Bitumen biomarkers in the Mid-Proterozoic Ilímaussaq intrusion, Southwest Greenland - A challenge to the mantle gas theory

GC and GC/MS/MS analysis on rock extracts has shown that the bitumen in the peralkaline Ilímaussaq intrusion, previously assumed to be abiogenic, is biotic in origin. A biotic origin is in accordance with previously published stable carbon isotopic data on bituminous matter in the rocks. The biomarker distribution in the bitumen, including the less common bicadinanes, resembles that of oil seeps on the central West Greenland coast 2200 km farther north, whose source rocks and migration history are relatively well established. We use a recent re-construction of the subsidence and later exhumation of the West Greenland coastal region during the Mesozoic-Cenozoic (Japsen et al., 2006a, b) to anticipate that hydrocarbons migrated from deeper parts of the basin offshore west of Greenland. The rocks of Ilímaussaq were probably more deeply invaded than the surrounding granites due to their higher proportion of corroded minerals, which may explain why bitumen has not been observed elsewhere in the area.Hydrocarbon gases (C1-C5) present in fluid inclusions were also analysed, after having been released by treatment with hydrochloric acid that resulted in an almost complete disintegration of the Ilímaussaq intrusion rocks. The acid extraction method proved generally more efficient than the crushing procedure applied by others, but gave similar results for the chemical composition of the gas (CH₄: 88-97%) and isotopic ratios (δ¹³C₄CH: −1.6 to −5.0‰; δ¹³CC₂H₆: −9.2 to −12.5‰), with the exception of hydrocarbons hosted in quartz, which showed significantly lower isotopic values for methane (Graser et al., 2008). Previous researchers have suggested an abiotic origin for these hydrocarbon gases, but we suggest a biotic origin for the majority of them, not just those in quartz, assuming that the isotopic ratio of the constituents have changed due to loss of gas by diffusion. The assumption of gas loss via diffusion is supported by published studies on micro-fissures in minerals typical of the Ilímaussaq and field investigations showing diffusive loss of gas from the peralkaline Khibina and Lovozero massifs on the Kola Peninsula, Russia, which are, in many respects of mineralogy and hydrocarbon content, similar to the Ilímaussaq intrusion.Both the hydrocarbon gases and bitumen in the Khibina and Lovozero massifs have been cited as prime examples of a deep mantle source, although the carbon isotopic ratio of the bitumen clearly pointed to an organic origin. The trends in carbon isotopic ratio of methane released with time from freshly exposed rocks also supports our hypothesis of ¹³C enrichment of the methane remaining within the rock. Thus, there is good evidence that the hydrocarbons in the Kola alkaline massifs are mostly biotic in origin, in which case the probability of finding economic hydrocarbon accumulations from a deep mantle source seems exceedingly small.     

Hydrocarbon generation and expulsion characteristics of Eocene source rocks in the Huilu area,northern Pearl River Mouth basin,South China Sea: Implications for tight oil potential

In recent years, new oil reservoirs have been discovered in the Eocene tight sandstone of the Huilu area, northern part of the Pearl River Mouth basin, South China Sea, indicating good prospects for tight oil exploration in the area. Exploration has shown that the Huilu area contains two main sets of source rocks: the Eocene Wenchang (E₂w) and Enping (E₂e) formations. To satisfy the requirements for further exploration in the Huilu area, particularly for tight oil in Eocene sand reservoirs, it is necessary to re-examine and analyze the hydrocarbon generation and expulsion characteristics. Based on mass balance, this study investigated the hydrocarbon generation and expulsion characteristics as well as the tight oil resource potential using geological and geochemical data and a modified conceptual model for generation and expulsion. The results show that the threshold and peak expulsion of the E₂w source rocks are at 0.6% vitrinite reflectance and 0.9% vitrinite reflectance, respectively. There were five hydrocarbon expulsion centers, located in the western, eastern, and northern Huizhou Sag and the southern and northern Lufeng Sag. The hydrocarbon yields attributed to E₂w source rocks are 2.4 × 10¹¹ tons and 1.6 × 10¹¹ tons, respectively, with an expulsion efficiency of 65%. The E₂e source rock threshold and peak expulsion are at 0.65% vitrinite reflectance and 0.93% vitrinite reflectance, respectively, with hydrocarbon expulsion centers located in the centers of the Huizhou and Lufeng sags. The yields attributed to E₂e source rocks are 1.1 × 10¹¹ tons and 0.2 × 10¹¹ tons, respectively, with an expulsion efficiency of 20%. Using an accumulation coefficient of 7%–13%, the Eocene tight reservoirs could contain approximately 1.3 × 10¹⁰ tons to 2.3 × 10¹⁰ tons, with an average of 1.8 × 10¹⁰ tons, of in-place tight oil resources (highest recoverable coefficient can reach 17–18%), indicating that there is significant tight oil potential in the Eocene strata of the Huilu area.     

