A polymetallic layer is usually developed at the bottom of the early Cambrian black shale in Guizhou Province.The mineral that makes up the polymetallic layer is related to the sedimentary facies.To analyze the differ...A polymetallic layer is usually developed at the bottom of the early Cambrian black shale in Guizhou Province.The mineral that makes up the polymetallic layer is related to the sedimentary facies.To analyze the differentiation mechanism between polymetallic deposits(Ni-Mo and V),the Zhijin Gezhongwu profile located in the outer shelf and the Sansui Haishan V deposit located in the lower slope are selected to study the in situ sulfur isotopes and trace elements of pyrite.The results show that δ^(34)S values of pyrite vary widely from−7.8‰to 28‰in the Gezhongwu profile,while the δ^(34)S values are relatively uniform(from 27.8‰to 38.4‰)in the Haishan profile.The isotopic S composition is consistent with the transition that occurs in the sedimentary phase from the shelf to the deep sea on the transgressive Yangtze platform;this indicates that the δ^(34)SO_(4)^(2−)values in seawater must be differently distributed in depositional environments.The sulfur in the Ni-Mo layer is produced after the mixing of seawater and hydrothermal fluid,while the V layer mainly originates from seawater.Overall,the Ni-Mo and V deposits have been differentiated primarily on the basis of the combined effect of continental weathering and hydrothermal fluid.展开更多
The Early Cambrian represents a critical time period characterized by extraordinary biological innovations and dynamic redox conditions in seawaters.Nitrogen isotopic signatures of ancient sediments have the potential...The Early Cambrian represents a critical time period characterized by extraordinary biological innovations and dynamic redox conditions in seawaters.Nitrogen isotopic signatures of ancient sediments have the potential to elucidate the evolutionary path of marine redox states and the biogeochemical nitrogen cycle within the water column of the Early Cambrian ocean.While existing research on this topic has predominantly focused on South China,the exploration of other continental margins has been limited,leaving contradictory hypotheses untested.In this study,pairedδ^(15)N andδ^(13)C org analyses were performed on the Lower Cambrian successions from the Shiairike section(inner ramp)and Well Tadong 2(deep shelf/basin)in the northwestern and eastern Tarim Basin,respectively.Our data from the Shiairike section reveal a discernible shift in the operation of different nitrogen cycles for the black chert-shale unit,also referred to as the black rock series in Chinese literature,of the Yurtus Formation(Fortunian stage to lower Stage 3).Oscillatingδ^(15)N values for its lower part are suggestive of alternating anaerobic assimilation of NH 4+and denitrification/anammox.This is likely attributed to a shallow,unstable chemocline consistent with the upwelling and incursion of deep,anoxic waters during a major transgression.In contrast,aerobic nitrogen cycling,indicated by positiveδ^(15)N values of>2‰,dominated the upper part alongside a reduction in upwelling intensity.On the other hand,theδ^(15)N signatures of Xishanbulake and Xidashan Formations of Well Tadong 2,which encompass a time interval from the Cambrian Fortunian Age to Age 4,are indicative of N_(2)fixation by diazotrophs as the major nitrogen source.The two studied intervals,although not time-equivalent,exhibit separated states of nitrogen cycling at least during the deposition of the Yurtus black rock series.The spatially different nitrogen cycling of the studied sections is compatible with a redox-stratified ocean during the deposition of the Yurtus black rock series.The build-up of a NO_(3)−reservoir and aerobic nitrogen cycling in seawater was largely restricted to near-shore settings whereas anaerobic nitrogen cycling dominated by N_(2)fixation served as the main nitrogen uptake pathway in off-shore settings.展开更多
The molybdenum-nickel deposits in Shuidong District of Nayong County (Guizhou Province, Southwest China) are found mainly in black shale series of Lower Cambrian Niutitang Formation, which is another Mo-Ni-rich regi...The molybdenum-nickel deposits in Shuidong District of Nayong County (Guizhou Province, Southwest China) are found mainly in black shale series of Lower Cambrian Niutitang Formation, which is another Mo-Ni-rich region besides Zunyi District (Guizhou province). Our systematic study on the Mo-Ni deposits in Tangjiaba of Nayong reveals that layered coarse-grained limestones, spherical beaded limestones concretions are hosted at the lower seam of the Mo-Ni deposits. Its strong negative carbon isotope anomaly (the carbon isotope value of the coarse-grained limestones varies from -2.148‰ to 8.223‰) is similar to that in the modern submarine black smoker chimney. The carbon in the coarse-grained limestones from black rock series of Nayong County might be deep source inorganic carbon. The seams, coarse-grained limestones, ore-bearing coarse-grained limestones and the roof and floor of the deposits are characterized by co-variation on the trace element spider diagram, showing good homology. The extraordinary enrichment of Ag, As and Sb resembles hydrothermal sedimentation. Pro-Earth's core elements Se is strongly enriched in Ni-Mo ore-bearing coarse-grained limestones. The ore-bearing rock series has an extremely low Th/U value (0.012-0.19); in the logU-logTh Cartesian Coordinates, the samples of the roof and floor of the deposits and ore-bearing coarse-grained limestones are found in the East Pacific tise; and the samples of coarse-grained limestones are found between the paleo-hydrothermal dedimentary area and the East Pacific tise. The chondrite-normalized rare earth element patterns of the Ni-Mo deposits show LREE enrichment, Ce negative anomaly, and Eu negative anomaly (which is supposed to be influenced by the deep magmatic processes in an extensional environment) resembles the rare earth element distribution patterns of the fluid and its sediments in modern submarine hydrothermal system. It proves that coarse-grained limestones is characterized by typical hydrothermal limestones, being closely related with the genesis of Mo-Ni deposits in Nayong County, which provides new evidence for hydrothermal sedimentary genesis of Mo-Ni deposit and negative carbon anomaly in the basal Cambrian on a global scale.展开更多
Control of various factors, including mineral components, primary productivity and redox level, on the total organic carbon(TOC) in the lower Cambrian black shale from southeastern margin of Upper Yangtze(Taozichong, ...Control of various factors, including mineral components, primary productivity and redox level, on the total organic carbon(TOC) in the lower Cambrian black shale from southeastern margin of Upper Yangtze(Taozichong, Longbizui and Yanbei areas) is discussed in detail in this article. Mineral components in the study strata are dominated by quartz and clay minerals. Quartz in the Niutitang Formation is mainly of biogenic origin, and the content is in positive correlation with TOC, while the content of clay minerals is negatively correlated with TOC. Primary productivity, represented by the content of Mobio(biogenic molybdenum), Babio(biogenic barium) and phosphorus, is positively correlated with TOC. The main alkanes in studied samples are nCC, and odd–even priority values are closed to 1(0.73–1.13), which suggest the organic matter source was marine plankton. Element content ratios of U/Th and Ni/Co and compound ratio Pr/Ph indicate dysoxic–anoxic bottom water, with weak positive relative with TOC. In total, three main points can be drawn to explain the relationship between data and the factors affecting organic accumulation:(1) quartz-rich and clay-mineral-poor deep shelf–slope–basin environment was favorable for living organisms;(2) high productivity provided the material foundation for organic generation;(3) the redox conditions impact slightly on the content of organic matter under high productivity and dysoxic–anoxic condition.展开更多
