The types,occurrence and composition of authigenic clay minerals in argillaceous limestone of sepiolite-bearing strata of the first member of the Middle Permian Maokou Formation(Mao-1 Member)in eastern Sichuan Basin w...The types,occurrence and composition of authigenic clay minerals in argillaceous limestone of sepiolite-bearing strata of the first member of the Middle Permian Maokou Formation(Mao-1 Member)in eastern Sichuan Basin were investigated through outcrop section measurement,core observation,thin section identification,argon ion polishing,X-ray diffraction,scanning electron microscope,energy spectrum analysis and laser ablation-inductively coupled plasma-mass spectrometry.The diagenetic evolution sequence of clay minerals was clarified,and the sedimentary-diagenetic evolution model of clay minerals was established.The results show that authigenic sepiolite minerals were precipitated in the Si4+and Mg2+-rich cool aragonite sea and sepiolite-bearing strata were formed in the Mao-1 Member.During burial diagenesis,authigenic clay minerals undergo two possible evolution sequences.First,from the early diagenetic stage A to the middle diagenetic stage A1,the sepiolite kept stable in the shallow-buried environment lack of Al3+.It began to transform into stevensite in the middle diagenetic stage A2,and then evolved into disordered talc in the middle diagenetic stage B1and finally into talc in the period from the middle diagenetic stage B2to the late diagenetic stage.Thus,the primary diagenetic evolution sequence of authigenic clay minerals,i.e.sepiolite-stevensite-disordered talc-talc,was formed in the Mao-1 Member.Second,in the early diagenetic stage A,as Al3+carried by the storm and upwelling currents was involved in the diagenetic process,trace of sepiolite started to evolve into smectite,and a part of smectite turned into chlorite.From the early diagenetic stage B to the middle diagenesis stage A1,a part of smectite evolved to illite/smectite mixed layer(I/S).The I/S evolved initially into illite from the middle diagenesis stage A2to the middle diagenesis stage B2,and then totally into illite in the late diagenesis stage.Thus,the secondary diagenetic evolution sequence of authigenic clay minerals,i.e.sepiolite-smectite-chlorite/illite,was formed in the Mao-1 Member.The types and evolution of authigenic clay minerals in argillaceous limestone of sepiolite-bearing strata are significant for petroleum geology in two aspects.First,sepiolite can adsorb and accumulate a large amount of organic matters,thereby effectively improving the quality and hydrocarbon generation potential of the source rocks of the Mao-1 Member.Second,the evolution from sepiolite to talc is accompanied by the formation of numerous organic matter pores and clay shrinkage pores/fractures,as well as the releasing of the Mg2+-rich diagenetic fluid,which allows for the dolomitization of limestone within or around the sag.As a result,the new assemblages of self-generation and self-accumulation,and lower/side source and upper/lateral reservoir,are created in the Middle Permian,enhancing the hydrocarbon accumulation efficiency.展开更多
The Cenozoic evolution history of Guizhou Province, which is located on the southeastern flank of the Qinghai-Tibet Plateau, is unclear because of the lack of sedimentation records. The red weathering crusts widesprea...The Cenozoic evolution history of Guizhou Province, which is located on the southeastern flank of the Qinghai-Tibet Plateau, is unclear because of the lack of sedimentation records. The red weathering crusts widespread on the Yunnan-Guizhou Plateau may bear critical information about their evolution history. This work firstly determined the ages of four red weathering crusts in eastern, central and northern Guizhou. The material used in fission track dating is well-crystallized quartz occurring in many in-situ weathering crusts of carbonate rocks. The results showed that the fission track ages of quartz vary over a wide range from 1 to 25 Ma in the four profiles, significantly younger than the ages of the Triassic and Cambrian parent rocks. In combination with the evolution history of the regional geology during the period from 25 to 1 Ma, the ages of quartz can exclude the possibility that the origin of quartz has nothing to do with primary clastic minerals in parent rocks, authigenesis during diagenesis and hydrothermal precipitation or roplacement by volcanic activities. It is deduced that the well-crystallized quartz was precipitated from Si-rich weathering fluids during the weathering process of carbonate rocks. The recorded ages of quartz from the four profiles are consistent with the episodes of the planation surfaces on the Qinghai-Tibet Plateau, the forming stages of red soil in the tropics of South China, the tectonically stable periods in Guizhou, and the ages of weathering in other parts of the world during the Cenozoic era. That is to say, the ages of authigenic quartz dated by the fission track method are well feasible and credible.展开更多
The Tarim Basin in China comprises eight sets of sandstone reservoirs, five of which are investigated in detail in this study. The main purpose of this study is to investigate the hydrocarbon charging histories of res...The Tarim Basin in China comprises eight sets of sandstone reservoirs, five of which are investigated in detail in this study. The main purpose of this study is to investigate the hydrocarbon charging histories of reservoirs by applying K-Ar dating of authigenic illites. The ages of authigenic illites from the Lower Silurian bituminous sandstones in the Central Uplift area range from 383.5 to 235.2 Ma, suggesting that the Silurian oil accumulations were formed from the late Caledonian till the late Hercynian. The ages of authigenic illites from the Upper Devonian Donghe Sandstone reservoirs range from 263.8 to 231.3 Ma, indicating that hydrocarbon accumulations within the Donghe sandstone were formed mainly in the late Hercynian. The authigenic illites ages from the Lower Jurassic Yangxia Group sandstones in the Yinan-2 gas reservoir (Yinan-2, Kuqa Depression) range from 28.1 to 23.9 Ma, suggesting that the initial hydrocarbon charging occurred in the Miocene. The ages of the authigenic illites from the Lower Cretaceous sandstones in the Akemomu gas field (Ake-1, Kashi Sag, Southwest Depression) range from 22.6 to 18.8 Ma, indicating a probable early oil accumulation or early migration of hydrocarbon within this area. The illites from the Paleogene sandstones in the Dina-2 gas reservoir (Dina-201, Kuqa Depression) have a detrital origin; they cannot be used to study the hydrocarbon charging histories. The ages of authigenic illites in the underlying Cretaceous sandstones in the same well (Dina-201) range from 25.5 to 15.5 Ma, indicating that hydrocarbon charging in this reservoir probably occurred within the Miocene. This study highlights the potential of applying K-Ar dating of authigenic illites to investigate the timing of hydrocarbon charging histories of the Tarim Basin reservoir sandstones.展开更多
Authigenic gypsum crystals, along with pyrite and carbonate mineralization, predominantly calcites were noticed in distinct intervals in a 32 m long piston core, collected in the gas hydratebearing sediments in the no...Authigenic gypsum crystals, along with pyrite and carbonate mineralization, predominantly calcites were noticed in distinct intervals in a 32 m long piston core, collected in the gas hydratebearing sediments in the northern portion of the Krishna-Godavari basin, eastern continental margin of India at a water depth of 1691 m. X-ray diffraction and energy dispersive spectrum studies confirm presence of pyrite, gypsum, calcite, and other mineral aggregates. The occurrence of gypsum in such deep sea environment is intriguing, because gypsum is a classical evaporite mineral and is under saturated with respect to sea water. Sedimentological, geochemical evidences point to diagenetic formation of the gypsum due to oxidation of sulphide minerals （i.e. pyrite）. Euhedral, transparent gypsum crystals, with pyrite inclusions are cemented with authigenic carbonates, possibly indicating that they were formed authigenically in situ in the gas hydrate-influenced environment due to late burial diagenesis involving sulphate reduction and anaerobic oxidation of methane （AOM）. Therefore, the authigenic gypsums found in sediments of the Krishna-Godavari and Mahanadi offshore regions could be seen as one of the parameters to imply the presence of high methane flux possibly from gas hydrate at depth.展开更多
