegradation on the composition and physical properties of crude oil have been well studied, effects of in-reservoir petroleum biodegradation on molecular and isotopic compositions of crude oils are not yet clearly understood. The Alberta Basin, in western Canada, is one of the world’s largest petroleum accumulations and constitutes an ideal example of a natural suite of sequentially biodegraded oils. The basin hosts moderately to severely biodegraded petroleum, regionally distributed and in single, more or less continuous, oil columns. In this study, a series of oil samples from the Alberta heavy oil and oil sands provinces, with varying degrees of biodegradation, were analyzed to assess the impact of progressive biodegradation on the molecular and C, H, N, and S isotopic compositions of oils. The results of the molecular characterization of the hydrocarbon fraction of the studied oils show that the oils have suffered biodegradation levels from 2 to 10⁺ (toward the Alberta–Saskatchewan border) on the Peters and Moldowan scale of biodegradation (abbreviated PM 2 to PM 10) and from tens to hundreds on the Manco scale. Within single reservoirs, increasing biodegradation was observed from top to bottom of the oil columns at all sites studied. The whole oil stable isotopic compositions of the samples varied in the ranges δ¹³C = −31.2‰ to −29.0‰, δ²H = −147‰ to −133‰, δ¹⁵N = 0.3–4.7‰ and δ³⁴S = 0.4–6.4‰. The maximum differences between δ values of samples (Δ) within single oil columns were Δ¹³C = 1.4‰, Δ²H = 7‰, Δ¹⁵N = 1.7‰ and Δ³⁴S = 1.0‰. Regional variations in the isotopic compositions of oil samples from different wells (averaged values from top to bottom) were 1.2‰ for δ¹³C, 12‰ for δ²H, 4.1‰ for δ¹⁵N and 5.5‰ for δ³⁴S and hence generally significantly larger variations were seen than variations observed within single oil columns, especially for N and S. It appears that even severe levels of biodegradation do not cause observable systematic variations in carbon, nitrogen or sulfur isotope composition of whole oils. This indicates that sulfur and nitrogen isotopic compositions may be used in very degraded oils as indicators for oil charge from different source rock facies.     

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field,Central Mexico

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T_mi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T_h)  = 325 ± 5 °C. The boiling zone shows T_h = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO₂. Positive clathrate melting temperatures (fusion) with T_h = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO₂ (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ¹⁸O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ¹⁸O is due to the rock–water interaction at relatively high temperatures. δ¹³C stable isotope data show a magmatic source with a minor meteoric contribution for CO₂. The initial isotopic value δ³⁴S_RES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ³⁴S (FeS₂) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ¹⁸O.     

Petrogenesis of ore-forming and pre/post-ore granitoids from the Kounrad,Borly and Sayak porphyry/skarn Cu deposits,Central Kazakhstan

