Geochemical characteristics and isotopic reversal of natural gases in eastern Kopeh-Dagh,NE Iran

Natural gas samples from two gas fields located in Eastern Kopeh-Dagh area were analyzed for molecular and stable isotope compositions. The gaseous hydrocarbons in both Lower Cretaceous clastic reservoir and Upper Jurassic carbonate reservoir are coal-type gases mainly derived from type III kerogen, however enriched δD values of methane implies presence of type II kerogen related material in the source rock. In comparison Upper Jurassic carbonate reservoir gases show higher dryness coefficient resulted through TSR, while presence of C₁C₅ gases in Lower Cretaceous clastic reservoir exhibit no TSR phenomenon. Carbon isotopic values indicate gas to gas cracking and TSR occurrence in the Upper Jurassic carbonate reservoir, as the result of elevated temperature experienced, prior to the following uplifts in last 33–37 million years. The δ¹³C of carbon dioxide and δ³⁴S of hydrogen sulfide in Upper Jurassic carbonate reservoir do not primarily reflect TSR, as uplift related carbonate rock dissolution by acidic gases and reaction/precipitation of light H₂S have changed these values severely. Gaseous hydrocarbons in both reservoirs exhibit enrichment in C₂ gas member, with the carbonate reservoir having higher values resulted through mixing with highly-mature-completely-reversed shale gases. It is likely that the uplifts have lifted off the pressure on shale gases, therefore facilitated the migration of the gases into overlying horizons. However it appears that the released gases during the first major uplift (33–37 million years ago) have migrated to both reservoirs, while the second migrated gases have only mixed with Upper Jurassic carbonate reservoir gases. The studied data suggesting that economic accumulations of natural gas/shale gases deeper than Upper Jurassic carbonate reservoir would be unlikely.     

夏季大亚湾悬浮颗粒有机物碳、氮同位素组成及其物源指示

2015年夏季开展了大亚湾悬浮颗粒有机物碳（POC）、氮含量（PN）及其同位素组成的研究,结果表明,δ13C_POC和δ15N_PN的变化范围分别为-25.7‰~-17.4‰和-6.3‰~10.4‰,平均值分别为-20.2‰和8.2‰。大亚湾悬浮颗粒有机物含量及其碳氮同位素组成的空间变化反映了不同有机质来源的影响:喜洲岛附近海域表现出高POC、PN、δ13C_POC和δ15N_PN的特征,指征着浮游植物水华的主导贡献;东北部范和港附近海域具有高POC、PN、低δ13C_POC和高δ15N_PN的特征,反映了河流/河口水生有机物的影响;湾顶白寿湾附近海域的δ13C_POC和δ15N_PN出现低值,体现了陆源有机质和人类污水排放的影响。借助δ13C_POC和δ15N_PN的三端元混合模型,定量出海洋自生有机质、陆源有机质、河流/河口水生有机质等3个来源的贡献平均分别为70%、13%和17%,其中海洋自生有机质是夏季大亚湾悬浮颗粒有机物的最主要来源。从这3种来源颗粒有机物含量的空间变化看,海洋自生有机质含量由湾内向湾外减少,与初级生产力的空间变化相对应;河流/河口水生有机质含量在大亚湾东北部出现高值;陆源有机质含量在表、底层出现不同态势,表层陆源有机物含量在湾中部海域最低,而底层则呈现出自湾内向湾口增加的趋势,主要受控于离岸距离和珠江冲淡水、粤东沿岸上升流输送的影响。     

南海东沙东北部甲烷缺氧氧化作用的生物标志化合物及其碳同位素组成

南海东沙东北部碳酸盐岩和泥质沉积物中的生物标志化合物组合及其碳同位素组成分析表明,研究区内甲烷缺氧氧化作用(anaerobic oxidation of methane-AOM)发育.研究区内碳酸盐岩中含丰富的AOM标志化合物,2,6,11,15-四甲基十六烷(Crocetane-Cr.)、2,6,10,15,19-五甲基番茄烷(Pentamethylicosane-PMI)和2,6,10,15,19,23-六甲基二十四烷(Squalane-Sq角鲨烷)的13C亏损强烈(δ13C值介于-74.2‰~-119.0‰PDB之间),表明碳酸盐岩形成于AOM,同时反映该研究区曾发生过强烈、持续的富CH₄流体释放活动.柱状泥质沉积物中,AOM生物标志化合物在硫酸岩-甲烷过渡带(SMI-Sulfate-Methane Interface)边界附近相对丰度高,SMI之上样品中含量低,或未检出,表明现代环境在SMI附近有大量嗜甲烷微生物生长,使得深部上升的甲烷被大量消耗,很少有甲烷逸出海底.AOM生物标志化合物可用来指示SMI边界.不同站位、不同岩性AOM生物标志化合物组成(包括碳同位素组成)的差异反映了嗜甲烷古细菌组成的不同.     