Occurrence of baddeleyite（ZrO_2） which is a rare mineral has been recorded in ferromanganese nodules of Central Indian Ocean Basin（CIOB）.The mineral occurs either as independent isolated sub-rounded to elliptical ...Occurrence of baddeleyite（ZrO_2） which is a rare mineral has been recorded in ferromanganese nodules of Central Indian Ocean Basin（CIOB）.The mineral occurs either as independent isolated sub-rounded to elliptical grains or in clusters forming fine subhedral crystals（〈3μm） within ferromanganese concretionary growth bands.The mode of occurrence,texturai features and chemistry of the mineral suggest detrital and possibly an authigenic origin for baddeleyite.For authigenic origin it is proposed that zirconium might have got released either from the terrigenous sediments or the altered seafloor rocks forming halogen complexes and subsequently it has re-precipitated in me form of baddeleyite within manganese nodules under oxic to sub-oxic conditions.展开更多
The Late Paleozoic Ice Age across Carboniferous and Permian had a significant impact on the Kungurian （Upper Cisuralian series of Permian） Chihsia Formation in South China. This re- suited in a unique interval with ...The Late Paleozoic Ice Age across Carboniferous and Permian had a significant impact on the Kungurian （Upper Cisuralian series of Permian） Chihsia Formation in South China. This re- suited in a unique interval with features such as the lack of reef in Chihsian limestone, widespread stinkstone and nodular/bedded chert. The Chihsia limestone （Kungurian stage） deposited during a time of cooling was resulted from oceanic upwelling. Here we present evidence for this upwelling using sev- eral geochemical analyses： bulk organic carbon isotope, biomarker molecular geochemical data, and authigenic silica of the stinkstone member in the lower Chihsia Formation of the Kuangurian stage from the Enshi Section in western Hubei Province, South China. The lower part of the stinkstone member shows a rapid organic carbon isotope excursion with a -3%o shift triggered by the upwelling of 13C-depleted bottom water. The concurrent rapid increasing of authigenic silica content resulted from the enhanced supply of dissolved silica in the upwelling water mass. This upwelling at the Enshi Section also led to relative high TOC content, accounting for the widespread stinkstone in the lower Chihsia Formation during the Kungurian stage in Permian.展开更多
The Silurian bituminous sandstones（SBS） in the Tarim Basin, China are important basinwide reservoirs with an estimated area of approximately 249000 km^2. We investigated the ages of authigenic illites in the SBS res...The Silurian bituminous sandstones（SBS） in the Tarim Basin, China are important basinwide reservoirs with an estimated area of approximately 249000 km^2. We investigated the ages of authigenic illites in the SBS reservoirs and constrained their formation timing by using the 40^Ar/39^Ar step wise heating method. The age spectra, 39^Ar recoil loss and their controlling factors were investigated systematically. The 40^Ar/39^Ar ages were compared with the conventional K/Ar ages of identical clay fractions. The clay in the SBS reservoirs is dominated by orderly mixed-layer illite/smectite（I/S） with 5%–30% smectite layers. The I/S minerals morphology comprises primarily honeycomb, short filamentous and curved-lath particles, characteristic of authigenic illites. The unencapsulated 40^Ar/39^Ar total gas ages（UTGA） of the authigenic illites range from 188.56 ± 6.20 Ma to 491.86 ± 27.68 Ma, which are 7% to 103% older than the corresponding K/Ar ages of 124.87 ± 1.11 Ma to 383.45 ± 2.80 Ma, respectively. The K-Ar ages indicate multistage accumulations with distinct distribution patterns in the Tarim Basin： older（late Caledonian-early Hercynian） around the basin margin, younger（late Hercynian） in the basin centre, and the youngest（middle to late Yanshanian） in the Ha-6 well-block, central area of the North Uplift. The age difference is believed to have been caused by the 39^Ar recoil loss during the irradiation process. Compared with the K/Ar ages, the estimated 39^Ar recoil losses in this study are in the range from 7% to 51%. The 39^Ar recoil loss appears to increase not only with the decreasing particle sizes of the I/S, but also with increasing percentage of smectite layers（IR） of the I/S, and smectite layer content（SLC） of the samples. We conclude that due to significant 39^Ar recoil losses, UTGA may not offer any meaningful geological ages of the authigenic illite formation in the SBS and thus can not be used to represent the hydrocarbon charge timing. 39^Ar recoil losses during 40^Ar/39^Ar dating can not be neglected when dating fine authigenic illite, especially when the ordered mixed-layer I/S containing small amount of smectite layers（IR30%） in the reservoir formations. Compared with the unencapsulated Ar-Ar method, the conventional K-Ar method is less complicated, more accurate and reliable in dating authigenic illites in petroleum reservoirs.展开更多
Radiogenic isotope dating of illitic clays has been widely used to reconstruct thermal and fluid flow events in siliciclastic sedimentary basins,the information of which is critical to investigate mechanisms of hydroc...Radiogenic isotope dating of illitic clays has been widely used to reconstruct thermal and fluid flow events in siliciclastic sedimentary basins,the information of which is critical to investigate mechanisms of hydrocarbon maturation.This study carried out Rb-Sr and^(40)Ar-^(39)Ar dating of authigenic illitic clay samples separated from the Palaeogene sandstone in the northern South China Sea.Our Rb-Sr data further confirm the previously reported three periods of fluid flow events(at 34.5±0.9,31.2±0.6,and 23.6±0.8 Ma,respectively)in the northern South China Sea,which are related to regional episodic tectonism.However,^(40)Ar-^(39)Ar ages of illite obtained in this study are significantly younger than the corresponding Rb-Sr ages.The significantly younger^(40)Ar-^(39)Ar ages were probably due to ^(40)Ar loss caused by later dry heating events on the Hainan Island that have not affected the Rb-Sr isotopic systematics.The inconsistency between Rb-Sr and^(40)Ar-^(39)Ar data should be attributed to different isotopic behaviors of K-Ar and Rb-Sr isotopic systematics in illite.Our results indicate that Rb-Sr isotopic dating method may be a preferential approach for clay dating in geological settings where exist younger dry heating events.展开更多
Taking lake basin shales of the Triassic Yanchang Formation in the Ordos Basin,NW China and the Cretaceous Qingshankou Formation in the Songliao Basin,NE China as research objects,the characteristics and origins of di...Taking lake basin shales of the Triassic Yanchang Formation in the Ordos Basin,NW China and the Cretaceous Qingshankou Formation in the Songliao Basin,NE China as research objects,the characteristics and origins of different types of silica in the shales have been studied by means of core observation,thin section identification,cathodoluminescence,X-ray diffraction analysis,scanning electron microscope(SEM),electron probe and rock pyrolysis.The results shows that the origins of silica include felsic mineral dissolution,tuffite devitrification,clay mineral transformation and siliceous mineral metasomatism.The silica formed by feldspar dissolution commonly appears as spots and veins,with low degree of crystallization,and is largely aqueous opal mineral,with an average Si O2 content of 67.2%.Silica formed by devitrification of tuffite mainly occurs in two forms,amorphous silica and authigenic quartz with better crystal shape.The authigenic silica formed during the transformation of clay minerals is embedded in the clay minerals in the form of micron-scale plates and small flakes,or mixed with clay minerals in a dispersed state.The authigenic quartz formed by siliceous mineral metasomatism is in better angular crystal shape,and has an average Si O2 content of 87%.The authigenic siliceous mineral content is positively correlated with the content of terrigenous felsic minerals.The pressure solution of felsic minerals is the main source of authigenic siliceous minerals,followed by the transformation of clay minerals,and the organic matter has some boost on the formation of authigenic silica.The authigenic siliceous materials of different origins have different geological characteristics and occurrence states from terrigenous quartz,which would affect the storage performance,seepage capacity and fracturing effect of continental shale.Although the organic-rich shale has high silica content,different from terrigenous quartz,authigenic silica in this kind of shale mostly floats and disperse in clay minerals,which would have negative effect on the formation of complex fractures in fracturing,fracture support ability after fracturing,and formation of effective seepage channels.Calculating the brittleness index of shale intervals only based on the composition of brittle minerals cannot accurately characterize mechanical characteristics of continental shale oil reservoirs,and would affect comprehensive evaluation and selection of continental shale oil“sweet spots”.展开更多