Ore-forming porphyries and barren granitoids from porphyry Cu deposits differ in many ways, particularly with respect to their adakitic affinity and calc-alkaline characteristics. In this study, zircon U–Pb and molybdenite Re–Os dating, whole rock geochemistry, whole rock Sr–Nd–Pb and zircon O–Hf isotopic analyses were carried out on the ore-forming granitoids from the Kounrad, Borly and Sayak deposits, and also on pre-ore and post-ore granitoids in adjacent regions of Central Kazakhstan. Geochronology results indicate that pre-ore magmatism occurred in the Late Devonian to Early Carboniferous (361.3–339.4 Ma), followed by large scale Cu mineralization (325.0–327.3 Ma at Kounrad, 311.4–315.2 Ma at Borly and 309.5–311.4 Ma at Sayak), and finally, emplacement of the Late Carboniferous post-ore barren granitoids (305.0 Ma). The geochemistry of these rocks is consistent with calc-alkaline arc magmatism characterized by strong depletions in Nb, Ta and Ti and enrichments in light rare earth elements and large ion lithophile elements, suggesting a supra-subduction zone setting. However, the ore-forming rocks at Kounrad and Sayak show adakitic characteristics with high Sr (517.5–785.3 ppm), Sr/Y (50.60–79.26), (La/Yb)_N (9.37–19.62) but low Y (6.94–11.54 ppm) and Yb (0.57–1.07 ppm), whereas ore-forming rocks at Borly and barren rocks from northwest of Borly and Sayak have normal arc magma geochemical features. The Sr–Nd–Hf–O isotopic compositions show three different signatures: (1) Sayak granitoids have very young juvenile lower crust-derived compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.70384 to 0.70451, ɛ_Nd (t) = + 4.9 to + 6.0; T_DM2 (Nd) = 580 to 670 Ma, ɛ_Hf (t) = + 11.3 to + 15.5; T_DM^C (Hf) = 330 to 600 Ma, δ¹⁸O = 6.0 to 8.1‰), and were probably generated from depleted mantle-derived magma with 5–15% sediment melt addition in the magma source; (2) the Kt-1 granite from northwest of Sayak shows extremely enriched Sr–Nd isotopic compositions ((⁸⁷Sr/⁸⁶Sr)_i = 0.71050, ɛ_Nd (t) = − 7.8, T_DM2 (Nd) = 1700 Ma), likely derived from partial melting of ancient continental crust; (3) other granitoids have transitional Sr–Nd compositions between the Sayak and Kt-1 samples, indicating a juvenile lower crust source with the addition of 10–30% of ancient crustal material. The pre-ore magmatism was probably related to partial melting of juvenile lower crust due to northward subduction of the Junggar–Balkhash Ocean, whereas the ore-forming adakitic rocks at Aktogai, Kounrad and Sayak formed by partial melting of thickened lower crust which subsequently delaminated. The ore-forming rocks at Borly, and the later post-ore barren granites, formed by partial melting of juvenile lower crust with normal thickness. This tectonic setting supports the existence of an Andean-type magmatic arc in the Devonian to the Late Carboniferous, resulting from the subduction of the Junggar–Balkhash oceanic plate. The link between whole rock geochemistry and scale of mineralization suggests a higher metallogenic potential for adakitic rocks than for normal arc magmatism.     

Distribution and significance of novel low molecular weight sterenes in an immature evaporitic sediment from the Jinxian Sag,North China

An unusual series of C₂₂–C₂₇ monounsaturated sterenes and C₂₄–C₃₀ tetracyclic terpanes (17,21-secohopanes) were detected in relatively high concentrations in an immature evaporitic marl sediment of the Jinxian Sag, Bohai Bay Basin, North China. The site of unsaturation in these novel sterenes is assigned tentatively to the D ring on the basis of mass spectral interpretation, which also distinguishes them from reported unsaturated sterenes. Other hydrocarbon biomarker or stable isotope characteristics are indicative of microbial (e.g. methyl hopanes), phytoplankton or higher plant (depleted δ¹³C values of isoprenoids and hopanes) inputs and an anoxic carbonate depositional environment (hexacyclic hopanes; tetracyclic terpanes). The hydrocarbon composition showed no obvious biodegradation and the relatively high concentration of unsaturated terpenoids (e.g. gammacerene) and low values of other established maturity parameters (T_s/T_m = 0.23; R_o = 0.44%; T_max = 417 °C), are consistent with sediments of low maturity. The novel, low molecular weight sterenes and the tetracyclic terpanes may be early diagenetic products of microbial sources in a carbonate environment.     