Thermal maturity,source rock potential and kinetics of hydrocarbon generation in Permian shales from the Damodar Valley basin,Eastern India

This study investigates the source rock characteristics of Permian shales from the Jharia sub-basin of Damodar Valley in Eastern India. Borehole shales from the Raniganj, Barren Measure and Barakar Formations were subjected to bulk and quantitative pyrolysis, carbon isotope measurements, mineral identification and organic petrography. The results obtained were used to predict the abundance, source and maturity of kerogen, along with kinetic parameters for its thermal breakdown into simpler hydrocarbons.The shales are characterized by a high TOC (>3.4%), mature to post-mature, heterogeneous Type II–III kerogen. Raniganj and Barren Measure shales are in mature, late oil generation stage (Rr%_Raniganj = 0.99–1.22; Rr%_{Barren Measure} = 1.1–1.41). Vitrinite is the dominant maceral in these shales. Barakar shows a post-mature kerogen in gas generation stage (Rr%_Barakar = 1.11–2.0) and consist mainly of inertinite and vitrinite. The δ¹³C_org value of kerogen concentrate from Barren Measure shale indicates a lacustrine/marine origin (−24.6–−30.84‰ vs. VPDB) and that of Raniganj and Barakar (−22.72–−25.03‰ vs. VPDB) show the organic provenance to be continental. The δ¹³C ratio of thermo-labile hydrocarbons (C₁–C₃) in Barren Measure suggests a thermogenic source.Discrete bulk kinetic parameters indicate that Raniganj has lower activation energies (ΔE = 42–62 kcal/mol) compared to Barren Measure and Barakar (ΔE = 44–68 kcal/mol). Temperature for onset (10%), middle (50%) and end (90%) of kerogen transformation is least for Raniganj, followed by Barren Measure and Barakar. Mineral content is dominated by quartz (42–63%), siderite (9–15%) and clay (14–29%). Permian shales, in particular the Barren Measure, as inferred from the results of our study, demonstrate excellent properties of a potential shale gas system.     

Thermal maturity of Miocene organic matter from the Carpathian Foredeep in the Czech Republic: 1D and 3D models

A three-dimensional reconstruction of burial and palaeogeothermal conditions is presented for Miocene sediments of the Carpathian Foredeep beneath the Outer Western Carpathians fold and trust belt in the eastern part of the Czech Republic. The sedimentary units involved include autochthonous Paleozoic sequences, Miocene deposits of the Carpathian Foredeep and of the Western Carpathian nappe system. Reservoir rocks with economic oil and gas accumulations occur in the fractured crystalline basement and in the Neogene Carpathian Foredeep. The studied Vizovice area, is characterized by rocks representing both Variscan and Carpathian orogenic cycles. The 3D thermal maturity and subsidence model presented allows the significance of both tectonic events to be evaluated. The model, calibrated by vitrinite reflectance from eight boreholes proved that eroded units related to the Variscan orogeny approach, in amount, those eroded during the Carpathian orogeny. The thickness of the eroded rocks does not exceed 300 m in either case. Vitrinite reflectance data from representative core samples of the Miocene organic matter show that R_r values increase with depth from 0.36 to 0.58%. A re-evaluation of archival data on the quantity and quality of organic matter shows that total organic carbon ranges from 0.20 to 2.92 wt%, and residual hydrocarbons (S₂) from 0.04 to 8.48 mg HC/g rock. These results lead to the conclusion that Neogene Unit II that was interpreted as coastline-through to shallow-marine deposition environment within the Carpathian Foredeep in the Czech Republic is potential source rock for hydrocarbon accumulations.     