Objective Authigenic pyrite often develops extensively in marine sediments,which is an important product of sulfate reduction in an anoxic environment.It has a specific appearance and complicated sulfur isotopic prope...Objective Authigenic pyrite often develops extensively in marine sediments,which is an important product of sulfate reduction in an anoxic environment.It has a specific appearance and complicated sulfur isotopic properties,and acts as important evidence of methane seep in marine sediments.Strong AOM（anaerobic oxidation of methane）activity has developed in the Okinawa Trough.展开更多
Generation, morphology, and distribution of authigenic minerals directly reflect sedimentary environment and material sources. Surface sediments were collected from the western Gulf of Thailand during 2011–2012, and ...Generation, morphology, and distribution of authigenic minerals directly reflect sedimentary environment and material sources. Surface sediments were collected from the western Gulf of Thailand during 2011–2012, and 159 samples were analyzed to determine detrital minerals. Authigenic minerals, including siderite, pyrite, and glauconite, are abundant whereas secondary minerals, such as chlorite and limonite, are distributed widely in the study area. Siderite has a maximum content of 19.98 g/kg and appears in three types from nearshore to continental shelf, showing the process of forming-maturity-oxidation. In this process, the Mn O content in siderite decreases, but FeOand Mg O content increase. Colorless or transparent siderite pellets are fresh grains generated within a short time and widely distributed throughout the region; high content appears in coastal area where river inputs are discharged. Translucent cemented double pellets appearing light yellow to red are mature grains; high content is observed in the central shelf. Red-brown opaque granular pellets are oxidized grains,which are concentrated in the eastern gulf. Pyrite is mostly distributed in the central continental shelf with an approximately north–south strip. Pyrite are mainly observed in foraminifera shell and distributed in clayey silt sediments, which is similar to that in the Yangtze River mouth and the Yellow Sea. The pyrite in the gulf is deduced from genetic types associated with sulfate reduction and organic matter decomposition. Majority of glauconite are granular with few laminar. Glauconite is concentrated in the northern and southern parts within the boundary of 9.5° to 10.5°N and is affected by river input diffusion. The distribution of glauconite is closely correlated with that of chlorite and plagioclase, indicating that glauconite is possibly derived from altered products of chlorite and plagioclase. The KO content of glauconite is low or absent, indicating its short formation time.展开更多
Studies on the origin of shale brittleness are of great significance to understanding shale gas accumulation laws.The current studies,however,mostly focus on the improvement of shale brittleness by biological quartz e...Studies on the origin of shale brittleness are of great significance to understanding shale gas accumulation laws.The current studies,however,mostly focus on the improvement of shale brittleness by biological quartz enrichment,but rarely on the recrystallization of quartz in the process of diagenetic evolution.In this paper,a series of researches were carried out on the Lower Silurian Longmaxi Fm marine shale in the Changning block of the Sichuan Basin.Firstly,shale pore,mineral component and bedding characteristics were observed by means of cathodoluminescence(CL),scanning electron microscope(SEM)and so on.Then,the control effects of quartz origin,overpressure environment and diagenetic evolution on shale brittleness were investigated by analyzing the mineral composition and siliceous composition of shale microscopically.Finally,the authigenic embrittlement model of marine shale was put forward and the geological significance of authigenic microcrystalline quartz to the improvement of shale brittleness in the process of diagenesis was illustrated.The following results were obtained.First,during the sedimentation,burial and diagenetic evolution,shale experiences diagenetic changes which help increase quartz content and form concealed fracture networks,thus benefiting the formation of complex flow pathways in later stimulation.Second,organic matters play a positive role in improving shale brittleness in the process of geological evolution.It promotes the formation of authigenic microcrystalline quartz and improves the brittleness of shale.In conclusion,due to the authigenic embrittlement of shale in the process of diagenesis,rock structure is changed,rock strength is enhanced and shale porosity is preserved.Consequently,reservoir space in shale is improved and the enrichment state of shale gas is modified.Therefore,the preservation condition under the control of tectonic movement factors is vital to geological evaluation on shale gas.In addition,marine shale is certainly well brittle after authigenic embrittlement in the process of diagenesis as long as its organic matter content is abundant.展开更多
The clastic rocks in the depth of 2800-6000 m of the Paleogene in Jiyang sub-basin had undergone the middle diagenesis and late diagenesis.The reservoirs in main areas of the sub-basin developed 2-6 secondary pores zo...The clastic rocks in the depth of 2800-6000 m of the Paleogene in Jiyang sub-basin had undergone the middle diagenesis and late diagenesis.The reservoirs in main areas of the sub-basin developed 2-6 secondary pores zones.The reservoirs in the stage A of middle diagenesis of Bonan fault zone in Zhanhua depression and of the gentle slope belt of Chezhen depression are controlled by the acidic diagenetic medium and developed one secondary pores zone in each diagenetic sub-stage respectively.The contents ofautogenic quartz,pyrite and kaolinite are quite high in these reservoirs.The reservoirs’展开更多
Characteristic gypsum micro-sphere and granular mass were discovered by bin-ocular microscope in the gas hydrate-associated sediments at cores SO143-221 and SO143/TVG40-2A respectively on Hydrate Ridge of Cascadia mar...Characteristic gypsum micro-sphere and granular mass were discovered by bin-ocular microscope in the gas hydrate-associated sediments at cores SO143-221 and SO143/TVG40-2A respectively on Hydrate Ridge of Cascadia margin, the eastern North Pacific. XRD patterns and EPA analyses show both micro-sphere and granular mass of the crystals have the typical peaks and the typical main chemical compositions of gypsum, although their weight percents are slightly less than the others in the non-gas hydrate-associated marine regions. SEM pictures show that the gypsum crystals have clear crystal boundaries, planes, edges and cleav-ages of gypsum in form either of single crystal or of twin crystals. In view of the fact that there are meanwhile gas hydrate-associated authigenic carbonates and SO42--rich pore water in the same sediment cores, it could be inferred reasonably that the gypsums formed also authigenically in the gas hydrate-associated environment too, most probably at the interface between the down-ward advecting sulfate-rich seawater and the below gas hydrate, which spilled calcium during its formation on Hydrate Ridge. The two distinct forms of crystal intergrowth, which are the granular mass of series single gypsum crystals at core SO143/TVG40-2A and the microsphere of gypsum crystals accompanied with detrital components at core SO143-221 respectively, indicate that they precipitated most likely in different interstitial water dynamic environments. So, the distinct authigenic gypsums found in gas hydrate-associated sediments on Hydrate Ridge could also be believed as one of the parameters which could be used to indicate the presence of gas hydrate in an unknown marine sediment cores.展开更多