A LREE-depleted component in the Afar plume: Further evidence from Quaternary Djibouti basalts

Major, trace element and isotopic (Sr, Nd, Pb) data and unspiked K–Ar ages are presented for Quaternary (0.90–0.95 Ma old) basalts from the Hayyabley volcano, Djibouti. These basalts are LREE-depleted (La_n/Sm_n = 0.76–0.83), with ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.70369 to 0.70376, and rather homogeneous ¹⁴³Nd/¹⁴⁴Nd (ε_Nd = + 5.9–+ 7.3) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.47–18.55, ²⁰⁷Pb/²⁰⁴Pb = 15.52–15.57, ²⁰⁸Pb/²⁰⁴Pb = 38.62–38.77). They are very different from the underlying enriched Tadjoura Gulf basalts, and from the N-MORB erupted from the nascent oceanic ridges of the Red Sea and Gulf of Aden. Their compositions closely resemble those of (1) depleted Quaternary Manda Hararo basalts from the Afar depression in Ethiopia and (2) one Oligocene basalt from the Ethiopian Plateau trap series. Their trace element and Sr, Nd, Pb isotope systematics suggest the involvement of a discrete but minor LREE-depleted component, which is probably an intrinsic part of the Afar plume.     

The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

Isotopic characteristics of river sediments on the Tibetan Plateau

We systematically collected 40 modern clastic sediment samples from rivers in different tectonic units of the Tibetan Plateau and measured their Sr–Nd isotopic compositions. The isotopic characteristics provide insight into the controversial paleo-tectonic affinity of terranes of the Tibetan Plateau and the provenance of Songpan–Ganzi flysch complex. The Qilian Terrane and Himalaya Terrane have more negative ε_Nd(0) values (from ? 14.3 to ? 11.8 and from ? 20.64 to ? 13.26, respectively) and high ⁸⁷Sr/⁸⁶Sr values (from 0.719674 to 0.738818 and from 0.721020 to 0.824959, respectively), reflecting old and mature continental crust origin of these two terranes. The southern Lhasa Terrane is more radiogenic in ε_Nd(0) values (from ? 8.82 to ? 3.8) and low in ⁸⁷Sr/⁸⁶Sr values (from 0.711504 to 0.719489), implying the combined impact of the Neo-Tethys mantle and Himalaya old continental crust. Sr–Nd isotopic compositions of the Qilian Terrane are similar to those in the Yangtze Craton, indicating that the Qilian Terrane was probably separated from the Yangtze Craton. Sr–Nd isotopic characteristics of the Songpan–Ganzi Terrane are similar to the Yangtze Craton and are remarkably different to those in the North China Craton, eastern Kunlun–Qaidam and the central Qiangtang metamorphic belt, implying that the widely distributed flysch complex of the Songpan–Ganzi Terrane was sourced from the Yangtze Craton.     

Geology and isotope geochemistry (C–O–S) of the Diyadin gold deposit,Eastern Turkey: A newly-discovered Carlin-like deposit

Diyadin mineralization is the first reported gold deposit located in a collisional tectonic environment in Eastern Anatolia. The mineralization is related to N–S and N10–20°W-trending fault systems and hosted within the Paleozoic metamorphic basement rocks of the Anatolide–Toride microcontinent. Calc-schist, dolomitic marble and Miocene and Quaternary volcanic rocks comprise the exposed units in the mineralized area. Geochemical signatures, alteration types and host rock characteristics of the Diyadin gold deposit resemble those of Carlin-type deposits. Mineralization is constrained by alteration of overlying volcanic rocks to younger than ~ 14 Ma (K–Ar).Carbon and oxygen stable isotope measurements of carbonate rocks were made on six drill holes (n = 81) with an additional four samples of fresh carbonate rocks from surface outcrops. Background carbonate rocks have δ¹³C_V-PDB ~ 1.8‰ and δ¹⁸O_V-SMOW ~ 27‰. Isotopically-altered host rock samples have decreased δ¹⁸O (down to ~+11.4‰) and variable δ¹³C (from − 3.6 to + 4.8‰). Postore carbonate veins and cave-fill material have distinctly different isotopic signatures, particularly carbon (from δ¹³C = + 8.4 to + 9.8‰). Whether this post-ore carbonate is simply very late in mineralization associated with the gold system, or is a completely different, younger system utilizing the same pathways, is unclear at present. Within the host rock sample set, there is no correlation between gold and δ¹³C, and a weak correlation between gold and δ¹⁸O, indicative of water–rock interaction and isotopic alteration. Both the isotopic data and structural mapping suggest that the main upflow zone for the deposit is near the northern portion of the drill fence. Additional data at multiple scales are required to clarify the relationship(s) between fluid flow and mineralization.     