Charging of the Penglai 9-1 oil field,Bohai Bay basin,China: Functions of the delta on accumulating petroleum

The Penglai 9-1 (PL9-1) oil field, which contains China's third largest offshore oil accumulation (in-place reserves greater than 2.28 × 10⁸ ton or 1.49 × 10⁹ bbl), was found in shallow reservoirs (700–1700 m, 2297–5577 ft) within the most active fault zone in east China. The PL9-1 field contains two oil-bearing series, the granite intrusions in Mesozoic (Mz) and both the sandstone reservoirs in Neogene Guantao (Ng) and Neogene Minghuazhen (Nm) Formation. The origins of the PL9-1 field, both in terms of source rock intervals and generative kitchens, were determined by analyzing biomarker distributions for 61 source rock samples and 33 oil samples. The Mesozoic granite intrusions, which hold more than 80% of the oil reserves in the field, were charged in the west by oil generated from the third member (Es₃) of the Shahejie Formation in the Bodong depression. The Neogene reservoirs of the PL9-1 field were charged in the west by oil generated from the third member (Es₃) of the Shahejie Formation in the Bodong depression and in the south by oil generated from the first member (Es₁) of the Shahejie Formation in the Miaoxibei depression. Interactive contact between the large fan delta and the mature source rocks residing in the Es₃ Formation of the Bodong depression resulted in a high expulsion efficiency from the source rocks and rapid oil accumulation in the PL9-1 field, which probably explains how can this large oil field accumulate and preserve within the largest and most active fault zone in east China.     

A geochemical traverse along the “Sperchios Basin – Evoikos Gulf” graben (Central Greece): Origin and evolution of the emitted fluids

The studied area is a 130 km long fast spreading graben in Central Greece. Its complex geodynamical setting includes both the presence of a subduction slab at depth responsible for the recent (Quaternary) volcanic activity in the area and the western termination of a tectonic lineament of regional importance (the North-Anatolian fault). A high geothermal gradient is made evident by the presence of many thermal springs with temperatures from 19 to 82 °C, that discharge along the normal faults bordering the graben.In the period 2004–2012, 58 gas and 69 water samples were collected and their chemical and isotopic analysis revealed a wide range of compositions.Two main groups of thermal waters can be distinguished on the basis of their chemical composition. The first, represented by dilute waters (E.C. <0.6 mS/cm) of the westernmost sites, is characterised by the presence of CH₄-rich and mixed N₂–CH₄ gases. The second displays higher salinities (E.C. from 12 to 56 mS/cm) due to mixing with a modified marine component. Reservoir temperatures of 150–160 °C were estimated with cationic geothermometers at the easternmost sites.Along the graben, from west to east, the gas composition changes from CH₄- to CO₂-dominated through mixed N₂–CH₄ and N₂–CO₂ compositions, while at the same time the He isotopic composition goes from typical crustal values (<0.1 R/R_A) up to 0.87 R/R_A, showing in the easternmost sites a small (3–11%) but significant mantle input. The δ¹³C values of the CO₂-rich samples suggest a mixed origin (mantle and marine carbonates).     

Prolonged Magmatic and Tectonic Development of the Caribbean Igneous Province Revealed by a Diving Submersible Survey

Using the diving submersible survey NAUTICA we investigated the central part of the Caribbean large igneous province (CLIP) to observe and sample internal portions of this proposed oceanic plateau. Most of the samples are gabbroic and doleritic rocks; basalts are scarce. Radiometric dating by ⁴⁰Ar/³⁹Ar incremental heating experiments indicate that the intrusive rocks are Campanian in age (81–75 Ma). In some places these intrusive rocks underlie older Santonian (85–83 Ma) extrusive basaltic rocks, suggesting that the Campanian rocks represent a sill injection and an underplating episode. Results of the diving program supplemented by information from ODP and DSDP drilling sites document a 20 m.y. period (94–75 Ma) of igneous activity in the submerged portion of the Caribbean large igneous province (CLIP). In the northern part of the Beata Ridge late Campanian and/or post Campanian uplift is documented by prominent Maastrichtian (71–65 Ma) erosion and the establishment of a Paleocene-middle Eocene (65–49 Ma) carbonate platform. During and after the uplift an extensional period is indicated by seismic images and the subsidence (3 km depth) of the carbonate platform. Paleocene ages (55–56 Ma) determined on some volcanic samples are attributed to localised decompression mantle melting that accompanied the extension. We document a prolonged period of magmatic and tectonic events that do not fit with the current models of short-lived plateau formation during mantle plume initiation but shares many similarities with the constructional histories of other oceanic large igneous provinces.     