A type of authigenic pyrites that fully fill or semi-fill the rock fractures of drillholes with gas hydrate anomalies are found in the Qilian Mountain permafrost; this type of pyrite is known as ＂fracture-filling＂ p...A type of authigenic pyrites that fully fill or semi-fill the rock fractures of drillholes with gas hydrate anomalies are found in the Qilian Mountain permafrost; this type of pyrite is known as ＂fracture-filling＂ pyrite. The occurrence of ＂fracture-filling＂ pyrite has a certain similarity with that of the hydrate found in this region, and the pyrite is generally concentrated in the lower part of the hydrate layer or the hydrate anomaly layer. The morphology, trace elements, rare earth elements, and sulfur isotope analyses of samples from drillhole DK-6 indicate that the ＂fracture-filling＂ pyrites are dominated by cubic ones mainly aligned in a step-like fashion along the surfaces of rock fractures and are associated with a circular structure, lower Co/Ni and Sr/Ba, lower ZREE, higher LREE, significant Eu negative anomalies, and 634ScDT positive bias. In terms of the pyrites＇ unique crys- tal morphology and geochemical characteristics and their relationship with the hydrate layers or abnormal layers, they are closely related with the accumulation system of the gas hydrate in the Qilian Mountain permafrost. As climate change is an important factor in affecting the stability of the gas hydrate, formation of fracture-filling pyrites is most likely closely related to the secondary change of the metastable gas hydrate under the regional climate warming. The distribution intensity of these py- rites indicates that when the gas hydrate stability zone （GHSZ） is narrowing, the hydrate decomposition at the bottom of the GHSZ is stronger than that at the top of the GHSZ, whereas the hydrate decomposition within the GHSZ is relatively weak. Thus, the zone between the shallowest and the deepest distribution of the fracture-filling pyrite recorded the largest possible original GHSZ.展开更多
The anaerobic oxidation of methane （AOM） has strongly developed at Core A, Site 79 of the middle Okinawa Trough, East China Sea, and a large amount of authigenic pyrite is preserved in the surface sediment. In this ...The anaerobic oxidation of methane （AOM） has strongly developed at Core A, Site 79 of the middle Okinawa Trough, East China Sea, and a large amount of authigenic pyrite is preserved in the surface sediment. In this study, we analyze the characteristics of the authigenic pyrite and its sulfur isotopic values. The authigenic pyrite is stripy and tubular, and there were foraminifera compartments filled with pyrite. The pyrite is extracted using chromium reduction, and the values of δ348 are found to lie between -41.20‰ and 8.92‰ V-CDT. The bulk pyrite tends to be more enriched in 348 with increasing depth. Particularly, the 834S value of the pyrite lies between -32.73%o and -41.20‰ V-CDT above 278 cmbsf, but it quickly increases below this depth （-21.49%o-8.92‰ V-CDT）. At the same time, the total sulfur content of the pyrite shows an abrupt increase above 100 cmbsf but is otherwise stable between 1.04% and 0.55% below 100 cmbsf. The stable and negative values of 8345 and the decreasing values of total sulfur above 278 cmbsf indicate reduced AOM activities in 17.18-5.3 ka. In addition, the increasing δ34S and pyrite content indicate strong AOM development and methane seep below 278 cmbsf in 18.8-17.18 ka. In particular, the highest positive value of δ34S occurring in 18.78 ka indicates the most intense AOM activity. The shallow sul- fate-methane interface （SMI） and high methane flux below marine sediments also strongly support this activity.展开更多
According to the data of the mineral assemblages, the sediment layers with authigenic glauconite were found in the X<sub>1</sub> core collected from the northeast of the Beibu Gulf. Pliocene sediment layer...According to the data of the mineral assemblages, the sediment layers with authigenic glauconite were found in the X<sub>1</sub> core collected from the northeast of the Beibu Gulf. Pliocene sediment layer containing a lot of foraminifera shows a shallow sea facies. Its thickness is larger than 30 m and is located at the depth below 59 m of the core.展开更多
Thin section and argon-ion polishing scanning electron microscope observations were used to analyze the sedimentary and diagenetic environments and main diagenesis of the Permian Fengcheng Formation shales in differen...Thin section and argon-ion polishing scanning electron microscope observations were used to analyze the sedimentary and diagenetic environments and main diagenesis of the Permian Fengcheng Formation shales in different depositional zones of Mahu Sag in the Junggar Basin,and to reconstruct their differential diagenetic evolutional processes.The diagenetic environment of shales in the lake-central zone kept alkaline,which mainly underwent the early stage(Ro<0.5%)dominated by the authigenesis of Na-carbonates and K-feldspar and the late stage(Ro>0.5%)dominated by the replacement of Na-carbonates by reedmergnerite.The shales from the marginal zone underwent a transition from weak alkaline to acidic diagenetic environments,with the early stage dominated by the authigenesis of Mg-bearing clay and silica and the late stage dominated by the dissolution of feldspar and carbonate minerals.The shales from the transitional zone also underwent a transition from an early alkaline diagenetic environment,evidenced by the formation of dolomite and zeolite,to a late acidic diagenetic environment,represented by the reedmergnerite replacement and silicification of feldspar and carbonate minerals.The differences in formation of authigenic minerals during early diagenetic stage determine the fracability of shales.The differences in dissolution of minerals during late diagenetic stage control the content of free shale oil.Dolomitic shale in the transitional zone and siltstone in the marginal zone have relatively high content of free shale oil and strong fracability,and are favorable“sweet spots”for shale oil exploitation and development.展开更多
The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxid...The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane（AOM） coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor（cmbsf） in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values（δ^34 S） of pyrite vary greatly（from –46.6‰ to –12.3‰ V-CDT） and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction（OSR） and is influenced by AOM with depth.The relative high abundance and δ^34 S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone（SMTZ）.The sulfur isotopic composition of gypsum（from–25‰ to –20.7‰） is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO2,iron（Ⅲ） and oxygen driven by the SMTZ location shift to great depths.The δ^34 S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.展开更多
Previous studies of gas hydrate in the Dongsha area mainly focused on the deep-seated gas hydrates that have a high energy potential,but cared little about the shallow gas hydrates occurrences.Shallow gas hydrates hav...Previous studies of gas hydrate in the Dongsha area mainly focused on the deep-seated gas hydrates that have a high energy potential,but cared little about the shallow gas hydrates occurrences.Shallow gas hydrates have been confirmed by drill cores at three sites(GMGS208,GMGS209 and GMGS216)during the GMGS2 cruise,which occur as veins,blocky nodules or massive layers,at 8–30 m below the seafloor.Gas chimneys and faults observed on the seismic sections are the two main fluid migration pathways.The deep-seated gas hydrate and the shallow hydrate-bearing sediments are two main seals for the migrating gas.The occurrences of shallow gas hydrates are mainly controlled by the migration of fluid along shallow faults and the presence of deep-seated gas hydrates.Active gas leakage is taking place at a relatively high-flux state through the vent structures identified on the geophysical data at the seafloor,although without resulting in gas plumes easily detectable by acoustic methods.The presence of strong reflections on the high-resolution seismic profiles and dim or chaotic layers in the subbottom profiles are most likely good indicators of shallow gas hydrates in the Dongsha area.Active cold seeps,indicated by either gas plume or seepage vent,can also be used as indicators for neighboring shallow gas hydrates and the gas hydrate system that is highly dynamic in the Dongsha area.展开更多