桂林洞穴滴水对应CaCO3沉积物的稳定同位素特征与环境意义

桂林地区降水及茅茅头大岩滴水滴速和现代碳酸盐的碳氧同位素研究表明:(1)滴水沉积的δ18O达到了同位素沉积平衡,洞穴滴水的δ18O与同期降雨的δ18O值呈正相关关系;(2)在旱季和湿季交替时,滴水δ18O值滞后于降雨δ18O受活塞效应的影响;(3)δ13C难以达到同位素沉积平衡,主要受滴水动力学影响;(4)同一洞穴不同滴水对环境的响应不同,如果洞穴顶板覆盖较厚,水分在土壤和岩层中滞留时间较长,滴水则反映受到平滑作用的降雨,反之则波动较大。     

Organic geochemistry of marine source rocks and pyrobitumen-containing reservoir rocks of the Sichuan Basin and neighbouring areas,SW China

Three bitumen fractions were obtained and systematically analysed for the terpane and sterane composition from 30 Paleozoic source rocks and 64 bitumen-containing reservoir rocks within the Upper Sinian, Lower Cambrian, Lower Silurian, Middle Carboniferous, Upper Permian and Lower Triassic strata in the Sichuan Basin and neighbouring areas, China. These bitumen fractions include extractable oils (bitumen I), oil-bearing fluid inclusions and/or closely associated components with the kerogen or pyrobitumen/mineral matrix, released during kerogen or pyrobitumen isolation and demineralization (bitumen II), and bound compounds within the kerogen or pyrobitumen released by confined pyrolysis (bitumen III). In addition, atomic H/C and O/C ratios and carbon isotopic compositions of kerogen and pyrobitumen from some of the samples were measured. Geochemical results and geological information suggest that: (1) in the Central Sichuan Basin, hydrocarbon gases in reservoirs within the fourth section of the Upper Sinian Dengying Formation were derived from both the Lower Cambrian and Upper Sinian source rocks; and (2) in the Eastern Sichuan Basin, hydrocarbon gases in Middle Carboniferous Huanglong Formation reservoirs were mainly derived from Lower Silurian source rocks, while those in Upper Permian and Lower Triassic reservoirs were mainly derived from both Upper Permian and Lower Silurian marine source rocks. For both the source and reservoir rocks, bitumen III fractions generally show relatively lower maturity near the peak oil generation stage, while the other two bitumen fractions show very high maturities based on terpane and sterane distributions. Tricyclic terpanes evolved from the distribution pattern C₂₀ < C₂₁ < C₂₃, through C₂₀ < C₂₁ > C₂₃, finally to C₂₀ > C₂₁ > C₂₃ during severe thermal stress. The concentration of C₃₀ diahopane in bitumen III (the bound components released from confined pyrolysis) is substantially lower than in the other two bitumen fractions for four terrigenous Upper Permian source rocks, demonstrating that this compound originated from free hopanoid precursors, rather than hopanoids bound to the kerogen.     

Jurassic source rocks in the Vienna Basin (Austria): Assessment of conventional and unconventional petroleum potential

The Upper Jurassic marlstones (Mikulov Fm.) and marly limestones (Falkenstein Fm.) are the main source rocks for conventional hydrocarbons in the Vienna Basin in Austria. In addition, the Mikulov Formation has been considered a potential shale gas play. In this paper, organic geochemical, petrographical and mineralogical data from both formations in borehole Staatz 1 are used to determine the source potential and its vertical variability. Additional samples from other boreholes are used to evaluate lateral trends. Deltaic sediments (Lower Quarzarenite Member) and prodelta shales (Lower Shale Member) of the Middle Jurassic Gresten Formation have been discussed as secondary sources for hydrocarbons in the Vienna Basin area and are therefore included in the present study.The Falkenstein and Mikulov formations in Staatz 1 contain up to 2.5 wt%TOC. The organic matter is dominated by algal material. Nevertheless, HI values are relative low (<400 mgHC/gTOC), a result of organic matter degradation in a dysoxic environment. Both formations hold a fair to good petroleum potential. Because of its great thickness (∼1500 m), the source potential index of the Upper Jurrasic interval is high (7.5 tHC/m²). Within the oil window, the Falkenstein and Mikulov formations will produce paraffinic-naphtenic-aromatic low wax oil with low sulfur content. Whereas vertical variations are minor, limited data from the deep overmature samples suggest that original TOC contents may have increased basinwards. Based on TOC contents (typically <2.0 wt%) and the very deep position of the maturity cut-off values for shale oil/gas production (∼4000 and 5000 m, respectively), the potential for economic recovery of unconventional petroleum is limited. The Lower Quarzarenite Member of the Middle Jurassic Gresten Formation hosts a moderate oil potential, while the Lower Shale Member is are poor source rock.     