The Ediacaran and early Cambrian black shales are widespread across the South China Craton (Yangtze and Cathaysia blocks). However, the trace element distribution patterns of the Ediacaran and early Cambrian black s...The Ediacaran and early Cambrian black shales are widespread across the South China Craton (Yangtze and Cathaysia blocks). However, the trace element distribution patterns of the Ediacaran and early Cambrian black shales in the Cathaysia Block are still unclear. In this study, thirty- four black shale samples in the Lechangxia Group (Ediacaran) and thirteen black shale samples in the lower Bacun Group (early Cambrian) from Guangning area, western Guangdong Province, South China, were analyzed for major and trace elements concentrations. Compared to the upper continental crust, the Ediacaran black shales exhibit strongly enriched Se, Ga, and As with enrichment factor values (EF) higher than 10, significantly enrichedBi and Rb (10〉EF〉5), weakly enriched Mo, Ba, Cs, V, In, Be, TI, and Th (5〉EF〉2), normal U, Cr, Cd, Sc, Pb, Cu, and Li (2〉EF〉0.5), and depleted Ni, Zn, Sr, and Co. Early Cambrian black shales display strongly enriched Se, Ga, and As, significantly enriched Ba, Bi, and Rb, weakly enriched Mo, Cs, Cd, V, U, Be, In, and TI, normal Sc, Th, Cr, Li, Cu, Ni, and Pb and depleted Co, Zn, and Sr. Moreover, Se is the most enriched trace element in the Ediacaran and early Cambrian black shales: concentrations vary from 0.25 to 30.09 ppm and 0.54 to 5.01 ppm, and averaging 4.84 and 1.72 ppm, with average EF values of 96.87 and 34.32, for the Ediacaran and early Cambrian shales respectively. The average concentration of Se in the Ediacaran black shales is 2.8 times higher than that of early Cambrian black shales. Se contents in the Ediacaran and early Cambrian black shales exhibit significant variation (P = 0.03). Provenance analysis showed that Se contents of both the Ediacaran and early Cambrian black shales were without detrital provenance and volcanoclastic sources, hut of hydrothermal origin. The deep sources of Se and the presence of pyrite may explain the higher Se contents in the Ediacaran black shales. Similar with the Se-rich characteristics of the contemporaneous black shales in the south Qingling Mountain and Yangtze block, the Ediacaran and early Cambrian black shales in Guangning area, Cathaysia, are also enriched in Se, which may provide a clue for looking for the selenium-rich resources in western Guangdong Province.展开更多
Abstract: A great amount of black rock series has been found in the Upper Sinian Members 2 and 4 of the Jinjiadong Formation, middle-upper Liuchapo Formation and the Lower Cambrian Xiaoyanxi Formation in West Hunan, w...Abstract: A great amount of black rock series has been found in the Upper Sinian Members 2 and 4 of the Jinjiadong Formation, middle-upper Liuchapo Formation and the Lower Cambrian Xiaoyanxi Formation in West Hunan, which is associated with periodic sea-level changes. By the studies of relationships between the distribution and development of the biota and the abundance of Au, Ag, U, V, Ni, Mo and Cu in the Upper Sinian and Early Cambrian black rock series in Cili, Dayong, Yuanling, Xupu and Qianyang of West Hunan, central China, it has been revealed that the enrichment of Ag, V, and Mo is related with the development of multi-cell plants and vendotaenides, and that of Cu and Ni is related to flourishing of bacteria and shelly fossils. The black rock series in the study area contains abundant organic matter, among which the siliceous shale contains the highest TOC, amounting to 4.51–13.4%. All the values of the equivalent vitrinite reflectance (medium values) determinated with the IR-spectroscopic method in the area are over 2.65%, indicating that the organic evolution was at an overmature stage. Due to the effect of enhancement of organic maturation by hydrothermal fluids, the Upper Sinian and Lower Cambrian had a reverse organic maturity profile in most areas of West Hunan. The enrichment of Ag, V, Ni, Mo and U is a result of organic absorption, and that of Au might be attributed to the migration by hydrothermal fluids.展开更多
A silicalite bed was found in the hanging wall and foot wall of the sulfide-rich bed ofthe Lower Cambrian black rock series in South China. Its origin was not described before. Onthe oxide (SiO2-Al2O3, SiO-2-MgO, SiO...A silicalite bed was found in the hanging wall and foot wall of the sulfide-rich bed ofthe Lower Cambrian black rock series in South China. Its origin was not described before. Onthe oxide (SiO2-Al2O3, SiO-2-MgO, SiO2-K2O+ Na2O) diagrams for discriminating silicalitesof chemical, biological and volcanic origins (Liu Xiufeng, 1991), most of the data points of silicalites fall within the areas representing silicaIites of chemical and volcanic origins. On the AlFe-Mn diagram for discriminating silicalites of hydrothermal and biological origins (Yamamoto,1987), the data points fall within the areas representing silicalites of hydrothermal and hydrothermal-biological origins. On the SiO2-Al2O3 diagram for discriminating silicalites of hydrothermal and hydrogenous origins (Bonatti, 1975 ), the data points mostly fall within thehydrothermal area. The ratios of SiO2Al2O3, SiO2/(K2O+Na2O), SiO2/MgO, and K2O/Na2O in the silicalites stand between those of volcanic sediments and of sea floor hydrothermalsediments. The total amount of rareuearth elements in the silicalites is low; the North American Shale-normalized REE patterns decline leftward with obvious negative Ce anomaly. Thetrace elements Mo, Zn, As, Sb, Se, U, and Ba are higher than those in non-hydrothermalsediments and U/Th≥1. The present authors think that the silicalites are derived fromseafloor hot brines which had attracted elements from igneous rocks.展开更多
Adsorption experiments were made at room temperature and neutral pH value on different types of min-erals associated with the Lower Cambrian black shale series polymetallic layers in Hunan and Guizhou provinces on nan...Adsorption experiments were made at room temperature and neutral pH value on different types of min-erals associated with the Lower Cambrian black shale series polymetallic layers in Hunan and Guizhou provinces on nanometer-sized Pt colloids and PtCl42--bearing ionic solutions with an attempt to constrain the relationship between the different types of minerals in the polymetallic layers and the enrichment of platinum group elements (PGEs). Experimental results showed that the different types of minerals show strong selectivity to the adsorption of nano-meter-sized Pt colloids and PtCl42--bearing ionic solutions. Metallic sulfides, organic matter and clay minerals are the strong adsorbents of PGEs, while quartz, albite, muscovite and other silicate minerals show a week adsorbility to both of them. This phenomenon is well consistent with the geological fact that metallic sulfides, organic matter and clay minerals in the polymetallic layers of the black shale series are the major carrier minerals of PGEs, giving a thorough explanation to the mechanism of enrichment of previous metal elements. Adsorption may be a principal mechanism of enrichment of precious metal elements under lower temperature conditions. The presence of the aforementioned strong adsorbents is the good geochemical barriers for the enrichment of PGEs.展开更多
In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platfo...In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platform with a width of ca. 200-400 km and a length of more than 1500 km, we present new paired δ13C data on carbonates (δ13Ccarb) and associated organic carbon (δ13Corg) and δ34Spy data on sedimentary pyrite in black shales from three sections (Ganziping, Shancha and Xiaohekou) located in NW Hunan, China. In these sections, a total of 82 Lower Cambrian black shale samples have δ13Ccarb values ranging from -4.0‰ to 1.7‰ with an average value of -2.1‰, and δ13Corg values between -34.9‰ and -28.8‰, averaging -31.9‰. The ?34Spy values of 16 separated sedi-mentary pyrite samples from the black shales vary between +10.2‰ and +28.7‰ with an average value of +19.5‰, presenting a small isotope fractionation between seawater sulfate and sedimentary sulfide. The model calculation based on credible data from the paired analyses for δ13Ccarb and δ13Corg of 11 black shale samples shows a high CO2 concentration in the Early Cambrian atmosphere, about 20 times higher than pre-industrial revolution values, consis-tent with previous global predictions. The small sulfur isotope fractionation between seawater sulfate and sedimen-tary sulfide in black shales, only 15.5‰ on average, implies a low sulfate level in the Early Cambrian seawater around 1 mmol. In combination with a high degree of pyritization (DOP) in the black shales, it is suggested that sul-fidic deep-ocean water could have lingered up to the earliest Cambrian in this area. The black shale deposition is envisaged in a stratified marine basin, with a surface euphotic and oxygenated water layer and sulfidic deeper water, controlled by a continental margin rift.展开更多