基金Supported by the Enterprise Innovation and Development Joint Fund of National Natural Science Foundation of China(U19B6003)National Natural Science Foundation of China(41872150)。
文摘The types,occurrence and composition of authigenic clay minerals in argillaceous limestone of sepiolite-bearing strata of the first member of the Middle Permian Maokou Formation(Mao-1 Member)in eastern Sichuan Basin were investigated through outcrop section measurement,core observation,thin section identification,argon ion polishing,X-ray diffraction,scanning electron microscope,energy spectrum analysis and laser ablation-inductively coupled plasma-mass spectrometry.The diagenetic evolution sequence of clay minerals was clarified,and the sedimentary-diagenetic evolution model of clay minerals was established.The results show that authigenic sepiolite minerals were precipitated in the Si4+and Mg2+-rich cool aragonite sea and sepiolite-bearing strata were formed in the Mao-1 Member.During burial diagenesis,authigenic clay minerals undergo two possible evolution sequences.First,from the early diagenetic stage A to the middle diagenetic stage A1,the sepiolite kept stable in the shallow-buried environment lack of Al3+.It began to transform into stevensite in the middle diagenetic stage A2,and then evolved into disordered talc in the middle diagenetic stage B1and finally into talc in the period from the middle diagenetic stage B2to the late diagenetic stage.Thus,the primary diagenetic evolution sequence of authigenic clay minerals,i.e.sepiolite-stevensite-disordered talc-talc,was formed in the Mao-1 Member.Second,in the early diagenetic stage A,as Al3+carried by the storm and upwelling currents was involved in the diagenetic process,trace of sepiolite started to evolve into smectite,and a part of smectite turned into chlorite.From the early diagenetic stage B to the middle diagenesis stage A1,a part of smectite evolved to illite/smectite mixed layer(I/S).The I/S evolved initially into illite from the middle diagenesis stage A2to the middle diagenesis stage B2,and then totally into illite in the late diagenesis stage.Thus,the secondary diagenetic evolution sequence of authigenic clay minerals,i.e.sepiolite-smectite-chlorite/illite,was formed in the Mao-1 Member.The types and evolution of authigenic clay minerals in argillaceous limestone of sepiolite-bearing strata are significant for petroleum geology in two aspects.First,sepiolite can adsorb and accumulate a large amount of organic matters,thereby effectively improving the quality and hydrocarbon generation potential of the source rocks of the Mao-1 Member.Second,the evolution from sepiolite to talc is accompanied by the formation of numerous organic matter pores and clay shrinkage pores/fractures,as well as the releasing of the Mg2+-rich diagenetic fluid,which allows for the dolomitization of limestone within or around the sag.As a result,the new assemblages of self-generation and self-accumulation,and lower/side source and upper/lateral reservoir,are created in the Middle Permian,enhancing the hydrocarbon accumulation efficiency.
基金This work was granted by the National Natural Science Foundation of China(Nos.40371012 and 49833002).
文摘The Cenozoic evolution history of Guizhou Province, which is located on the southeastern flank of the Qinghai-Tibet Plateau, is unclear because of the lack of sedimentation records. The red weathering crusts widespread on the Yunnan-Guizhou Plateau may bear critical information about their evolution history. This work firstly determined the ages of four red weathering crusts in eastern, central and northern Guizhou. The material used in fission track dating is well-crystallized quartz occurring in many in-situ weathering crusts of carbonate rocks. The results showed that the fission track ages of quartz vary over a wide range from 1 to 25 Ma in the four profiles, significantly younger than the ages of the Triassic and Cambrian parent rocks. In combination with the evolution history of the regional geology during the period from 25 to 1 Ma, the ages of quartz can exclude the possibility that the origin of quartz has nothing to do with primary clastic minerals in parent rocks, authigenesis during diagenesis and hydrothermal precipitation or roplacement by volcanic activities. It is deduced that the well-crystallized quartz was precipitated from Si-rich weathering fluids during the weathering process of carbonate rocks. The recorded ages of quartz from the four profiles are consistent with the episodes of the planation surfaces on the Qinghai-Tibet Plateau, the forming stages of red soil in the tropics of South China, the tectonically stable periods in Guizhou, and the ages of weathering in other parts of the world during the Cenozoic era. That is to say, the ages of authigenic quartz dated by the fission track method are well feasible and credible.
文摘The Tarim Basin in China comprises eight sets of sandstone reservoirs, five of which are investigated in detail in this study. The main purpose of this study is to investigate the hydrocarbon charging histories of reservoirs by applying K-Ar dating of authigenic illites. The ages of authigenic illites from the Lower Silurian bituminous sandstones in the Central Uplift area range from 383.5 to 235.2 Ma, suggesting that the Silurian oil accumulations were formed from the late Caledonian till the late Hercynian. The ages of authigenic illites from the Upper Devonian Donghe Sandstone reservoirs range from 263.8 to 231.3 Ma, indicating that hydrocarbon accumulations within the Donghe sandstone were formed mainly in the late Hercynian. The authigenic illites ages from the Lower Jurassic Yangxia Group sandstones in the Yinan-2 gas reservoir (Yinan-2, Kuqa Depression) range from 28.1 to 23.9 Ma, suggesting that the initial hydrocarbon charging occurred in the Miocene. The ages of the authigenic illites from the Lower Cretaceous sandstones in the Akemomu gas field (Ake-1, Kashi Sag, Southwest Depression) range from 22.6 to 18.8 Ma, indicating a probable early oil accumulation or early migration of hydrocarbon within this area. The illites from the Paleogene sandstones in the Dina-2 gas reservoir (Dina-201, Kuqa Depression) have a detrital origin; they cannot be used to study the hydrocarbon charging histories. The ages of authigenic illites in the underlying Cretaceous sandstones in the same well (Dina-201) range from 25.5 to 15.5 Ma, indicating that hydrocarbon charging in this reservoir probably occurred within the Miocene. This study highlights the potential of applying K-Ar dating of authigenic illites to investigate the timing of hydrocarbon charging histories of the Tarim Basin reservoir sandstones.
基金funded by National Gas Hydrate Program (NGHP), India
文摘Authigenic gypsum crystals, along with pyrite and carbonate mineralization, predominantly calcites were noticed in distinct intervals in a 32 m long piston core, collected in the gas hydratebearing sediments in the northern portion of the Krishna-Godavari basin, eastern continental margin of India at a water depth of 1691 m. X-ray diffraction and energy dispersive spectrum studies confirm presence of pyrite, gypsum, calcite, and other mineral aggregates. The occurrence of gypsum in such deep sea environment is intriguing, because gypsum is a classical evaporite mineral and is under saturated with respect to sea water. Sedimentological, geochemical evidences point to diagenetic formation of the gypsum due to oxidation of sulphide minerals （i.e. pyrite）. Euhedral, transparent gypsum crystals, with pyrite inclusions are cemented with authigenic carbonates, possibly indicating that they were formed authigenically in situ in the gas hydrate-influenced environment due to late burial diagenesis involving sulphate reduction and anaerobic oxidation of methane （AOM）. Therefore, the authigenic gypsums found in sediments of the Krishna-Godavari and Mahanadi offshore regions could be seen as one of the parameters to imply the presence of high methane flux possibly from gas hydrate at depth.