Fluid sources and stable isotope signatures in authigenic carbonates from the Northern Apennines,Italy

Authigenic carbonates are frequently associated with methane cold-seep systems, which extensively occur in various geologic settings worldwide. Of interest is the relation between the fluids involved in their formation and the isotopic signals recorded in the carbonate cements. Along the Northern Apennines foothills (Italy), hydrocarbons and connate waters still seeping nowadays are believed to be the primary sources for the formation of fossil authigenic carbonate found in Plio-Pleistocene marine sediments. Four selected outcrops of dolomitic authigenic carbonates were analysed to compare signature of seeping fluids with fractionation of stable carbon and oxygen isotopes recorded in the carbonate.Along the foothills, deep methane-rich fluids spontaneously rise to the surface through mud volcanoes or are exploited in wells drilled nearby to the fossil Plio-Pleistocene authigenic carbonates. The plumbing system providing fluids to present-day cold seeps was structurally achieved in Late Miocene and Plio-Pleistocene. δ¹³C values of methane, which vary from −51.9 to −43.0‰ VPDB, indicate that gas composition from the deep hydrocarbon reservoirs is relatively uniform along the foothills. On the contrary, δ¹³C in fossil authigenic carbonates strongly varies among different areas and also within the same outcrop.The different carbon sources that fed the investigated carbonates were identified and include: thermogenic methane from the deep Miocene reservoirs, ¹³C-enriched CO₂ derived from secondary methanogenesis and microbial methane from Pliocene successions buried in the Po Plain. The δ¹³C variability documented among samples from a single outcrop testifies that the authigenic carbonates might represent a record of varying biogeochemical processes in the hydrocarbon reservoirs. The sources of stable oxygen isotopes in authigenic carbonates are often ascribed to marine water. Oxygen isotopic fractionation in the dolomite cements indicates that marine pore water couldn't be the sole source of oxygen. δ¹⁸O values provide a preliminary evidence that connate waters had a role in the carbonates precipitation. The concomitant occurrence of active cold seepages and fossil record of former plumbing systems suggests that generation and migration of hydrocarbons are long-lasting and very effective processes along the Northern Apennines foothills.     

Sea,freshwater or saltpans? Foraging ecology of terns to assess mercury inputs in a wetland landscape: The Ebro Delta

The Ebro catchment, the largest river basin in Spain, includes various heavily industrialized areas. Among these is the Flix site, where a chemical plant has been operating since the beginning of the 20th century. This extended operational period, together with the construction of a dam next to the factory around 1960, resulted in the accumulation of large amounts of heavily polluted sediments in the adjacent riverbed, many of which are contaminated by mercury. Pollutants from Flix are carried downstream by the Ebro River to its delta. In order to assess the transfer of mercury to the complex river estuary ecosystem, we studied the ecology of the tern community living there as these birds segregate into a range of habitats. For this purpose, first we used stable isotope analysis (SIA) (δ³⁴S, δ¹³C, δ¹⁵N) of eggs to determine the trophic ecology and habitat partitioning of several tern species (Common, Sandwich, Little, Gull-Billed and Whiskered Tern) breeding sympatrically, in order to link their foraging ecology with habitat types. Next we measured mercury concentrations in eggs to monitor the input of this metal into the diverse habitats. With the exception of the Little Tern, the other terns used a restricted habitat range in the Ebro Delta, as shown by C and S isotopes; the Gull-Billed and Whiskered Tern foraged in freshwater habitats, while the Common and Sandwich Tern used marine habitats. This restricted feeding behavior of the Gull-Billed and Common Tern contrasts with previous reports in other breeding sites. The Little Tern, which showed a wide range of isotopic values, was found to be an opportunistic forager but fed mainly in saltpans, a feeding habitat not reported previously for this species in this area. We found that mercury concentrations are related to foraging habitat and diet, and are unexpectedly higher in species feeding on demersal prey in marine habitats and also higher in birds feeding in saltpans than in those feeding in freshwater habitats. The mercury concentrations found in the Little and Common Tern eggs sampled in “Punta de la Banya” may be sufficiently high to endanger breeding success.     

Chemosynthetic trophic support for the benthic community at an intertidal cold seep site at Mocha Island off central Chile

We analyzed C and N stable isotope ratios of benthic fauna and their potential food sources at an intertidal methane seep site and a control site without emanation at Mocha Island (central Chile). The objective was to trace the origin of the main food sources used by the local heterotrophic fauna, based on the hypothesis that chemosynthetic production could be partially fueling the local food web at the seep site. Food sources sampled at both sites included macroalgae, particulate organic matter and bacteria-like filaments found growing over the red algae Gelidium lingulatum within the areas of active methane release.     

页岩气成藏的关键因素

为了了解页岩气成藏的主控因素,对国内外页岩气的成藏条件进行了梳理,经综合分析认为,稳定的区域构造环境为泥、页岩的持续沉降提供了可容空间,奠定了页岩气成藏的物质基础;持续的沉降作用为泥、页岩的不间断受热和生烃提供了热力学条件;构造隆升幅度小为页岩气的保存提供了的保障,因此,区域构造稳定可能是页岩气成藏的关键。以美国福特沃斯盆地Barnett页岩的埋藏史为基础,通过四川盆地和鄂尔多斯盆地古生界泥页岩的埋藏史对比分析认为,鄂尔多斯盆地页岩气的成藏条件可能好于四川盆地,实现页岩气突破的可能性更大。