Geochemistry,Sr–Nd–Pb–Hf isotopes systematics and geochronological constrains on petrogenesis of the Xishan A-type granite and associated W–Sn mineralization in Guangdong Province,South China

The Xishan deposit, located in the western Guangdong Province in South China, is a quartz-vein type W-Sn deposit with an average Sn grade of 0.1–0.4 wt%. The deposit is temporally and spatially associated with Xishan alkali feldspar granite. The W–Sn mineralization is present mainly as veins that are hosted by the granite. In this paper we present new zircon U–Pb age, whole-rock geochemical data, Sr–Nd–Pb–Hf isotopic data and Re–Os age in order to constrain the nature and timing of magmatism and mineralization in the Xishan mining district with implications on geodynamic settings. LA–ICP–MS zircon U–Pb analyses yielded an age of 79.14 ± 0.31 Ma for the alkali feldspar granite, consistent with the molybdenite Re–Os age of 79.41 ± 1.11 Ma. The alkali feldspar granite shows high contents of SiO₂ (71.52–76.25 wt%), high total alkalis (Na₂O + K₂O = 9.35–13.51 wt%), high field strength elements (e.g. Zr = 95.4–116 ppm, Y = 97.1–138 ppm, Nb = 36.1–55.5 ppm, Ga = 97.1–138 ppm), and rare earth elements (total REE = 171.8–194.0 ppm) as well as high Ga/Al ratios (10,000 × Ga/Al = 3.23–3.82) suggesting that it has the geochemical characteristics of A-type granite and shows an A₂ subtype affinity. Sr–Nd isotopes of the alkali feldspar granite show that (⁸⁷Sr/⁸⁶Sr)_i values range from 0.7111 to 0.7183, and the ε_Nd(t) values and Nd model ages (T_2DM) vary from −6.8 to −6.5 and 1414 to 1433 Ma, respectively. The Pb isotopic compositions are variable, with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values ranging from 18.783 to 18.947, 15.709 to 15.722 and 38.969 to 39.244, respectively, indicating that the alkali feldspar granite was derived from a mantle-crust mixed source. In situ Hf isotopic analyses reveal that the alkali feldspar granite has ε_Hf(t) values ranging from −9.69 to −0.04 and two-stage Hf model ages from 1145 Ma to 1755 Ma, indicating that the alkali feldspar granite was formed by the partial melting of Mesoproterozoic crusts of the Cathaysia Block with additions of mantle-derived materials. These results, together with previously presented regional geological relationships, suggest that the formation of the Xishan granite and associated W–Sn mineralization is related to lithospheric extension and asthenospheric upwelling that are attributed to a directional change of Pacific plate motion.     

Petrogenesis and tectonic settings of the Late Carboniferous Jiamantieliek and Baogutu ore-bearing porphyry intrusions in the southern West Junggar,NW China

Porphyry Cu deposits occurred in the southern West Junggar of Xinjiang, NW China and are represented by the Baogutu and newly-discovered Jiamantieliek porphyry Cu deposits. Petrographical and geochemical studies show that both Jiamantieliek and Baogutu ore-bearing intrusions comprise main-stage diorite stock and minor late-stage diorite porphyry dikes and are the calc-alkaline intermediate intrusions. Based on U–Pb zircon SHRIMP analyses, the Jiamantieliek intrusion formed in 313 ± 4 Ma and 310 ± 5 Ma, while, based on U–Pb zircon SIMS analyses, the Baogutu intrusion formed in 313 ± 2 Ma and 312 ± 2 Ma. Rocks in the Jiamantieliek intrusion are enriched in light rare earth elements (LREE) and large ion lithophile elements (LILE) with negative Nb anomaly. Their isotopic compositions (ε_Nd(t) = +1.6 to +3.4, (⁸⁷Sr/⁸⁶Sr)_i = 0.70369–0.70401, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.31–5.41) suggest a mixing origin from depleted to enriched mantle sources. In the Baogutu intrusion, the rocks are similar to those of the Jiamantieliek intrusion. Their Sr-Nd-Pb isotopic composition (ε_Nd(t) = +4.4 to +6.0, (⁸⁷Sr/⁸⁶Sr)_i = 0.70368–0.70385, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.34–5.42) shows a more depleted mantle source. These features suggest generation in an island arc. The Jiamantieliek and Baogutu intrusions have similar characteristics, indicating that a relatively uniform and integrated source region has existed in the southern West Junggar since the Palaeozoic. A larger contribution of calc-alkaline magma would be required to generate the Jiamantieliek intrusion, which may reflect the development of magma arc maturation towards the western section of the southern West Junggar.     