The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on....The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic-lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province (China). All the saturated hydrocarbon fractions have a unimodal distribution of n-alkanes, a high content of short-chain alkanes and maximize at C 19 or C 20 (C 23 for sample Gzh00-1). The C 27 /C 29 sterane ratio ranges from 0.77 to 1.20 and 4-methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values (0.7) suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25-norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ 13 C org excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea-level rise.展开更多
Systematic analyses of noble metal elements in the Lower Cambrian black rock series of South China are reported. Correlations of w (Os)/ w (Ir), w (Au)/ w (Ir), w (Ag)/ w (Au), w (Pt+Pd)/ w (Os+R...Systematic analyses of noble metal elements in the Lower Cambrian black rock series of South China are reported. Correlations of w (Os)/ w (Ir), w (Au)/ w (Ir), w (Ag)/ w (Au), w (Pt+Pd)/ w (Os+Ru+Rh+Ir), relations of noble metal and platinum group element (PGE) distribution patterns reveal that the noble metals are not directly from extraterrestrial materials. Studying the data of 9 aspects, the authors conclude that the noble metals were mainly from ultramafic mafic igneous rocks and their enrichment in black rocks is mainly controlled by hydrothermal fluid.展开更多
To explore the genesis of the laminated calcite veins developed in the black shale of Chang 73 submember of the Ordos Basin,the petrology,microstructure and geochemistry of calcite veins are studied using thin section...To explore the genesis of the laminated calcite veins developed in the black shale of Chang 73 submember of the Ordos Basin,the petrology,microstructure and geochemistry of calcite veins are studied using thin sections,fluid inclusions,trace elements and isotopic geochemistry.The source,the time of formation,the mechanism of formation,and the dynamic background of the veins are discussed.The veins are mostly made up of calcite,mixed with lenticular or spindle-shape solid wall rock inclusions.Three structures are identified in the calcite minerals:fibrous,rhombic cleavage,and wedge-like structure.Trace elements and isotopes of carbon and oxygen confirm that the calcite veins were formed from a high density hydrothermal fluid.It is assumed that calcite veins formed prior to wall rock consolidation during the formation of the Qinling Orogenic Belt in the Middle and Late Triassic.The results show that the sedimentary sources of Chang 73 submember were influenced by hydrothermal materials besides terrigenous detritus.The fibrous calcite is different from the fibrous calcite reported in the morphology and mechanism of formation.In this way,the research complements and improves the morphology and the mechanism of formation of fibrous calcite.展开更多
Based on geochemical analysis results of core samples from the Triassic Chang 7 Member of Well Feng 75 drilled in the northwest margin of Ordos Basin,combined with geological characteristics of this region,the formati...Based on geochemical analysis results of core samples from the Triassic Chang 7 Member of Well Feng 75 drilled in the northwest margin of Ordos Basin,combined with geological characteristics of this region,the formation environment of the black shale and its control on shale oil enrichment are comprehensively studied.From the Chang 73 to Chang 71 Sub-members,the black shale have organic carbon contents decreasing from 5.70%to 3.55%,hydrogen indexes decreasing from 345 mg/g to 269 mg/g,while the oxygen indexes increasing gradually from 6 mg/g to 29 mg/g,indicating that the sedimentary environment during the depositional period of Chang 72 and Chang 73 Sub-members was anoxic.Biomarkers in the black shale change regu-larly,and have an obvious“inflection point”at the depth of 2753–2777 m in the Chang 73 Sub-member,indicating that the input of terrigenous organic matter increased.However,there is a negative drift about 2%of organic carbon isotopic composition near the“inflection point”,which is in conflict with the results of biomarker compounds.This is because the extreme thermal and anoxic events caused by continental volcanic activity in the ancient Qinling region caused negative drift of carbon isotopic composition of the black shale in the Ordos Basin.The volcanic activity caused rise of temperature,polluted air,extreme weathers,more floods and thus more input of terrigenous organic matter,and gave rise to extremely anoxic environment con-ducive to the preservation of organic matter.Terrigenous organic matter is more conducive to the formation of light oil than aquatic organic matter,so these sections in Yanchang Formation are major“sweet spots”for shale oil enrichment.展开更多
The systematic analyses of trace elements, REEs and PGEs of black shale at the bot-tom of the Lower Cambrian in Tarim Basin have been made for the first time in this work. The basic geochemical features are that some ...The systematic analyses of trace elements, REEs and PGEs of black shale at the bot-tom of the Lower Cambrian in Tarim Basin have been made for the first time in this work. The basic geochemical features are that some trace elements having something to do with the deep-level fluids are highly enriched, including V, Cr, Ni, Cu, Zn, Ge, As, Sr, Y, Mo, Ag, Cd, Sb, Ba, Pb and U, and the Th/U and Th/Sc ratios decreased compared with those in the same kind of rocks in the crust, that the enriched degrees of LREEs are reduced, Eu and Ce depleted distinctly in the chon-drite-normalized REE patterns, and that the contents of PGEs and Au are increased. These char-acteristics indicate that there were more mafic interior sources in the basin when the black shale was deposited. Generally, the interior sources show an extensional tectonic setting of lithosphere. It can be seen from the change of the characteristics of trace elements, REEs and PGEs along the black shale section that the quantity of interior source from inner earth is gradually increased upwards in the lower part of the section, reaches the peak value as shown by sample No. 4 (XCM7-1), and then decreased, which might indicate the episodic extension of lithosphere in the beginning of the Lower Cambrian.展开更多
Zhijin County in Western Guizhou is one of the most important production areas of phosphorites in China. In order to investigate genesis of the phosphorites, their REE compositions were analyzed by using inductively c...Zhijin County in Western Guizhou is one of the most important production areas of phosphorites in China. In order to investigate genesis of the phosphorites, their REE compositions were analyzed by using inductively coupled plasma emission mass spectrometry (ICP-MS) method. For comparison, phosphorites from the Lower Cambrian black rock series in Southern China, such as Zunyi in Guizhou and Zhangjiajie in Hunan Province, were also analyzed. The analytical data show that: (1) Xinhua phosphorites possess a quite high and greatly varied total rare earth elements (ΣREE), which varying between 164.23×10-6 and 1395.01×10-6 with average of 642.54×10-6, remarkable differentiation between light (LREE) and heavy rare earth elements (HREE), and the ΣLREE/ΣHREE ratios varying between 5.04 and 6.52. The ΣREE and ΣLREE/ΣHREE ratios of the Zunyi and Zhangjiajie phosphorites are 156.69×10-6~637.41×10-6 with average of 431 75×10-6 and 3.17~6.95 with average of 4.37 respectively; (2) All the phosphorites from Xinhua, Zunyi and Zhangjiajie show remarkable negative Ce anomalies. Besides, the Xinhua phosphorites possess lower δCe, which varying between 0.26 and 0.53 with average of 0.35, while δCe of the Zunyi and Zhangjiajie phosphorites are 0.30~0.66 with average of 0.47, suggesting that all of the phosphorites are typical marine sediments deposited mainly in ancient peri-continental seas, and the depositional position of the Xinhua phosphorite might be deeper; (3) Most phosphorites from Xinhua, Zunyi and Zhangjiajie possess unremarkable positive Eu anomaly, and only a few of samples show obvious ones. The δEu varies between 0.98 and 2.4, suggesting that hot (>200 ℃) and strong reductive hydrothermal fluids might have been involved in genesis of the phosphorites; (4) The Xinhua phosphorite is relatively depleted in HREE, and LaN/NdN and δY of most samples are >1 and >1.5 respectively. Besides, there exists no correlation between δY and δCe, suggesting that the phosphorite was subjected to quite strong weathering and leaching processes, and catagenesis do not greatly modify its REE compositions.展开更多