基金the"CSIR-Young Scientist Award Project"(OLP-0103 of NML) sanctioned to B.Nayak by CSIR,New Delhi
文摘Occurrence of baddeleyite（ZrO_2） which is a rare mineral has been recorded in ferromanganese nodules of Central Indian Ocean Basin（CIOB）.The mineral occurs either as independent isolated sub-rounded to elliptical grains or in clusters forming fine subhedral crystals（〈3μm） within ferromanganese concretionary growth bands.The mode of occurrence,texturai features and chemistry of the mineral suggest detrital and possibly an authigenic origin for baddeleyite.For authigenic origin it is proposed that zirconium might have got released either from the terrigenous sediments or the altered seafloor rocks forming halogen complexes and subsequently it has re-precipitated in me form of baddeleyite within manganese nodules under oxic to sub-oxic conditions.
基金supported by the National Natural Science Foundation of China (No. 41302021)the Science and Technology Research Project of Jiangxi Province Education Department (No. GJJ13452)+1 种基金Research by Hao Yu is supported by the National Natural Science Foundation of China (No. 41290260)the Ministry of Education of China (No. 20120001110052)
文摘The Late Paleozoic Ice Age across Carboniferous and Permian had a significant impact on the Kungurian （Upper Cisuralian series of Permian） Chihsia Formation in South China. This re- suited in a unique interval with features such as the lack of reef in Chihsian limestone, widespread stinkstone and nodular/bedded chert. The Chihsia limestone （Kungurian stage） deposited during a time of cooling was resulted from oceanic upwelling. Here we present evidence for this upwelling using sev- eral geochemical analyses： bulk organic carbon isotope, biomarker molecular geochemical data, and authigenic silica of the stinkstone member in the lower Chihsia Formation of the Kuangurian stage from the Enshi Section in western Hubei Province, South China. The lower part of the stinkstone member shows a rapid organic carbon isotope excursion with a -3%o shift triggered by the upwelling of 13C-depleted bottom water. The concurrent rapid increasing of authigenic silica content resulted from the enhanced supply of dissolved silica in the upwelling water mass. This upwelling at the Enshi Section also led to relative high TOC content, accounting for the widespread stinkstone in the lower Chihsia Formation during the Kungurian stage in Permian.
文摘The Silurian bituminous sandstones（SBS） in the Tarim Basin, China are important basinwide reservoirs with an estimated area of approximately 249000 km^2. We investigated the ages of authigenic illites in the SBS reservoirs and constrained their formation timing by using the 40^Ar/39^Ar step wise heating method. The age spectra, 39^Ar recoil loss and their controlling factors were investigated systematically. The 40^Ar/39^Ar ages were compared with the conventional K/Ar ages of identical clay fractions. The clay in the SBS reservoirs is dominated by orderly mixed-layer illite/smectite（I/S） with 5%–30% smectite layers. The I/S minerals morphology comprises primarily honeycomb, short filamentous and curved-lath particles, characteristic of authigenic illites. The unencapsulated 40^Ar/39^Ar total gas ages（UTGA） of the authigenic illites range from 188.56 ± 6.20 Ma to 491.86 ± 27.68 Ma, which are 7% to 103% older than the corresponding K/Ar ages of 124.87 ± 1.11 Ma to 383.45 ± 2.80 Ma, respectively. The K-Ar ages indicate multistage accumulations with distinct distribution patterns in the Tarim Basin： older（late Caledonian-early Hercynian） around the basin margin, younger（late Hercynian） in the basin centre, and the youngest（middle to late Yanshanian） in the Ha-6 well-block, central area of the North Uplift. The age difference is believed to have been caused by the 39^Ar recoil loss during the irradiation process. Compared with the K/Ar ages, the estimated 39^Ar recoil losses in this study are in the range from 7% to 51%. The 39^Ar recoil loss appears to increase not only with the decreasing particle sizes of the I/S, but also with increasing percentage of smectite layers（IR） of the I/S, and smectite layer content（SLC） of the samples. We conclude that due to significant 39^Ar recoil losses, UTGA may not offer any meaningful geological ages of the authigenic illite formation in the SBS and thus can not be used to represent the hydrocarbon charge timing. 39^Ar recoil losses during 40^Ar/39^Ar dating can not be neglected when dating fine authigenic illite, especially when the ordered mixed-layer I/S containing small amount of smectite layers（IR30%） in the reservoir formations. Compared with the unencapsulated Ar-Ar method, the conventional K-Ar method is less complicated, more accurate and reliable in dating authigenic illites in petroleum reservoirs.
基金supported by the National Natural Science Foundation of China(Nos.42072142,41702121,U19B2007)。
文摘Radiogenic isotope dating of illitic clays has been widely used to reconstruct thermal and fluid flow events in siliciclastic sedimentary basins,the information of which is critical to investigate mechanisms of hydrocarbon maturation.This study carried out Rb-Sr and^(40)Ar-^(39)Ar dating of authigenic illitic clay samples separated from the Palaeogene sandstone in the northern South China Sea.Our Rb-Sr data further confirm the previously reported three periods of fluid flow events(at 34.5±0.9,31.2±0.6,and 23.6±0.8 Ma,respectively)in the northern South China Sea,which are related to regional episodic tectonism.However,^(40)Ar-^(39)Ar ages of illite obtained in this study are significantly younger than the corresponding Rb-Sr ages.The significantly younger^(40)Ar-^(39)Ar ages were probably due to ^(40)Ar loss caused by later dry heating events on the Hainan Island that have not affected the Rb-Sr isotopic systematics.The inconsistency between Rb-Sr and^(40)Ar-^(39)Ar data should be attributed to different isotopic behaviors of K-Ar and Rb-Sr isotopic systematics in illite.Our results indicate that Rb-Sr isotopic dating method may be a preferential approach for clay dating in geological settings where exist younger dry heating events.
基金National Natural Science Foundation of China(42072186)Science and Technology Project of Petro China(2021-DJ2203)Scientific Research and Technology Development Project of Petro China(2022KT0302-1)。
文摘Taking lake basin shales of the Triassic Yanchang Formation in the Ordos Basin,NW China and the Cretaceous Qingshankou Formation in the Songliao Basin,NE China as research objects,the characteristics and origins of different types of silica in the shales have been studied by means of core observation,thin section identification,cathodoluminescence,X-ray diffraction analysis,scanning electron microscope(SEM),electron probe and rock pyrolysis.The results shows that the origins of silica include felsic mineral dissolution,tuffite devitrification,clay mineral transformation and siliceous mineral metasomatism.The silica formed by feldspar dissolution commonly appears as spots and veins,with low degree of crystallization,and is largely aqueous opal mineral,with an average Si O2 content of 67.2%.Silica formed by devitrification of tuffite mainly occurs in two forms,amorphous silica and authigenic quartz with better crystal shape.The authigenic silica formed during the transformation of clay minerals is embedded in the clay minerals in the form of micron-scale plates and small flakes,or mixed with clay minerals in a dispersed state.The authigenic quartz formed by siliceous mineral metasomatism is in better angular crystal shape,and has an average Si O2 content of 87%.The authigenic siliceous mineral content is positively correlated with the content of terrigenous felsic minerals.The pressure solution of felsic minerals is the main source of authigenic siliceous minerals,followed by the transformation of clay minerals,and the organic matter has some boost on the formation of authigenic silica.The authigenic siliceous materials of different origins have different geological characteristics and occurrence states from terrigenous quartz,which would affect the storage performance,seepage capacity and fracturing effect of continental shale.Although the organic-rich shale has high silica content,different from terrigenous quartz,authigenic silica in this kind of shale mostly floats and disperse in clay minerals,which would have negative effect on the formation of complex fractures in fracturing,fracture support ability after fracturing,and formation of effective seepage channels.Calculating the brittleness index of shale intervals only based on the composition of brittle minerals cannot accurately characterize mechanical characteristics of continental shale oil reservoirs,and would affect comprehensive evaluation and selection of continental shale oil“sweet spots”.
