The impact of organic fluids on the carbon isotopic compositions of carbonate-rich reservoirs: Case study of the Lucaogou Formation in the Jimusaer Sag,Junggar Basin,NW China     

《Marine and Petroleum Geology》2017

The processes involved in the interaction between organic fluids and carbonates, and the resulting effect on reservoir quality during the evolution and maturation of organic matter remain unclear despite the fact that these processes influence the carbon and oxygen isotopic compositions of carbonates. Here, we provide new insights into these processes using data obtained from a detailed analysis of a mixed dolomitic–clastic and organic-rich sedimentary sequence within the middle Permian Lucaogou Formation in the Junggar Basin of NW China. The techniques used during this study include drillcore observations, thin section petrography, scanning electron microscopy (SEM) and electron probe microanalysis, and carbon and oxygen isotope analyses. Oil grades and total organic carbon (TOC) contents represent the amount of oil charging and the abundance of organic fluids within a reservoir, respectively, and both negatively correlate with the whole-rock δ¹³C and δ¹⁸O of the carbonates in the study area, indicating that organic fluids have affected the reservoir rocks. Secondary carbonates, including sparry calcite and dolomite overgrowths and cements, are common within the Lucaogou Formation. Well-developed sparry calcite is present within dark mudstone whereas the other two forms of secondary carbonates are present within the dolomite-rich reservoir rocks in this formation. Comparing thin section petrology with δ¹³C compositions suggests that the carbon isotopic composition of matrix carbonates varies little over small distances within a given horizon but varies significantly with stratigraphic height as a result of the development of secondary carbonates. The net change in whole-rock δ¹³C as a result of these secondary carbonates ranges from 1.8‰ to 4.6‰, with the secondary carbonates having calculated δ¹³C compositions from −18.6‰ to −8.5‰ that are indicative of an organic origin. The positive correlation between the concentration of Fe within matrix and secondary carbonates within one of the samples suggests that the diagenetic system within the Lucaogou Formation was relatively closed. The correlation between δ¹³C and δ¹⁸O in carbonates is commonly thought to be strengthened by the influence of meteoric water as well as organic fluids. However, good initial correlation between δ¹³C and δ¹⁸O of whole rock carbonates within the Lucaogou Formation (resulted from the evaporitic sedimentary environment) was reduced by organic fluids to some extent. Consequently, the δ¹³C–δ¹⁸O covariations within these sediments are not always reliable indicators of diagenetic alteration by organic fluids or meteoric water.The characteristics and δ¹³C compositions of the sparry calcite within the formation is indicative of a genetic relationship with organic acids as a result of the addition of organic CO₂ to the reservoir. Further analysis suggests that both carbonate and feldspar were dissolved by interaction with organic CO₂. However, dissolved carbonate reprecipitated as secondary carbonates, meaning that the interaction between organic fluids and dolomites did not directly improve reservoir quality, although this process did enhance the dissolution of feldspar and increase porosity. This indicates that the δ¹³C and δ¹⁸O of secondary carbonates and their influence on whole-rock carbonate isotopic values can be used to geochemically identify the effect of organic fluids on closed carbonate-rich reservoir systems.  相似文献   

The oxygen and carbon isotope distribution in the Mediterranean water masses     

《Marine Geology》1999,153(1-4):41-55

The oxygen and carbon stable isotope compositions of the present-day Mediterranean waters have been measured in order to evaluate their variability, which is related to the specific climatic and hydrological conditions within the basin. The experimental equation between the δ¹⁸O value and the salinity of water, based on 300 measurements on surface, intermediate, and deep waters sampled during the VICOMED 2 and 3 cruises in the western, central and eastern Mediterranean, has a slope of 0.27, a value which is significantly lower than the slope of 0.45, as defined in the northeast Atlantic Ocean. This difference in the δ¹⁸O–salinity relationship, which occurs immediately in the Alboran basin, is basically a characteristic of the climatic regime of the Mediterranean, i.e., of an excess evaporation over fresh water input. The largest variations of these two parameters, δ¹⁸O of water and δ¹³C of ∑CO₂, are observed in the surface waters, mostly in the western Mediterranean. This evolution mirrors the progressive eastward restriction, which separates the less-evaporated and more-productive western basins from the more-evaporated and less-productive eastern basins. The intermediate waters constitute a homogeneous layer. However, their δ¹⁸O values decrease eastward by 0.35‰ at maximum, due to progressive dilution by mixing with overlying and underlying water masses; their δ¹³C values decrease also eastward by 0.35‰ at maximum, due to an increasing input of nutrients issued from the regeneration of sinking organic particles. The deep waters have similar δ¹⁸O values but slightly higher δ¹³C values (often by less than 0.1‰) than the overlying intermediate waters, indicating generally well ventilated conditions due to active winter convection.  相似文献   