The marine black shale formations of different epochs are widely seen in China. They usually come cul as ore-bearing horizon and contain different ore-forming element. Why are there so many different associated meta...The marine black shale formations of different epochs are widely seen in China. They usually come cul as ore-bearing horizon and contain different ore-forming element. Why are there so many different associated metallic elements in the marine black shale ? Evidence shows that the answer is bio-mineralization. The bio-mineralizahon in the process of formation of metalliferous black shales can be divided intp twp stages. The first stage is the bio-achvities occurring in the surface layer aquatic body of the ocean .The ore-forming elements could be absorbed by only a few species of organisms as a bioconcentrator. The second stage is the biogeochemical process. The anaerobic bacteria decomposed the organic remains and the metal elements were activated, and migrated and combined with organic matter or clay minerals or sulfide. After sediments were buried deeply, the organic matter were cracked by high earth temperature.The metal elements in organic compound were continuously acivated, and migrated to form matamorphic minerals or hydrothermal minerals in original rocks or quartz veins. The biogenetic marks in the black shale are changed or distorted beyond recognition and not easy to be found.展开更多
The shale at the bottom of the Lower Cambrian black series in South China is rich in nonferrous metals, noble metals, rare and dispersed elements and radioactive elements, known as polyelement-rich bed. In order to da...The shale at the bottom of the Lower Cambrian black series in South China is rich in nonferrous metals, noble metals, rare and dispersed elements and radioactive elements, known as polyelement-rich bed. In order to date and trace the source of the platinum group elements, 6 samples were collected from the Zhongnan region of Guizhou Province, and the Ganzi- ping-Sancha region of Hunan Province. The contents and isotopes of Re and Os were measured. Re and Os are positively correlated with each other and the correlation coefficient between 187Os/188Os and 187Re/188Os is 0.99856. On the 187Os/188Os-187Re/188Os diagram, 6 sample points are well-distributed along the (542±11) Ma fitting isochron in high coincidence and with 0.84±0.12 as the initial 187Os/188Os value. The result displays that the age value of the major mineralization of Re, Os and other platinum group elements is (542±11) Ma, which is identical with the stratigraphical age of the wall rocks; the polyelement beds in Hunan and Guizhou provinces bear high isochroneity; the differences of the forming times of different materials in the polyelement bed of the same area do not surpass the error limit permissible for Re-Os date fitting; there exists no distinct time interval between the formation of the diagenetic veinlets and that of the polyelement bed, or the Re-Os isotope composition has not been distinctly changed by the former process; basaltic crust might be the major source of Re, Os, other platinum group and trace elements in the Lower Cambrian polyelement bed of Hunan and Guizhou provinces.展开更多
Organic matter of the Sinian and early Cambrian black shales on the Yangtze Platform belongs to the light carhon group of isotopes with the δ13C values from - 27% to - 35 %, which are lower than those of the contempo...Organic matter of the Sinian and early Cambrian black shales on the Yangtze Platform belongs to the light carhon group of isotopes with the δ13C values from - 27% to - 35 %, which are lower than those of the contempomneously deposited carbonates and phosphorites. A carbon isotope-stratified paleooceanographic model caused by upwelling is proposed, which can be used not only to interpret the characteristies of organic carbon isotopic compositions of the black shales, but also to interpret the paleogeographic difference in the organic carbon isotope compositions of various types of sedimentary rocks.展开更多
The extensive transgression that occurred on the Yangtze Plate in Early Cambrian led to a massive organic carbon pool in the Niutitang Formation. A black shale core section from 3 251.08 to 3 436.08 m beneath the Eart...The extensive transgression that occurred on the Yangtze Plate in Early Cambrian led to a massive organic carbon pool in the Niutitang Formation. A black shale core section from 3 251.08 to 3 436.08 m beneath the Earth's surface was studied to estimate the contribution of oxygenic photosynthesis to organic carbon sink fluxes in Early Cambrian Upper Yangtze shallow sea. Results indicate that the oxygenic photosynthesis played the most important role in carbon fixation in Early Cambrian. Organic carbon sink was mainly contributed by photosynthetic microorganisms, e.g., cyanobacteria, algae and archaea. The Niutitang Formation was formed in a deep anoxic marine shelf sedimentary environment at a sedimentation rate of ~0.09±0.03 mm/yr. The initial TOC abundance in Niutitang shale ranged from 0.18% to 7.09%, with an average of 2.15%. In accordance with the sedimentation rate and initial TOC abundance, organic carbon sink fluxes were calculated and found to range from 0.21 to 8.10×10~3 kg/km^2·yr^(-1), especially the organic carbon sink fluxes in depth between 3 385 and 3 470 m range from 3.80 to 8.10×10~3 kg/km^2·yr^(-1), with an average of ~6.03×10~3 kg/km^2·yr^(-1), which is much higher than that of contemporary marine sediments. The organic carbon sink fluxes of Niutitang shale are equal to 0.56 to 21.61×10~3 kg/km^2·yr^(-1) net oxygen emitted into the Early Cambrian ocean and atmosphere, this emitted oxygen may have significantly promoted the oxygen level of the Earth's surface and diversification of metazoans.展开更多
There are different sulfur forms in the black shales from theEarly Cambrian of the Yangtze platform. With its emphasis on pyrite and organosulfur, this paper discusses their distribution and formation. The research sh...There are different sulfur forms in the black shales from theEarly Cambrian of the Yangtze platform. With its emphasis on pyrite and organosulfur, this paper discusses their distribution and formation. The research shows that sulfur phases take regular variations laterally as well as vertically in the research areas. In western researched profile with high terrigenous supply at the time it formed, there exists a larger amount of pyrite and less organosulfur, and pyrite amount declines while organosulfur content increases upwards along the profile. This black shale profile is characterized by relatively light sulfur isotope composition with evolution trend of becoming heavier both for pyrite and organosulfur from bottom to top along the profile. Opposite situation occurs in eastern profiles which were located farther away from terrigenous land. Here pyrite amount obviously decreases and organic matter has combined more sulfur, although these two kinds of sulfur species take similar trend in content variation along profiles to that for western profile. At the same time more 34S is accumulated in sulfur species of black shale samples from eastern profile, and sulfur isotope composition gradually turns lighter from bottom to top. In combination with other information of iron, organic carbon contents and petrographic features, it can be established that sea-level change, supply of terrigenous matters, tectonic background and natures of paleoceanic chemistry have exerted great influence on the distribution of sulfur species in these black shales.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.42272103,92062221,42063009,U1812402)the Guizhou Provincial Science and Technology Projects(Grant No.Qiankehejichu–ZK[2022]common 213)the Higher Education Scientific Research Projects of the Education Department of Guizhou Province(Grant No.Qianjiaoji[2022]157).