Stable carbon isotopic ratios of CH4-CO2-bearing fluid inclusions in fracture-fill mineralization from the Lower Saxony Basin (Germany) - A tool for tracing gas sources and maturity

The stable carbon isotopic ratios (δ¹³C) of methane (CH₄) and carbon dioxide (CO₂) of gas-rich fluid inclusions hosted in fracture-fill mineralization from the southern part of the Lower Saxony Basin, Germany have been measured online using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS). The data reveal that CH₄ trapped in inclusions seems to be derived from different source rocks with different organic matter types. The δ¹³C values of CH₄ in inclusions in quartz hosted by Carboniferous rocks range between −25 and −19‰, suggesting high-maturity coals as the source of methane. Methane in fluid inclusions in minerals hosted by Mesozoic strata has more negative carbon isotope ratios (−45 to −31‰) and appears to represent primary cracking products from type II kerogens, i.e., marine shales. There is a positive correlation between increasing homogenization temperatures of aqueous fluid inclusions and less negative δ¹³C(CH₄) values of in co-genetic gas inclusions probably indicating different mtaturity of the potential source rocks at the time the fluids were released. The CO₂ isotopic composition of CH₄-CO₂-bearing inclusions shows slight negative or even positive δ¹³C values indicating an inorganic source (e.g., water-rock interaction and dissolution of detrital, marine calcite) for CO₂ in inclusions. We conclude that the δ¹³C isotopic ratios of CH₄-CO₂-bearing fluid inclusions can be used to trace migration pathways, sources of gases, and alteration processes. Furthermore, the δ¹³C values of methane can be used to estimate the maturity of the rocks from which it was sourced. Results presented here are further supported by organic geochemical analysis of surface bitumens which coexist with the gas inclusion-rich fracture-fill mineralization and confirm the isotopic interpretations with respect to fluid source, type and maturity.     

Source rock characteristics and hydrocarbon generation modelling of Upper Cretaceous Mukalla Formation in the Jiza-Qamar Basin,Eastern Yemen

The Upper Cretaceous Mukalla coals and other organic-rich sediments which are widely exposed in the Jiza-Qamar Basin and believed to be a major source rocks, were analysed using organic geochemistry and petrology. The total organic carbon (TOC) contents of the Mukalla source rocks range from 0.72 to 79.90% with an average TOC value of 21.50%. The coals and coaly shale sediments are relatively higher in organic richness, consistent with source rocks generative potential. The samples analysed have vitrinite reflectance in the range of 0.84–1.10 %Ro and pyrolysis T_max in the range of 432–454 °C indicate that the Mukalla source rocks contain mature to late mature organic matter. Good oil-generating potential is anticipated from the coals and coaly shale sediments with high hydrogen indices (250–449 mg HC/g TOC). This is supported by their significant amounts of oil-liptinite macerals are present in these coals and coaly shale sediments and Py-GC (S₂) pyrograms with n-alkane/alkene doublets extending beyond nC₃₀. The shales are dominated by Type III kerogen (HI < 200 mg HC/g TOC), and are thus considered to be gas-prone.One-dimensional basin modelling was performed to analysis the hydrocarbon generation and expulsion history of the Mukalla source rocks in the Jiza-Qamar Basin based on the reconstruction of the burial/thermal maturity histories in order to improve our understanding of the of hydrocarbon generation potential of the Mukalla source rocks. Calibration of the model with measured vitrinite reflectance (Ro) and borehole temperature data indicates that the present-day heat flow in the Jiza-Qamar Basin varies from 45.0 mW/m² to 70.0 mW/m² and the paleo-heat flow increased from 80 Ma to 25 Ma, reached a peak heat-flow values of approximately 70.0 mW/m² at 25 Ma and then decreased exponentially from 25 Ma to present-day. The peak paleo-heat flow is explained by the Gulf of Aden and Red Sea Tertiary rifting during Oligocene-Middle Miocene, which has a considerable influence on the thermal maturity of the Mukalla source rocks. The source rocks of the Mukalla Formation are presently in a stage of oil and condensate generation with maturity from 0.50% to 1.10% Ro. Oil generation (0.5% Ro) in the Mukalla source rocks began from about 61 Ma to 54 Ma and the peak hydrocarbon generation (1.0% Ro) occurred approximately from 25 Ma to 20 Ma. The modelled hydrocarbon expulsion evolution suggested that the timing of hydrocarbon expulsion from the Mukalla source rocks began from 15 Ma to present-day.     