Oxygen isotopic distribution along the otolith growth axis by secondary ion mass spectrometry: Applications for studying ontogenetic change in the depth inhabited by deep-sea fishes     

《Deep Sea Research Part I: Oceanographic Research Papers》2014

This study using tuna otoliths as working standards established a high lateral resolution and precision analysis to measure δ¹⁸O_otolith by secondary ion mass spectrometry. This analytical approach of the ion probe was applied to deep-sea fishes to reconstruct the likely depths inhabited by the fishes at different life history stages based on the measured δ¹⁸O_otolith values as a proxy of water temperature. Dramatic increases up to 5–6‰ in δ¹⁸O_otolith, representing a temperature decrease of approximately 20 °C, were detected in a blind cusk eel (Barathronus maculatus) otolith and in the otoliths of Synaphobranchus kaupii during leptocephalus metamorphosis to glass eel, inferred from the drop of otolith Sr/Ca ratios and increase of otolith growth increment width. δ¹⁸O_otolith profiles clearly divided the fish's life history into a planktonic stage in the mixed layer of the ocean and a benthic stage on the deep-sea ocean bottom. The habitat shift signal was recorded within a 150 µm width of otolith growth zone, which was too narrow to be clearly detected by mechanical drilling and conventional isotopic ratio mass spectrometry. However, variations down to −7‰ were found in δ¹⁸O_otolith profiles as the result of Cs²⁺ beam sputter in the core and larval portions of the otoliths. Carbon mapping by electron probe microanalyzer and staining by toluidine blue suggested abundant proteins existed in the areas with anomaly negative δ¹⁸O_otolith values, which cannot be interpreted as a habitat change but due to the isotopic fractionation by O emission from the proteins. These results implied that careful design and understanding of the chemical composition of the analytical areas or tracks on the heterogeneous otolith was essential for highly accurate and precise analysis.  相似文献   

Authigenic carbonates from active methane seeps offshore southwest Africa   总被引：2，自引：1，他引：1  

Catherine Pierre  Marie-Madeleine Blanc-Valleron  Jér?me Demange  Omar Boudouma  Jean-Paul Foucher  Thomas Pape  Tobias Himmler  Noemi Fekete  Volkhard Spiess 《Geo-Marine Letters》2012,32(5-6):501-513

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2–5?m length indicates a maximum age of about 60,000–80,000?years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (–61.0?<?δ¹³C ‰ V-PDB?<?–40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4?<?δ¹⁸O ‰ V-PDB?<?+6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ¹⁸O values might reflect the contribution of ¹⁸O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca²⁺ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ¹⁸O–δ¹³C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial–interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation–decomposition.  相似文献   

Geochemistry,origin and accumulation of natural gases in the deepwater area of the Qiongdongnan Basin,South China Sea     