Evolution of rare-earth mineralization in the Bear Lodge carbonatite,Wyoming: Mineralogical and isotopic evidence

The Bear Lodge alkaline complex in northeastern Wyoming (USA) is host to potentially economic rare-earth mineralization in carbonatite and carbonatite-related veins and dikes that intrude heterolithic diatreme breccias in the Bull Hill area of the Bear Lodge Mountains. The deposit is zoned and consists of pervasively oxidized material at and near the surface, which passes through a thin transitional zone at a depth of ~ 120–183 m, and grades into unaltered carbonatites at depths greater than ~ 183–190 m. Carbonatites in the unoxidized zone consist of coarse and fine-grained calcite that is Sr-, Mn- and inclusion-rich and are characterized by the presence of primary burbankite, early-stage parisite and synchysite with minor bastnäsite that have high (La/Nd)cn and (La/Ce)_cn values. The early minerals are replaced with polycrystalline pseudomorphs consisting of secondary rare-earth fluorocarbonates and ancylite with minor monazite. Different secondary parageneses can be distinguished on the basis of the relative abundances and composition of individual minerals. Variations in key element ratios, such as (La/Nd)_cn, and chondrite-normalized profiles of the rare-earth minerals and calcite record multiple stages of hydrothermal deposition involving fluids of different chemistry. A single sample of primary calcite shows mantle-like δ¹⁸O_V-SMOW and δ¹³C_V-PDB values, whereas most other samples are somewhat depleted in ¹³C (δ¹³C_V-PDB ≈ − 8 to − 10‰) and show a small positive shift in δ¹⁸O_V-SMOW due to degassing and wall-rock interaction. Isotopic re-equilibration is more pronounced in the transitional and oxidized zones; large shifts in δ¹⁸O_V-SMOW (to ~ 18‰) reflect the input of meteoric water during pervasive hydrothermal reworking and supergene oxidation. The textural relations, mineral chemistry and C and O stable-isotopic variations record a polygenetic sequence of rare-earth mineralization in the deposit. With the exception of one Pb-poor sample showing an appreciable positive shift in ²⁰⁸Pb/²⁰⁴Pb value (~ 39.2), the Bear Lodge carbonatites are remarkably uniform in their Nd, Sr and Pb isotopic composition: ¹⁴³Nd/¹⁴⁴Nd_t = 0.512591–0.512608; εNd_t = 0.2–0.6; ⁸⁷Sr/⁸⁶Sr_t = 0.704555–0.704639; εSr_t = − 1.5–2.7; ²⁰⁶Pb/²⁰⁴Pb_t = 18.071–18.320; ²⁰⁷Pb/²⁰⁴Pb_t = 15.543–15.593; and ²⁰⁸Pb/²⁰⁴Pb_t = 38.045–39.165. These isotopic characteristics indicate that the source of the carbonatitic magma was in the subcontinental lithospheric mantle, and modified by subduction-related metasomatism. Carbonatites are interpreted to be generated from small degrees of partial melt that may have been produced via interaction of upwelling asthenosphere giving a small depleted MORB component, with an EM1 component likely derived from subducted Farallon crust.