冲绳海槽浮岩中碳、氢同位素组成特征

利用分阶段热解释放气体质谱分析法研究了冲绳海槽浮岩热解释放气中CO₂和H₂O的碳、氢同位素组成,结果显示:浮岩中原生CO₂和H₂O主要释放于400～1 000℃,CO₂的碳同位素组成介于-6.7×10-3～-22.7×10-3,H₂O的氢同位素组成从-45×10-3变到-71×10-3,均落入幔源火山岩的变化范围,而且浮岩的氢同位素组成与海槽区玄武岩的氢同位素组成非常接近,这表明冲绳海槽浮岩与玄武岩之间具有密切的成因联系,浮岩岩浆和玄武岩岩浆是同源岩浆不同程度结晶分异的产物.另外,这些浮岩较洋中脊玄武岩要贫13C,并富集D,同时具有从洋中脊玄武岩向岛弧玄武岩变化的趋势,这表明浮岩岩浆在形成或上升过程中可能受到俯冲板块释放流体的影响.     

Origin of the hydrocarbon gases carbon dioxide and hydrogen sulfide in Dodan Field (SE-Turkey)

Gas occurrences consisting of carbon dioxide (CO₂), hydrogen sulfide (H₂S), and hydrocarbon (HC) gases and oil within the Dodan Field in southeastern Turkey are located in Cretaceous carbonate reservoir rocks in the Garzan and Mardin Formations. The aim of this study was to determine gas composition and to define the origin of gases in Dodan Field. For this purpose, gas samples were analyzed for their molecular and isotopic composition. The isotopic composition of CO₂, with values of −1.5‰ and −2.8‰, suggested abiogenic origin from limestone. δ³⁴S values of H₂S ranged from +11.9 to +13.4‰. H₂S is most likely formed from thermochemical sulfate reduction (TSR) and bacterial sulfate reduction (BSR) within the Bakuk Formation. The Bakuk Formation is composed of a dolomite dominated carbonate succession also containing anhydrite. TSR may occur within an evaporitic environment at temperatures of approximately 120–145 °C. Basin modeling revealed that these temperatures were reached within the Bakuk Formation at 10 Ma. Furthermore, sulfate reducing bacteria were found in oil–water phase samples from Dodan Field. As a result, the H₂S in Dodan Field can be considered to have formed by BSR and TSR.As indicated by their isotopic composition, HC gases are of thermogenic origin and were generated within the Upper Permian Kas and Gomaniibrik Formations. As indicated by the heavier isotopic composition of methane and ethane, HC gases were later altered by TSR. Based on our results, the Dodan gas field may have formed as a result of the interaction of the following processes during the last 7–8 Ma: 1) thermogenic gas generation in Permian source rocks, 2) the formation of thrust faults, 3) the lateral-up dip migration of HC-gases due to thrust faults from the Kas Formation into the Bakuk Formation, 4) the formation of H₂S and CO₂ by TSR within the Bakuk Formation, 5) the vertical migration of gases into reservoirs through the thrust fault, and 6) lateral-up dip migration within reservoir rocks toward the Dodan structure.     

Specific pathways for the incorporation of dissolved barium and molybdenum into the bivalve shell: An isotopic tracer approach in the juvenile Great Scallop (Pecten maximus)

Dissolved barium and molybdenum incorporation in the calcite shell was investigated in the Great Scallop Pecten maximus. Sixty six individuals were exposed for 16 days to two successive dissolved Ba and Mo concentrations accurately differentiated by two different isotopic enrichments (⁹⁷Mo, ⁹⁵Mo; ¹³⁵Ba, ¹³⁷Ba). Soft tissue and shell isotopic composition were determined respectively by quantitative ICP-MS (Inductively Coupled Plasma Mass Spectrometer) and laser ablation – ICP-MS. Results from Ba enrichment indicate the direct incorporation of dissolved Ba into the shell in proportion to the levels in the water in which they grew with a 6–8 day delay. The low spike contributions and the low partition coefficient (D_Mo = 0.0049 ± 0.0013), show that neither the soft tissue nor the shell were significantly sensitive to Mo enrichment. These results eliminate direct Mo shell enrichment by the dissolved phase, and favour a trophic uptake that will be investigated using the successive isotopic enrichment approach developed in this study.     

Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of pH and ionic strength

The sorption of yttrium and the rare earth elements (YREEs) by amorphous ferric hydroxide at low ionic strength (0.01 M ≤ I ≤ 0.09 M) was investigated over a wide range of pH (3.9 ≤ pH ≤ 7.1). YREE distribution coefficients, defined as _iK_Fe = [MS_i]_T / (M_T[Fe³⁺]_S), where [MS_i]_T is the concentration of YREE sorbed by the precipitate, M_T is the total YREE concentration in solution, and [Fe³⁺]_S is the concentration of precipitated iron, are weakly dependent on ionic strength but strongly dependent on pH. For each YREE, the pH dependence of log _iK_Fe is highly linear over the investigated pH range. The slopes of log _iK_Fe versus pH regressions range between 1.43 ± 0.04 for La and 1.55 ± 0.03 for Lu. Distribution coefficients are well described by an equation of the form _iK_Fe = (_Sβ₁[H⁺]^− 1 + _Sβ₂[H⁺]^− 2) / (_SK₁[H⁺] + 1), where _Sβ_n are stability constants for YREE sorption by surface hydroxyl groups and _SK₁ is a ferric hydroxide surface protonation constant. Best-fit estimates of _Sβ_n for each YREE were obtained with log _SK₁ = 4.76. Distribution coefficient predictions, using this two-site surface complexation model, accurately describe the log _iK_Fe patterns obtained in the present study, as well as distribution coefficient patterns obtained in previous studies at near-neutral pH. Modeled log _iK_Fe results were used to predict YREE sorption patterns appropriate to the open ocean by accounting for YREE solution complexation with the major inorganic YREE ligands in seawater. The predicted log _iK_Fe′ pattern for seawater, while distinctly different from log _iK_Fe observations in synthetic solutions at low ionic strength, is in good agreement with results for natural seawater obtained by others.     

Precise determination of the cerium isotopic compositions of surface seawater in the Northwest Pacific Ocean and Tokyo Bay

We succeeded in determining the Ce isotopic composition (¹³⁸Ce/¹⁴²Ce) in seawater with an error of 2σ_m = 0.3–0.7 of ε unit. In this study, 1000–3000 L of seawater samples were passed through MnO₂ fibers to concentrate Ce and Nd for precise measurement of their isotope ratios. Four surface seawater samples of the northwestern Pacific and a coastal sample in Tokyo Bay were analyzed. Most Ce isotope ratios in the surface water showed positive ε_Ce values (+ 0.8 to + 1.4) in the northwestern Pacific Ocean. These values indicate that Ce in the surface water originates from the continental crust preferentially over mantle-derived materials. We examined binary mixing model between the continental crust and mid-ocean ridge basalt. However the model could not explain both isotopic compositions and concentrations, which implies that the atmospheric input was a possible pathway for Ce into the ocean. A negative ε_Ce value was observed in Tokyo Bay, suggesting mantle-derived sources.     

Relationships between porosity,organic matter,and mineral matter in mature organic-rich marine mudstones of the Belle Fourche and Second White Specks formations in Alberta,Canada

This study presents approaches for evaluating hybrid source rock/reservoirs within tight-rock petroleum systems. The emerging hybrid source rock/reservoir shale play in the Upper Cretaceous Second White Specks and Belle Fourche formations in central Alberta, Canada is used as an example to evaluate organic and inorganic compositions and their relationships to pore characteristics. Nineteen samples from a 77.5 m-long core were analyzed using organic petrography, organic geochemistry, several methods of pore characterization, and X-ray powder diffraction (XRD). The lower part of the studied section includes quartz- and clay-rich mudrocks of the Belle Fourche Formation with low carbonate content, whereas the upper portion contains calcareous mudrocks of the Second White Specks Formation. Strata are mineralogically composed of quartz plus albite (18–56 wt. %), carbonates (calcite, dolomite, ankerite; 1–65 wt. %), clays (illite, kaolinite, chlorite; 15–46 wt. %), and pyrite (2–12 wt. %). Petrographic examinations document that organic matter represents marine Type II kerogen partly biodegraded with limited terrestrial input. Vitrinite reflectance R_o (0.74–0.87%), T_max values (438–446 °C) and biomarkers indicate mid-maturity within the oil window. The relatively poor remaining hydrocarbon potential, expressed as an S2 value between 2.1 and 6.5 mg HC/g rock, may result from an estimated 60–83% of the original kerogen having been converted to hydrocarbons, with the bulk having migrated to adjacent sandstone reservoirs. However, the present-day remaining total organic carbon TOC_pd content remains relatively high (1.7–3.6 wt. %), compared with the estimated original TOC_o of 2.4–5.0 wt. %. The calculated transformation ratio of 60–83% suggests that the remaining 17–40 wt. % of kerogen is able to generate more hydrocarbons. The studied section is a tight reservoir with an average Swanson permeability of 3.37·10⁻⁵ mD (measured on two samples) and total porosity between 1.7 and 5.0 vol. % (3 vol. % on average). The upper part of the sandy Belle Fourche Formation, with slightly elevated porosity values (3.5–5 vol. %), likely represents the interval with the best reservoir properties in the studied core interval. Total pore volume ranges between 0.0065 and 0.0200 cm³/g (measured by a combination of helium pycnometry and mercury immersion). Mesopores (2–50 nm ∅) are the most abundant pores and occupy 34–67% of total porosity or a volume of 0.0030–0.0081 cm³/g. In comparison, micropores (<2 nm ∅) cover a wide range from 6 to 60% (volume 0.0007–0.0053 cm³/g), and macropores (>50 nm ∅) reach up to 57% with the exception of some samples failing to indicate the presence of this pore fraction (volume 0.0000–0.0107 cm³/g). Macroporosity is mostly responsible for variations in total porosity, as suggested by macroporosity's strongest correlation with total porosity within the section. The relatively narrow ranges of TOC and minerals contents among measured samples limit our ability to further deconvolute factors that influence changes in total porosity and pore size distribution.     