文摘A polymetallic layer is usually developed at the bottom of the early Cambrian black shale in Guizhou Province.The mineral that makes up the polymetallic layer is related to the sedimentary facies.To analyze the differentiation mechanism between polymetallic deposits(Ni-Mo and V),the Zhijin Gezhongwu profile located in the outer shelf and the Sansui Haishan V deposit located in the lower slope are selected to study the in situ sulfur isotopes and trace elements of pyrite.The results show that δ^(34)S values of pyrite vary widely from−7.8‰to 28‰in the Gezhongwu profile,while the δ^(34)S values are relatively uniform(from 27.8‰to 38.4‰)in the Haishan profile.The isotopic S composition is consistent with the transition that occurs in the sedimentary phase from the shelf to the deep sea on the transgressive Yangtze platform;this indicates that the δ^(34)SO_(4)^(2−)values in seawater must be differently distributed in depositional environments.The sulfur in the Ni-Mo layer is produced after the mixing of seawater and hydrothermal fluid,while the V layer mainly originates from seawater.Overall,the Ni-Mo and V deposits have been differentiated primarily on the basis of the combined effect of continental weathering and hydrothermal fluid.
基金supported by the Fundamental Research Funds for the Central Universities(No.B200202009).
文摘The Early Cambrian represents a critical time period characterized by extraordinary biological innovations and dynamic redox conditions in seawaters.Nitrogen isotopic signatures of ancient sediments have the potential to elucidate the evolutionary path of marine redox states and the biogeochemical nitrogen cycle within the water column of the Early Cambrian ocean.While existing research on this topic has predominantly focused on South China,the exploration of other continental margins has been limited,leaving contradictory hypotheses untested.In this study,pairedδ^(15)N andδ^(13)C org analyses were performed on the Lower Cambrian successions from the Shiairike section(inner ramp)and Well Tadong 2(deep shelf/basin)in the northwestern and eastern Tarim Basin,respectively.Our data from the Shiairike section reveal a discernible shift in the operation of different nitrogen cycles for the black chert-shale unit,also referred to as the black rock series in Chinese literature,of the Yurtus Formation(Fortunian stage to lower Stage 3).Oscillatingδ^(15)N values for its lower part are suggestive of alternating anaerobic assimilation of NH 4+and denitrification/anammox.This is likely attributed to a shallow,unstable chemocline consistent with the upwelling and incursion of deep,anoxic waters during a major transgression.In contrast,aerobic nitrogen cycling,indicated by positiveδ^(15)N values of>2‰,dominated the upper part alongside a reduction in upwelling intensity.On the other hand,theδ^(15)N signatures of Xishanbulake and Xidashan Formations of Well Tadong 2,which encompass a time interval from the Cambrian Fortunian Age to Age 4,are indicative of N_(2)fixation by diazotrophs as the major nitrogen source.The two studied intervals,although not time-equivalent,exhibit separated states of nitrogen cycling at least during the deposition of the Yurtus black rock series.The spatially different nitrogen cycling of the studied sections is compatible with a redox-stratified ocean during the deposition of the Yurtus black rock series.The build-up of a NO_(3)−reservoir and aerobic nitrogen cycling in seawater was largely restricted to near-shore settings whereas anaerobic nitrogen cycling dominated by N_(2)fixation served as the main nitrogen uptake pathway in off-shore settings.
基金sponsored by the Doctoral Fund of Ministry of Education of China (Grant no.20105201110002)Research Fund of Guizhou Province and Doctoral Programme Fund of Guizhou University
文摘The molybdenum-nickel deposits in Shuidong District of Nayong County (Guizhou Province, Southwest China) are found mainly in black shale series of Lower Cambrian Niutitang Formation, which is another Mo-Ni-rich region besides Zunyi District (Guizhou province). Our systematic study on the Mo-Ni deposits in Tangjiaba of Nayong reveals that layered coarse-grained limestones, spherical beaded limestones concretions are hosted at the lower seam of the Mo-Ni deposits. Its strong negative carbon isotope anomaly (the carbon isotope value of the coarse-grained limestones varies from -2.148‰ to 8.223‰) is similar to that in the modern submarine black smoker chimney. The carbon in the coarse-grained limestones from black rock series of Nayong County might be deep source inorganic carbon. The seams, coarse-grained limestones, ore-bearing coarse-grained limestones and the roof and floor of the deposits are characterized by co-variation on the trace element spider diagram, showing good homology. The extraordinary enrichment of Ag, As and Sb resembles hydrothermal sedimentation. Pro-Earth's core elements Se is strongly enriched in Ni-Mo ore-bearing coarse-grained limestones. The ore-bearing rock series has an extremely low Th/U value (0.012-0.19); in the logU-logTh Cartesian Coordinates, the samples of the roof and floor of the deposits and ore-bearing coarse-grained limestones are found in the East Pacific tise; and the samples of coarse-grained limestones are found between the paleo-hydrothermal dedimentary area and the East Pacific tise. The chondrite-normalized rare earth element patterns of the Ni-Mo deposits show LREE enrichment, Ce negative anomaly, and Eu negative anomaly (which is supposed to be influenced by the deep magmatic processes in an extensional environment) resembles the rare earth element distribution patterns of the fluid and its sediments in modern submarine hydrothermal system. It proves that coarse-grained limestones is characterized by typical hydrothermal limestones, being closely related with the genesis of Mo-Ni deposits in Nayong County, which provides new evidence for hydrothermal sedimentary genesis of Mo-Ni deposit and negative carbon anomaly in the basal Cambrian on a global scale.