基金supported by the National Natural Science Foundation of China (grants No.41306062 and 41474119)the Key Laboratory of Gas Hydrate Foundation (grant No.SHW[2014]-DX-04)
文摘Objective Authigenic pyrite often develops extensively in marine sediments,which is an important product of sulfate reduction in an anoxic environment.It has a specific appearance and complicated sulfur isotopic properties,and acts as important evidence of methane seep in marine sediments.Strong AOM（anaerobic oxidation of methane）activity has developed in the Okinawa Trough.
基金The National Programme on Global Change and Air-sea Interaction under contract No.GASI-02-SCS-CJ03China Geological Survey:Continental Shelf Drilling Program under contract No.GZH201100202China-Thailand Cooperation Project"Research on Vulnerability of Coastal Zones"
文摘Generation, morphology, and distribution of authigenic minerals directly reflect sedimentary environment and material sources. Surface sediments were collected from the western Gulf of Thailand during 2011–2012, and 159 samples were analyzed to determine detrital minerals. Authigenic minerals, including siderite, pyrite, and glauconite, are abundant whereas secondary minerals, such as chlorite and limonite, are distributed widely in the study area. Siderite has a maximum content of 19.98 g/kg and appears in three types from nearshore to continental shelf, showing the process of forming-maturity-oxidation. In this process, the Mn O content in siderite decreases, but FeOand Mg O content increase. Colorless or transparent siderite pellets are fresh grains generated within a short time and widely distributed throughout the region; high content appears in coastal area where river inputs are discharged. Translucent cemented double pellets appearing light yellow to red are mature grains; high content is observed in the central shelf. Red-brown opaque granular pellets are oxidized grains,which are concentrated in the eastern gulf. Pyrite is mostly distributed in the central continental shelf with an approximately north–south strip. Pyrite are mainly observed in foraminifera shell and distributed in clayey silt sediments, which is similar to that in the Yangtze River mouth and the Yellow Sea. The pyrite in the gulf is deduced from genetic types associated with sulfate reduction and organic matter decomposition. Majority of glauconite are granular with few laminar. Glauconite is concentrated in the northern and southern parts within the boundary of 9.5° to 10.5°N and is affected by river input diffusion. The distribution of glauconite is closely correlated with that of chlorite and plagioclase, indicating that glauconite is possibly derived from altered products of chlorite and plagioclase. The KO content of glauconite is low or absent, indicating its short formation time.
基金supported by the National Major Science and Technology Project“Shale gas enrichment conditions and play evaluation technologies and their application in the Sichuan Basin and its periphery”(No.:2017ZX05035).
文摘Studies on the origin of shale brittleness are of great significance to understanding shale gas accumulation laws.The current studies,however,mostly focus on the improvement of shale brittleness by biological quartz enrichment,but rarely on the recrystallization of quartz in the process of diagenetic evolution.In this paper,a series of researches were carried out on the Lower Silurian Longmaxi Fm marine shale in the Changning block of the Sichuan Basin.Firstly,shale pore,mineral component and bedding characteristics were observed by means of cathodoluminescence(CL),scanning electron microscope(SEM)and so on.Then,the control effects of quartz origin,overpressure environment and diagenetic evolution on shale brittleness were investigated by analyzing the mineral composition and siliceous composition of shale microscopically.Finally,the authigenic embrittlement model of marine shale was put forward and the geological significance of authigenic microcrystalline quartz to the improvement of shale brittleness in the process of diagenesis was illustrated.The following results were obtained.First,during the sedimentation,burial and diagenetic evolution,shale experiences diagenetic changes which help increase quartz content and form concealed fracture networks,thus benefiting the formation of complex flow pathways in later stimulation.Second,organic matters play a positive role in improving shale brittleness in the process of geological evolution.It promotes the formation of authigenic microcrystalline quartz and improves the brittleness of shale.In conclusion,due to the authigenic embrittlement of shale in the process of diagenesis,rock structure is changed,rock strength is enhanced and shale porosity is preserved.Consequently,reservoir space in shale is improved and the enrichment state of shale gas is modified.Therefore,the preservation condition under the control of tectonic movement factors is vital to geological evaluation on shale gas.In addition,marine shale is certainly well brittle after authigenic embrittlement in the process of diagenesis as long as its organic matter content is abundant.
文摘The clastic rocks in the depth of 2800-6000 m of the Paleogene in Jiyang sub-basin had undergone the middle diagenesis and late diagenesis.The reservoirs in main areas of the sub-basin developed 2-6 secondary pores zones.The reservoirs in the stage A of middle diagenesis of Bonan fault zone in Zhanhua depression and of the gentle slope belt of Chezhen depression are controlled by the acidic diagenetic medium and developed one secondary pores zone in each diagenetic sub-stage respectively.The contents ofautogenic quartz,pyrite and kaolinite are quite high in these reservoirs.The reservoirs’
基金This work was supported jointly by the Key Laboratory of Submarine Geosciences, SOA (Grant No. 2002-3) the National Natural Science Foundation of China (Grant No. 40272052) China Scholarship Council (CSC).
文摘Characteristic gypsum micro-sphere and granular mass were discovered by bin-ocular microscope in the gas hydrate-associated sediments at cores SO143-221 and SO143/TVG40-2A respectively on Hydrate Ridge of Cascadia margin, the eastern North Pacific. XRD patterns and EPA analyses show both micro-sphere and granular mass of the crystals have the typical peaks and the typical main chemical compositions of gypsum, although their weight percents are slightly less than the others in the non-gas hydrate-associated marine regions. SEM pictures show that the gypsum crystals have clear crystal boundaries, planes, edges and cleav-ages of gypsum in form either of single crystal or of twin crystals. In view of the fact that there are meanwhile gas hydrate-associated authigenic carbonates and SO42--rich pore water in the same sediment cores, it could be inferred reasonably that the gypsums formed also authigenically in the gas hydrate-associated environment too, most probably at the interface between the down-ward advecting sulfate-rich seawater and the below gas hydrate, which spilled calcium during its formation on Hydrate Ridge. The two distinct forms of crystal intergrowth, which are the granular mass of series single gypsum crystals at core SO143/TVG40-2A and the microsphere of gypsum crystals accompanied with detrital components at core SO143-221 respectively, indicate that they precipitated most likely in different interstitial water dynamic environments. So, the distinct authigenic gypsums found in gas hydrate-associated sediments on Hydrate Ridge could also be believed as one of the parameters which could be used to indicate the presence of gas hydrate in an unknown marine sediment cores.