Variation of Icelandic and Hawaiian magmatism: evidence for co-pulsation of mantle plumes?

Based on published estimates of areal extent, thickness and dating of igneous rocks related to formation of the North Atlantic Volcanic Province, we calculate the magmatic production since the first reported magmatism at 70 Ma until present. We relate the magmatism to the Icelandic Plume and estimate the total volumetric production to 22.1 × 10⁶ km³. The magmatic production varied significantly with time, with a clear maximum of 55.5 m³/s around continental break-up at ca. 54 Ma. The lowest production is estimated at 4 m³/s, increasing to 7 m³/s at ca. 23 Ma. Two other pulses with increased activity are found around 40 Ma and in the late Miocene (10–5 Ma). The variations in productivity are consistent with a plume pulsing with a periodicity of ca. 15 million years. The same periodicity and relative timing is found for the Hawaiian Plume. If confirmed, these observations suggest that both plumes originate within the thin boundary layer near the Core-Mantle Boundary. This hypothesis may imply periodic heating of the earth’s core with subsequent heat-release to the mantle and increased global plume activity.     

Mantle source heterogeneity and magmatic evolution at Carlsberg Ridge (3.7°N): constrains from elemental and isotopic (Sr,Nd, Pb) data

We present new major element, ICP-MS trace element, and Sr–Nd–Pb isotope data of basalts from four locations along the Carlsberg Ridge (CR), northern Indian Ocean. The basalts are low-K tholeiites with 7.52–9.51 wt% MgO, 49.40–50.60 wt% SiO₂, 0.09–0.27 wt% K₂O, 2.55–2.90 wt% Na₂O, and 0.60–0.68 Mg^#. Trace element contents of the basalts show characteristics similar to those of average normal MORB, such as LREE depleted patterns with (La/Sm)_N ratio of 0.55–0.69; however, some samples are enriched in large-ion lithophile elements such as K and Rb, suggesting probable modification of the mantle source. Poor correlations between the compatible elements [e.g. Ni, Cr, and Sr (related to olivine, clinopyroxene and plagioclase, respectively)] and the incompatible elements (e.g. Zr and Y), and positive correlations in the Zr versus Zr/Y and Nb versus Nb/Y plots suggest a magmatic evolution controlled mainly by mantle melting rather than fractional crystallization. Our results extend the CR basalt range to higher radiogenic Pb isotopes and lower ¹⁴³Nd/¹⁴⁴Nd. These basalts and basalts from the northern Indian Ocean Ridge show lower ¹⁴³Nd/¹⁴⁴Nd and higher ⁸⁷Sr/⁸⁶Sr values than those of the depleted mantle (DM), defining a trend towards pelagic sediment composition. The Pb isotopic ratios of basalts from CR 3–4°N lie along the compositional mixing lines between the DM and the upper continental crust. However, the low radiogenic Pb of basalts from CR 9–10°N lie on the mixing line between the DM and lower continental crust. Since the Pb isotopic ratio of MORB would decrease if the source mantle was contaminated by continental lithospheric mantle, we suggest that CR contains continental lithospheric material, resulting in heterogeneous mantle beneath different ridge segments. The continental lithospheric material was introduced into the asthenosphere before or during the breakup of the Gondwana. These results support the long-term preservation of continental material in the oceanic mantle which would significantly influence the isotopic anomaly of the Indian Ocean MORB.     