基金supported by the National Natural Science Foundation Research (Grant 41672130, 41728004)the National Key S&T Special Projects (Grant 2016ZX05061-003-001)+1 种基金the National Postdoctoral Innovative Talent Support Program (Grant BX201700289)China Postdoctoral Science Foundation (Grant 2017M620296)
文摘Control of various factors, including mineral components, primary productivity and redox level, on the total organic carbon(TOC) in the lower Cambrian black shale from southeastern margin of Upper Yangtze(Taozichong, Longbizui and Yanbei areas) is discussed in detail in this article. Mineral components in the study strata are dominated by quartz and clay minerals. Quartz in the Niutitang Formation is mainly of biogenic origin, and the content is in positive correlation with TOC, while the content of clay minerals is negatively correlated with TOC. Primary productivity, represented by the content of Mobio(biogenic molybdenum), Babio(biogenic barium) and phosphorus, is positively correlated with TOC. The main alkanes in studied samples are nCC, and odd–even priority values are closed to 1(0.73–1.13), which suggest the organic matter source was marine plankton. Element content ratios of U/Th and Ni/Co and compound ratio Pr/Ph indicate dysoxic–anoxic bottom water, with weak positive relative with TOC. In total, three main points can be drawn to explain the relationship between data and the factors affecting organic accumulation:(1) quartz-rich and clay-mineral-poor deep shelf–slope–basin environment was favorable for living organisms;(2) high productivity provided the material foundation for organic generation;(3) the redox conditions impact slightly on the content of organic matter under high productivity and dysoxic–anoxic condition.
基金the National Natural Science Foundation of China (Grant No.41172310, 41472322 and 40872210)the National Basic Research Program of China (Grant No.2014CB238906)the Local Science and Technology Tasks "Distribution Patterns and Prospect of Exploitation and Utilization of Selenium in Foshan area, Guangdong" and "Construction for Laboratory of Selenium Resources Comprehensive Utilization"
文摘The Ediacaran and early Cambrian black shales are widespread across the South China Craton (Yangtze and Cathaysia blocks). However, the trace element distribution patterns of the Ediacaran and early Cambrian black shales in the Cathaysia Block are still unclear. In this study, thirty- four black shale samples in the Lechangxia Group (Ediacaran) and thirteen black shale samples in the lower Bacun Group (early Cambrian) from Guangning area, western Guangdong Province, South China, were analyzed for major and trace elements concentrations. Compared to the upper continental crust, the Ediacaran black shales exhibit strongly enriched Se, Ga, and As with enrichment factor values (EF) higher than 10, significantly enrichedBi and Rb (10〉EF〉5), weakly enriched Mo, Ba, Cs, V, In, Be, TI, and Th (5〉EF〉2), normal U, Cr, Cd, Sc, Pb, Cu, and Li (2〉EF〉0.5), and depleted Ni, Zn, Sr, and Co. Early Cambrian black shales display strongly enriched Se, Ga, and As, significantly enriched Ba, Bi, and Rb, weakly enriched Mo, Cs, Cd, V, U, Be, In, and TI, normal Sc, Th, Cr, Li, Cu, Ni, and Pb and depleted Co, Zn, and Sr. Moreover, Se is the most enriched trace element in the Ediacaran and early Cambrian black shales: concentrations vary from 0.25 to 30.09 ppm and 0.54 to 5.01 ppm, and averaging 4.84 and 1.72 ppm, with average EF values of 96.87 and 34.32, for the Ediacaran and early Cambrian shales respectively. The average concentration of Se in the Ediacaran black shales is 2.8 times higher than that of early Cambrian black shales. Se contents in the Ediacaran and early Cambrian black shales exhibit significant variation (P = 0.03). Provenance analysis showed that Se contents of both the Ediacaran and early Cambrian black shales were without detrital provenance and volcanoclastic sources, hut of hydrothermal origin. The deep sources of Se and the presence of pyrite may explain the higher Se contents in the Ediacaran black shales. Similar with the Se-rich characteristics of the contemporaneous black shales in the south Qingling Mountain and Yangtze block, the Ediacaran and early Cambrian black shales in Guangning area, Cathaysia, are also enriched in Se, which may provide a clue for looking for the selenium-rich resources in western Guangdong Province.
基金This study was financially supported by CAGS(Project No:97-8)China National Petroleum Corporation(Project No:GJ9471908-2)
文摘Abstract: A great amount of black rock series has been found in the Upper Sinian Members 2 and 4 of the Jinjiadong Formation, middle-upper Liuchapo Formation and the Lower Cambrian Xiaoyanxi Formation in West Hunan, which is associated with periodic sea-level changes. By the studies of relationships between the distribution and development of the biota and the abundance of Au, Ag, U, V, Ni, Mo and Cu in the Upper Sinian and Early Cambrian black rock series in Cili, Dayong, Yuanling, Xupu and Qianyang of West Hunan, central China, it has been revealed that the enrichment of Ag, V, and Mo is related with the development of multi-cell plants and vendotaenides, and that of Cu and Ni is related to flourishing of bacteria and shelly fossils. The black rock series in the study area contains abundant organic matter, among which the siliceous shale contains the highest TOC, amounting to 4.51–13.4%. All the values of the equivalent vitrinite reflectance (medium values) determinated with the IR-spectroscopic method in the area are over 2.65%, indicating that the organic evolution was at an overmature stage. Due to the effect of enhancement of organic maturation by hydrothermal fluids, the Upper Sinian and Lower Cambrian had a reverse organic maturity profile in most areas of West Hunan. The enrichment of Ag, V, Ni, Mo and U is a result of organic absorption, and that of Au might be attributed to the migration by hydrothermal fluids.
文摘A silicalite bed was found in the hanging wall and foot wall of the sulfide-rich bed ofthe Lower Cambrian black rock series in South China. Its origin was not described before. Onthe oxide (SiO2-Al2O3, SiO-2-MgO, SiO2-K2O+ Na2O) diagrams for discriminating silicalitesof chemical, biological and volcanic origins (Liu Xiufeng, 1991), most of the data points of silicalites fall within the areas representing silicaIites of chemical and volcanic origins. On the AlFe-Mn diagram for discriminating silicalites of hydrothermal and biological origins (Yamamoto,1987), the data points fall within the areas representing silicalites of hydrothermal and hydrothermal-biological origins. On the SiO2-Al2O3 diagram for discriminating silicalites of hydrothermal and hydrogenous origins (Bonatti, 1975 ), the data points mostly fall within thehydrothermal area. The ratios of SiO2Al2O3, SiO2/(K2O+Na2O), SiO2/MgO, and K2O/Na2O in the silicalites stand between those of volcanic sediments and of sea floor hydrothermalsediments. The total amount of rareuearth elements in the silicalites is low; the North American Shale-normalized REE patterns decline leftward with obvious negative Ce anomaly. Thetrace elements Mo, Zn, As, Sb, Se, U, and Ba are higher than those in non-hydrothermalsediments and U/Th≥1. The present authors think that the silicalites are derived fromseafloor hot brines which had attracted elements from igneous rocks.
基金supported jointly by the National Natural Science Foundation of China(Grant No.40773035)special Research Fund of State Key Laboratory of Ore Deposit Geochemistry,Institute of Geochemistry of Chinese Academa of Sciences
文摘Adsorption experiments were made at room temperature and neutral pH value on different types of min-erals associated with the Lower Cambrian black shale series polymetallic layers in Hunan and Guizhou provinces on nanometer-sized Pt colloids and PtCl42--bearing ionic solutions with an attempt to constrain the relationship between the different types of minerals in the polymetallic layers and the enrichment of platinum group elements (PGEs). Experimental results showed that the different types of minerals show strong selectivity to the adsorption of nano-meter-sized Pt colloids and PtCl42--bearing ionic solutions. Metallic sulfides, organic matter and clay minerals are the strong adsorbents of PGEs, while quartz, albite, muscovite and other silicate minerals show a week adsorbility to both of them. This phenomenon is well consistent with the geological fact that metallic sulfides, organic matter and clay minerals in the polymetallic layers of the black shale series are the major carrier minerals of PGEs, giving a thorough explanation to the mechanism of enrichment of previous metal elements. Adsorption may be a principal mechanism of enrichment of precious metal elements under lower temperature conditions. The presence of the aforementioned strong adsorbents is the good geochemical barriers for the enrichment of PGEs.