基金supported by National Natural Science Foundation of China(Grant Nos.41102021,41202099)National Special Research Fund(Grant No.GZHL20110308)
文摘A type of authigenic pyrites that fully fill or semi-fill the rock fractures of drillholes with gas hydrate anomalies are found in the Qilian Mountain permafrost; this type of pyrite is known as ＂fracture-filling＂ pyrite. The occurrence of ＂fracture-filling＂ pyrite has a certain similarity with that of the hydrate found in this region, and the pyrite is generally concentrated in the lower part of the hydrate layer or the hydrate anomaly layer. The morphology, trace elements, rare earth elements, and sulfur isotope analyses of samples from drillhole DK-6 indicate that the ＂fracture-filling＂ pyrites are dominated by cubic ones mainly aligned in a step-like fashion along the surfaces of rock fractures and are associated with a circular structure, lower Co/Ni and Sr/Ba, lower ZREE, higher LREE, significant Eu negative anomalies, and 634ScDT positive bias. In terms of the pyrites＇ unique crys- tal morphology and geochemical characteristics and their relationship with the hydrate layers or abnormal layers, they are closely related with the accumulation system of the gas hydrate in the Qilian Mountain permafrost. As climate change is an important factor in affecting the stability of the gas hydrate, formation of fracture-filling pyrites is most likely closely related to the secondary change of the metastable gas hydrate under the regional climate warming. The distribution intensity of these py- rites indicates that when the gas hydrate stability zone （GHSZ） is narrowing, the hydrate decomposition at the bottom of the GHSZ is stronger than that at the top of the GHSZ, whereas the hydrate decomposition within the GHSZ is relatively weak. Thus, the zone between the shallowest and the deepest distribution of the fracture-filling pyrite recorded the largest possible original GHSZ.
基金supported by the National Natural Science Foundation of China(Grand Nos.4130606241104086)+2 种基金the Key Laboratory of Gas Hydrate Foundation(Grand Nos.SHW[2014]-DX-03SHW[2014]-DX-04)the Key Laboratory of Marine Hydrocarbon Resources and Environmental Geology Foundation(Grand No.MRE 201213)
文摘The anaerobic oxidation of methane （AOM） has strongly developed at Core A, Site 79 of the middle Okinawa Trough, East China Sea, and a large amount of authigenic pyrite is preserved in the surface sediment. In this study, we analyze the characteristics of the authigenic pyrite and its sulfur isotopic values. The authigenic pyrite is stripy and tubular, and there were foraminifera compartments filled with pyrite. The pyrite is extracted using chromium reduction, and the values of δ348 are found to lie between -41.20‰ and 8.92‰ V-CDT. The bulk pyrite tends to be more enriched in 348 with increasing depth. Particularly, the 834S value of the pyrite lies between -32.73%o and -41.20‰ V-CDT above 278 cmbsf, but it quickly increases below this depth （-21.49%o-8.92‰ V-CDT）. At the same time, the total sulfur content of the pyrite shows an abrupt increase above 100 cmbsf but is otherwise stable between 1.04% and 0.55% below 100 cmbsf. The stable and negative values of 8345 and the decreasing values of total sulfur above 278 cmbsf indicate reduced AOM activities in 17.18-5.3 ka. In addition, the increasing δ34S and pyrite content indicate strong AOM development and methane seep below 278 cmbsf in 18.8-17.18 ka. In particular, the highest positive value of δ34S occurring in 18.78 ka indicates the most intense AOM activity. The shallow sul- fate-methane interface （SMI） and high methane flux below marine sediments also strongly support this activity.
文摘According to the data of the mineral assemblages, the sediment layers with authigenic glauconite were found in the X<sub>1</sub> core collected from the northeast of the Beibu Gulf. Pliocene sediment layer containing a lot of foraminifera shows a shallow sea facies. Its thickness is larger than 30 m and is located at the depth below 59 m of the core.
基金Supported by the National Natural Science Foundation of China(42272117,42002116).
文摘Thin section and argon-ion polishing scanning electron microscope observations were used to analyze the sedimentary and diagenetic environments and main diagenesis of the Permian Fengcheng Formation shales in different depositional zones of Mahu Sag in the Junggar Basin,and to reconstruct their differential diagenetic evolutional processes.The diagenetic environment of shales in the lake-central zone kept alkaline,which mainly underwent the early stage(Ro<0.5%)dominated by the authigenesis of Na-carbonates and K-feldspar and the late stage(Ro>0.5%)dominated by the replacement of Na-carbonates by reedmergnerite.The shales from the marginal zone underwent a transition from weak alkaline to acidic diagenetic environments,with the early stage dominated by the authigenesis of Mg-bearing clay and silica and the late stage dominated by the dissolution of feldspar and carbonate minerals.The shales from the transitional zone also underwent a transition from an early alkaline diagenetic environment,evidenced by the formation of dolomite and zeolite,to a late acidic diagenetic environment,represented by the reedmergnerite replacement and silicification of feldspar and carbonate minerals.The differences in formation of authigenic minerals during early diagenetic stage determine the fracability of shales.The differences in dissolution of minerals during late diagenetic stage control the content of free shale oil.Dolomitic shale in the transitional zone and siltstone in the marginal zone have relatively high content of free shale oil and strong fracability,and are favorable“sweet spots”for shale oil exploitation and development.
基金The Qingdao National Laboratory for Marine Science and Technology under contract No.QNLM2016ORP0210the National Natural Science Foundation of China under contract Nos 41306061,41473080 and 41376076the Scientific Cooperative Project by China National Petroleum Corporation and Chinese Academic of Sciences under contract No.2015A-4813
文摘The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane（AOM） coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor（cmbsf） in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values（δ^34 S） of pyrite vary greatly（from –46.6‰ to –12.3‰ V-CDT） and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction（OSR） and is influenced by AOM with depth.The relative high abundance and δ^34 S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone（SMTZ）.The sulfur isotopic composition of gypsum（from–25‰ to –20.7‰） is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO2,iron（Ⅲ） and oxygen driven by the SMTZ location shift to great depths.The δ^34 S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.
基金The Laboratory for Marine Mineral ResourcesQingdao National Laboratory for Marine Science and Technology under contract No.MMRKF201810+1 种基金the National Key Research&Development Program of China under contract Nos2018YFC0310000 and 2017YFC0307406the Shandong Province“Taishan Scholar”Construction Project
文摘Previous studies of gas hydrate in the Dongsha area mainly focused on the deep-seated gas hydrates that have a high energy potential,but cared little about the shallow gas hydrates occurrences.Shallow gas hydrates have been confirmed by drill cores at three sites(GMGS208,GMGS209 and GMGS216)during the GMGS2 cruise,which occur as veins,blocky nodules or massive layers,at 8–30 m below the seafloor.Gas chimneys and faults observed on the seismic sections are the two main fluid migration pathways.The deep-seated gas hydrate and the shallow hydrate-bearing sediments are two main seals for the migrating gas.The occurrences of shallow gas hydrates are mainly controlled by the migration of fluid along shallow faults and the presence of deep-seated gas hydrates.Active gas leakage is taking place at a relatively high-flux state through the vent structures identified on the geophysical data at the seafloor,although without resulting in gas plumes easily detectable by acoustic methods.The presence of strong reflections on the high-resolution seismic profiles and dim or chaotic layers in the subbottom profiles are most likely good indicators of shallow gas hydrates in the Dongsha area.Active cold seeps,indicated by either gas plume or seepage vent,can also be used as indicators for neighboring shallow gas hydrates and the gas hydrate system that is highly dynamic in the Dongsha area.