YREE sorption on hydrous ferric oxide in 0.5 M NaCl solutions: A model extension

Distribution coefficients, _iK_Fe, were measured for sorption of yttrium and the rare earth elements (YREEs) on hydrous ferric oxide (HFO) in 0.5 M NaCl solutions over the pH range 3.9–8.4 (T = 25 °C). An existing, non-electrostatic model [Quinn, K.A., Byrne, R.H., Schijf, J., 2006. Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: influence of pH and ionic strength. Mar. Chem. 99, 128–150] was modified to account for sorption of YREE–chloride complexes, as well as YREE–hydroxide complexes at elevated pH. The extended model, which allows calculation of _iK_Fe as a function of [H⁺], contains two parameters, _SK₁ and _SK₂, to describe the equilibrium between positive, neutral, and negative forms of the hydroxyl functional groups on the HFO surface. In addition, it contains several composite, conditional stability constants, A_n, that represent YREE bonding to the neutral groups with release of n protons and/or to the negatively charged groups with release of n ? 1 protons.In 0.5 M NaCl solutions, YREE sorption on HFO is weaker and less pH dependent, yielding only 0.7–0.9 protons per YREE cation on average, vs. about 1.5 at low ionic strength. This is due to enhanced deprotonation of the HFO surface (_SK₁ ~ 0, p_SK₂ = 6.16), leading to an increase in the proportion of negatively charged groups, which release fewer protons per YREE cation sorbed. On a logarithmic scale, _iK_Fe is a nearly linear function of pH, except at pH > 8 where cumulative sorption of YREE–hydroxide complexes causes it to rise more rapidly, especially for the heavy REEs. Both our own data and prior results from the literature are well described by the extended model, using only three adjustable parameters, A₁–A₃. The constant A₃, representing YREE bonding to the negatively charged groups with release of two protons, shows an excellent linear free-energy relation when plotted against the first YREE hydrolysis constant, β₁*. There is no evidence for YREE bonding to the positively charged groups (i.e., A₀ = 0).     

冲绳海槽中部伊平屋脊火山岩地球化学和Sr-Nd-Pb同位素组成：对岩石成因和地幔源区的指示

As an active back-arc basin, the Okinawa Trough is located in the southeastern region of the East China Sea shelf and is strongly influenced by the subduction of the Philippine Sea Plate. Major element, trace element and Sr-NdPb isotopic composition data are presented for volcanic rocks from the Iheya Ridge(IR), the middle Okinawa Trough. The IR rocks record large variations in major elements and range from basalts to rhyolites. Similar trace element distribution characteristics together with small variations in ~(87)Sr/~(86)Sr(0.703 862–0.704 884), ~(144)Nd/~(143)Nd(0.512 763–0.512 880) and Pb isotopic ratios, demonstrate that the IR rocks are derived from a similar magma source. The fractional crystallization of olivine, clinopyroxene, plagioclase, and amphibole, as well as accessory minerals, can reasonably explain the compositional variations of these IR rocks. The simulations suggest that approximately 60% and 75% fractionation of an evolved basaltic magma can produce trace element compositions similar to those of the intermediate rocks and acid rocks, respectively. The analysis of their Sr-Nd-Pb isotopic content ratios suggest that the source of the rocks from the IR is close to the depleted mantle(DM) but extends to the enriched mantle(EMII), indicating that the mantle source of these rocks is a mixture between the DM and EMII end members. The simulations show that the source of the IR volcanic rocks can be best interpreted as the result of the mixing of approximately 0.8%–2.0% subduction sediment components and 98.0%–99.2% mantlederived melts.     

The distribution and characteristics of the igneous complexes in the northern East China Sea Shelf Basin and their implications for hydrocarbon potential

This paper presents results of two-dimensional seismic mapping of the northern East China Sea Shelf Basin. Various igneous features such as sills, volcanic edifices and stocks were identified by the geophysical exploration. The sills are most common, and are observed at more than 90 locations. Most mapped sills in the study area are characterized by high-amplitude continuous reflections with distinct terminations. Saucer- and cup-shaped sills are observed locally. The stocks are discordant (nearly vertical) igneous bodies and they are characterized by seismic transparency, with upturned host rocks and uplifted overburden. The volcanic edifices and/or necks consist of irregular mounds and peaks and are characterized by strong positive top reflections with chaotic internal facies. The oldest igneous activity in the northern East China Sea Shelf Basin is Early Cretaceous (123.3 ± 3.7). This igneous activity coincides with those observed in eastern China which has been related mainly to the subduction of the Pacific Plate beneath Eurasia Plate. The Miocene igneous activity is well constrained based on seismic stratigraphic relationships within the folded stratigraphy, age dating, and the occurrence of igneous sills. The timing of this intrusion is coincident with the intensive igneous activity as previously suggested for the eastern China. Igneous rocks can produce hydrocarbon traps, reservoirs and they can act as a seal, and therefore are of great importance in petroleum study.