基金supported jointly by the National Basic Research Program of China (No. 2007CB411301)Doctoral Fund of Ministry of Education of China (No. 20060284039)
文摘In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platform with a width of ca. 200-400 km and a length of more than 1500 km, we present new paired δ13C data on carbonates (δ13Ccarb) and associated organic carbon (δ13Corg) and δ34Spy data on sedimentary pyrite in black shales from three sections (Ganziping, Shancha and Xiaohekou) located in NW Hunan, China. In these sections, a total of 82 Lower Cambrian black shale samples have δ13Ccarb values ranging from -4.0‰ to 1.7‰ with an average value of -2.1‰, and δ13Corg values between -34.9‰ and -28.8‰, averaging -31.9‰. The ?34Spy values of 16 separated sedi-mentary pyrite samples from the black shales vary between +10.2‰ and +28.7‰ with an average value of +19.5‰, presenting a small isotope fractionation between seawater sulfate and sedimentary sulfide. The model calculation based on credible data from the paired analyses for δ13Ccarb and δ13Corg of 11 black shale samples shows a high CO2 concentration in the Early Cambrian atmosphere, about 20 times higher than pre-industrial revolution values, consis-tent with previous global predictions. The small sulfur isotope fractionation between seawater sulfate and sedimen-tary sulfide in black shales, only 15.5‰ on average, implies a low sulfate level in the Early Cambrian seawater around 1 mmol. In combination with a high degree of pyritization (DOP) in the black shales, it is suggested that sul-fidic deep-ocean water could have lingered up to the earliest Cambrian in this area. The black shale deposition is envisaged in a stratified marine basin, with a surface euphotic and oxygenated water layer and sulfidic deeper water, controlled by a continental margin rift.
基金supported by the "CAS Hundred Talents"Foundation of the Chinese Academy of Sciences to H.Z.,National Natural Science Foundation of China (Grant No.41102066, 40972084)Natural Science Foundation Project of CQ CSTC (Grant No. 2009BB7383)Opening Foundation of the State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences
文摘The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic-lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province (China). All the saturated hydrocarbon fractions have a unimodal distribution of n-alkanes, a high content of short-chain alkanes and maximize at C 19 or C 20 (C 23 for sample Gzh00-1). The C 27 /C 29 sterane ratio ranges from 0.77 to 1.20 and 4-methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values (0.7) suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25-norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ 13 C org excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea-level rise.
文摘Systematic analyses of noble metal elements in the Lower Cambrian black rock series of South China are reported. Correlations of w (Os)/ w (Ir), w (Au)/ w (Ir), w (Ag)/ w (Au), w (Pt+Pd)/ w (Os+Ru+Rh+Ir), relations of noble metal and platinum group element (PGE) distribution patterns reveal that the noble metals are not directly from extraterrestrial materials. Studying the data of 9 aspects, the authors conclude that the noble metals were mainly from ultramafic mafic igneous rocks and their enrichment in black rocks is mainly controlled by hydrothermal fluid.
文摘To explore the genesis of the laminated calcite veins developed in the black shale of Chang 73 submember of the Ordos Basin,the petrology,microstructure and geochemistry of calcite veins are studied using thin sections,fluid inclusions,trace elements and isotopic geochemistry.The source,the time of formation,the mechanism of formation,and the dynamic background of the veins are discussed.The veins are mostly made up of calcite,mixed with lenticular or spindle-shape solid wall rock inclusions.Three structures are identified in the calcite minerals:fibrous,rhombic cleavage,and wedge-like structure.Trace elements and isotopes of carbon and oxygen confirm that the calcite veins were formed from a high density hydrothermal fluid.It is assumed that calcite veins formed prior to wall rock consolidation during the formation of the Qinling Orogenic Belt in the Middle and Late Triassic.The results show that the sedimentary sources of Chang 73 submember were influenced by hydrothermal materials besides terrigenous detritus.The fibrous calcite is different from the fibrous calcite reported in the morphology and mechanism of formation.In this way,the research complements and improves the morphology and the mechanism of formation of fibrous calcite.
基金Supported by the National Science and Technology Major Project(2016ZX05050)Scientific Research and Technology Development Program of the Research Institute of Petroleum Exploration and Development,Petrochina(No.2018YCQ02)。
文摘Based on geochemical analysis results of core samples from the Triassic Chang 7 Member of Well Feng 75 drilled in the northwest margin of Ordos Basin,combined with geological characteristics of this region,the formation environment of the black shale and its control on shale oil enrichment are comprehensively studied.From the Chang 73 to Chang 71 Sub-members,the black shale have organic carbon contents decreasing from 5.70%to 3.55%,hydrogen indexes decreasing from 345 mg/g to 269 mg/g,while the oxygen indexes increasing gradually from 6 mg/g to 29 mg/g,indicating that the sedimentary environment during the depositional period of Chang 72 and Chang 73 Sub-members was anoxic.Biomarkers in the black shale change regu-larly,and have an obvious“inflection point”at the depth of 2753–2777 m in the Chang 73 Sub-member,indicating that the input of terrigenous organic matter increased.However,there is a negative drift about 2%of organic carbon isotopic composition near the“inflection point”,which is in conflict with the results of biomarker compounds.This is because the extreme thermal and anoxic events caused by continental volcanic activity in the ancient Qinling region caused negative drift of carbon isotopic composition of the black shale in the Ordos Basin.The volcanic activity caused rise of temperature,polluted air,extreme weathers,more floods and thus more input of terrigenous organic matter,and gave rise to extremely anoxic environment con-ducive to the preservation of organic matter.Terrigenous organic matter is more conducive to the formation of light oil than aquatic organic matter,so these sections in Yanchang Formation are major“sweet spots”for shale oil enrichment.
基金This work was jointly supported by the Ministry of Science and Technology of China (Grant No. G1999043304) the National Natural Science Foundation of China (Grant No. 40172042) and the Special Foundation for Doctoral Subjects in China (Grant No. 2000
文摘The systematic analyses of trace elements, REEs and PGEs of black shale at the bot-tom of the Lower Cambrian in Tarim Basin have been made for the first time in this work. The basic geochemical features are that some trace elements having something to do with the deep-level fluids are highly enriched, including V, Cr, Ni, Cu, Zn, Ge, As, Sr, Y, Mo, Ag, Cd, Sb, Ba, Pb and U, and the Th/U and Th/Sc ratios decreased compared with those in the same kind of rocks in the crust, that the enriched degrees of LREEs are reduced, Eu and Ce depleted distinctly in the chon-drite-normalized REE patterns, and that the contents of PGEs and Au are increased. These char-acteristics indicate that there were more mafic interior sources in the basin when the black shale was deposited. Generally, the interior sources show an extensional tectonic setting of lithosphere. It can be seen from the change of the characteristics of trace elements, REEs and PGEs along the black shale section that the quantity of interior source from inner earth is gradually increased upwards in the lower part of the section, reaches the peak value as shown by sample No. 4 (XCM7-1), and then decreased, which might indicate the episodic extension of lithosphere in the beginning of the Lower Cambrian.