《Marine and Petroleum Geology》2016

The Qiongdongnan Basin, South China Sea has received huge thickness (>12 km) of Tertiary-Quaternary sediments in the deepwater area to which great attention has been paid due to the recent discoveries of the SS22-1 and the SS17-2 commercial gas fields in the Pliocene-Upper Miocene submarine canyon system with water depth over 1300 m. In this study, the geochemistry, origin and accumulation models of these gases were investigated. The results reveal that the gases are predominated by hydrocarbon gases (98%–99% by volume), with the ratio of C₁/C_1-5 ranging from 0.92 to 0.94, and they are characterized by relatively heavy δ¹³C₁ (−36.8‰ to −39.4‰) and δD_CH4 values (−144‰ to −147‰), similar to the thermogenic gases discovered in the shallow water area of the basin. The C_5-7 light hydrocarbons associated with these gases are dominated by isoparaffins (35%–65%), implying an origin from higher plants. For the associated condensates, carbon isotopic compositions and high abundance of oleanane and presence of bicadinanes show close affinity with those from the YC13-1 gas field in the shallow water area. All these geochemical characteristics correlate well with those found in the shales of the Oligocene Yacheng Formation in the Qiongdongnan Basin. The Yacheng Formation in the deepwater area has TOC values in the range of 0.4–21% and contains type II_b–III gas-prone kerogens, indicating an excellent gas source rock. The kinetic modeling results show that the δ¹³C₁ values of the gas generated from the Yacheng source rock since 3 or 4 Ma are well matched with those of the reservoir gases, indicating that the gas pool is young and likely formed after 4 Ma. The geologic and geochemical data show that the mud diapirs and faults provide the main pathways for the upward migration of gases from the deep gas kitchen into the shallow, normally pressured reservoirs, and that the deep overpressure is the key driving force for the vertical and lateral migration of gas. This gas migration pattern implies that the South Low Uplift and the No.2 Fault zone near the deepwater area are also favorable for gas accumulation because they are located in the pathway of gas migration, and therefore more attention should be paid to them in the future.  相似文献   

Stable Isotopic Composition of Particulate Organic Carbon in the Caspian Sea     

M. D. Kravchishina  A. A. Klyuvitkin  L. A. Pautova  N. V. Politova  A. Yu. Lein 《Oceanology》2018,58(1):45-56

The data on the isotopic composition of particulate organic carbon (δ¹³C_POC) in the Caspian Sea water in summer–autumn 2008, 2010, 2012, and 2013 are discussed in the paper. These data allowed as to reveal the predominant genesis of organic carbon in suspended particulate matter of the active seawater layer (from 0 to 40 m). The δ¹³C_POC =–27‰ (PDB) and δ¹³C_POC =–20.5‰ (PDB) values were taken as the reference data for terrigenous and planktonogenic organic matter, respectively. Seasonal (early summer, late summer, and autumn) variations in the composition of suspended particulate matter in the active sea layer were revealed. A shift of δ¹³C_POC towards greater values was seen in autumn (with a slight outburst in the development (bloom) of phytoplankton) in comparison with summer (with large accumulations and an extraordinary phytoplankton bloom confined to the thermocline area). The seasonal dynamics of autochthonous and allochthonous components in the suspended particulate matter of the Middle and Southern Caspian Sea was studied with the use of data on the concentration of particulate matter and chlorophyll a, the phytoplankton biomass and the POC content.  相似文献   

Carbon cycle and sea-water palaeotemperature evolution at the Middle–Late Jurassic transition,eastern Paris Basin (France)     

《Marine and Petroleum Geology》2014

A very high-resolution carbon and oxygen stable isotope analysis (bulk-carbonate) of a biostratigraphically well-constrained Callovian–Oxfordian series is provided here for the first time. The homogeneity of the clayey series and the weak diagenetic alteration allow the isotopic signal variations to be considered as primary in origin. A prominent and brief negative excursion in the δ¹³C curve (−2‰), occurring at the start of the Middle Callovian (Jason Zone – Obductum Subzone) and correlated regionally, suggests a possible methane release. The increasing δ¹³C values thereafter up to the Early Oxfordian, concomitant with a warming episode, highlight the burial of carbon in organic-rich layers which, in return, may have triggered a decrease in atmospheric pCO₂. At higher frequencies, observed fluctuations of the δ¹³C and δ¹⁸O values are orbitally driven (405-kyr and 100-kyr eccentricity cycles) and may correspond to the salinity and temperature variability recorded in sea water. The δ¹⁸O isotopic measurements from well-preserved diagenetically screened belemnites and bivalves along the series, compared to available data from Tethyan domains, agree with the scenario of a global cooling at the Middle-Late Jurassic transition. The well-dated δ¹⁸O isotopic curve suggests that the onset of this cooling event occurred at the end of the Coronatum Zone (Middle Callovian).  相似文献   

Mechanisms of sulfur incorporation and isotope fractionation during early diagenesis in sediments of the gulf of California     

M.B. Goldhaber  I.R. Kaplan 《Marine Chemistry》1980,9(2):95-143

Sediment cores were taken from the Gulf of California, and pore waters recovered by mechanical squeezing. The chemistry and isotopic abundance of sulfur in these pore fluids were compared with coexisting solid phases to deduce the mechanisms involved in pyrite formation. The results suggest that burrowing activities of benthonic organisms supply sulfate sulfur to sediments to depths of approximately 0.5 m from the surface. This is inferred from essentially constant pore water concentration profiles of dissolved ions in horizons where sulfate reduction is demonstrated by the presence of iron sulfides.For a core from Pescadero Basin, it is estimated that beneath the mixed zone, diffusion adds 0.4% sulfur by dry weight of sediment, whereas burial of sulfate adds less than 0.1% sulfur. It is shown that diffusion can add isotopically light sulfur to sediments, due to more rapid relative addition of ³²SO₄^2? compared to ³⁴SO₄^2? down a concentration gradient maintained by bacterial processes. The overall net isotopic value of the sulfate so added is $\text{δ}{}^{34}\text{S = ?4.5‰}$. The depth distribution of S-isotope in sulfur is controlled by the balance between a bacterial kinetic isotope effect preferentially removing ³²S relative to ³⁴S, and the supply of sulfate by diffusion. The isotopic fractionation factor, α, calculated by a mathematical formulation which takes diffusion into account, is larger (1.060±0.010) than when sulfate reduction is assumed to occur in a closed system (1.035). The larger value is supported by the sulfur isotope distribution in metastable iron sulfide. Essentially, the same open-system α was calculated for a core from Carmen Basin.  相似文献   

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

《Marine and Petroleum Geology》2017

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.  相似文献   

Oxygen and carbon stable isotope tracers of Weddell Sea water masses: new data and some paleoceanographic implications     

《Deep Sea Research Part I: Oceanographic Research Papers》2001,48(6):1401-1422

Stable oxygen isotopic composition of sea water and stable carbon isotopes of dissolved inorganic carbon (DIC) on the continental shelf in the southern Weddell Sea are presented. Using the stations sampled during the summer 1995 two sections can be constructed, one closely parallel to the ice shelf edge and the other perpendicular to the upper continental slope. Generally, δ¹⁸O values clearly separate between different shelf water masses depending on the content of meteoric meltwater added during melting of glacial ice. Extrapolation of the mixing line between the cores of High Salinity Shelf Water (HSSW) and supercooled Ice Shelf Water (ISW) reveals δ¹⁸O values of the glacial ice of −27‰, whereas extrapolation of the mixing line between the δ¹⁸O values of the most-saline HSSW and lowest temperature ISW results in δ¹⁸O values of −34‰ for glacial ice. These values point to an origin of meltwater from below the ice shelf, where ice is less depleted in ¹⁸O, since deep beneath the ice shelf close to the grounding line, values may reach −40‰. If values between −34 and −27‰ are used as δ¹⁸O end member values for glacial ice, the amount of meltwater from the ice shelf that adds to the formation of ISW off the Filchner–Ronne Ice Shelf ranges from 0.2 to 0.8%, in agreement with previous studies based on δ¹⁸O and ⁴He. Carbon isotopic fractionation due to gas exchange between the atmosphere and the ocean at cold temperatures results in Δδ¹³C_DIC values of 0.20±0.17‰ for Weddell Sea Deep Water, the water mass that ventilates the global abyssal ocean, typically defined as Antarctic Bottom Water (AABW). This confirms the low end of the range estimated previously (0.2–0.4‰), and thus corroborates the dominance of biology in shaping the deep and bottom water δ¹³C signal. It has been hypothesized that different modes of glacial/interglacial Antarctic bottom water formation may be separated by different stable isotopic compositions of deep-sea foraminiferal calcite. Here I show that differences between Δδ¹³C and δ¹⁸O values of HSSW and ISW, both of which contribute to bottom water formation today, are too small to be resolved in deep and bottom water masses. Therefore, glacial/interglacial changes in relative proportions of these water masses in Antarctic deep and bottom water cannot be separated by stable isotopes of fossil benthic foraminiferal calcite.  相似文献