文摘Zhijin County in Western Guizhou is one of the most important production areas of phosphorites in China. In order to investigate genesis of the phosphorites, their REE compositions were analyzed by using inductively coupled plasma emission mass spectrometry (ICP-MS) method. For comparison, phosphorites from the Lower Cambrian black rock series in Southern China, such as Zunyi in Guizhou and Zhangjiajie in Hunan Province, were also analyzed. The analytical data show that: (1) Xinhua phosphorites possess a quite high and greatly varied total rare earth elements (ΣREE), which varying between 164.23×10-6 and 1395.01×10-6 with average of 642.54×10-6, remarkable differentiation between light (LREE) and heavy rare earth elements (HREE), and the ΣLREE/ΣHREE ratios varying between 5.04 and 6.52. The ΣREE and ΣLREE/ΣHREE ratios of the Zunyi and Zhangjiajie phosphorites are 156.69×10-6~637.41×10-6 with average of 431 75×10-6 and 3.17~6.95 with average of 4.37 respectively; (2) All the phosphorites from Xinhua, Zunyi and Zhangjiajie show remarkable negative Ce anomalies. Besides, the Xinhua phosphorites possess lower δCe, which varying between 0.26 and 0.53 with average of 0.35, while δCe of the Zunyi and Zhangjiajie phosphorites are 0.30~0.66 with average of 0.47, suggesting that all of the phosphorites are typical marine sediments deposited mainly in ancient peri-continental seas, and the depositional position of the Xinhua phosphorite might be deeper; (3) Most phosphorites from Xinhua, Zunyi and Zhangjiajie possess unremarkable positive Eu anomaly, and only a few of samples show obvious ones. The δEu varies between 0.98 and 2.4, suggesting that hot (>200 ℃) and strong reductive hydrothermal fluids might have been involved in genesis of the phosphorites; (4) The Xinhua phosphorite is relatively depleted in HREE, and LaN/NdN and δY of most samples are >1 and >1.5 respectively. Besides, there exists no correlation between δY and δCe, suggesting that the phosphorite was subjected to quite strong weathering and leaching processes, and catagenesis do not greatly modify its REE compositions.
文摘The marine black shale formations of different epochs are widely seen in China. They usually come cul as ore-bearing horizon and contain different ore-forming element. Why are there so many different associated metallic elements in the marine black shale ? Evidence shows that the answer is bio-mineralization. The bio-mineralizahon in the process of formation of metalliferous black shales can be divided intp twp stages. The first stage is the bio-achvities occurring in the surface layer aquatic body of the ocean .The ore-forming elements could be absorbed by only a few species of organisms as a bioconcentrator. The second stage is the biogeochemical process. The anaerobic bacteria decomposed the organic remains and the metal elements were activated, and migrated and combined with organic matter or clay minerals or sulfide. After sediments were buried deeply, the organic matter were cracked by high earth temperature.The metal elements in organic compound were continuously acivated, and migrated to form matamorphic minerals or hydrothermal minerals in original rocks or quartz veins. The biogenetic marks in the black shale are changed or distorted beyond recognition and not easy to be found.
基金the National Natural Science Foundation of China(Grant Nos.49873013 , 40073012).
文摘The shale at the bottom of the Lower Cambrian black series in South China is rich in nonferrous metals, noble metals, rare and dispersed elements and radioactive elements, known as polyelement-rich bed. In order to date and trace the source of the platinum group elements, 6 samples were collected from the Zhongnan region of Guizhou Province, and the Ganzi- ping-Sancha region of Hunan Province. The contents and isotopes of Re and Os were measured. Re and Os are positively correlated with each other and the correlation coefficient between 187Os/188Os and 187Re/188Os is 0.99856. On the 187Os/188Os-187Re/188Os diagram, 6 sample points are well-distributed along the (542±11) Ma fitting isochron in high coincidence and with 0.84±0.12 as the initial 187Os/188Os value. The result displays that the age value of the major mineralization of Re, Os and other platinum group elements is (542±11) Ma, which is identical with the stratigraphical age of the wall rocks; the polyelement beds in Hunan and Guizhou provinces bear high isochroneity; the differences of the forming times of different materials in the polyelement bed of the same area do not surpass the error limit permissible for Re-Os date fitting; there exists no distinct time interval between the formation of the diagenetic veinlets and that of the polyelement bed, or the Re-Os isotope composition has not been distinctly changed by the former process; basaltic crust might be the major source of Re, Os, other platinum group and trace elements in the Lower Cambrian polyelement bed of Hunan and Guizhou provinces.
基金Project supported by the National Natural Science Foundation of China (Grant No. 49472114)the Open Laboratory of Or ganic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences.
文摘Organic matter of the Sinian and early Cambrian black shales on the Yangtze Platform belongs to the light carhon group of isotopes with the δ13C values from - 27% to - 35 %, which are lower than those of the contempomneously deposited carbonates and phosphorites. A carbon isotope-stratified paleooceanographic model caused by upwelling is proposed, which can be used not only to interpret the characteristies of organic carbon isotopic compositions of the black shales, but also to interpret the paleogeographic difference in the organic carbon isotope compositions of various types of sedimentary rocks.
基金supported by the National Natural Science Foundation of China (No. 41302023)the Doctoral Program of Higher Education (Specialized Research Fund) of China (No. 20125121130001)+1 种基金the Science Foundation of Education Department of Sichuan Province (No. 13ZB0190)the Karst Dynamics Laboratory, MLR and GZAR (No. KDL2011-04)
文摘The extensive transgression that occurred on the Yangtze Plate in Early Cambrian led to a massive organic carbon pool in the Niutitang Formation. A black shale core section from 3 251.08 to 3 436.08 m beneath the Earth's surface was studied to estimate the contribution of oxygenic photosynthesis to organic carbon sink fluxes in Early Cambrian Upper Yangtze shallow sea. Results indicate that the oxygenic photosynthesis played the most important role in carbon fixation in Early Cambrian. Organic carbon sink was mainly contributed by photosynthetic microorganisms, e.g., cyanobacteria, algae and archaea. The Niutitang Formation was formed in a deep anoxic marine shelf sedimentary environment at a sedimentation rate of ~0.09±0.03 mm/yr. The initial TOC abundance in Niutitang shale ranged from 0.18% to 7.09%, with an average of 2.15%. In accordance with the sedimentation rate and initial TOC abundance, organic carbon sink fluxes were calculated and found to range from 0.21 to 8.10×10~3 kg/km^2·yr^(-1), especially the organic carbon sink fluxes in depth between 3 385 and 3 470 m range from 3.80 to 8.10×10~3 kg/km^2·yr^(-1), with an average of ~6.03×10~3 kg/km^2·yr^(-1), which is much higher than that of contemporary marine sediments. The organic carbon sink fluxes of Niutitang shale are equal to 0.56 to 21.61×10~3 kg/km^2·yr^(-1) net oxygen emitted into the Early Cambrian ocean and atmosphere, this emitted oxygen may have significantly promoted the oxygen level of the Earth's surface and diversification of metazoans.
基金This project was financially supported by the National Natural Science Foundation of China (Grant No. 49502032). This paper has benefited from anonymous reviewers.
文摘There are different sulfur forms in the black shales from theEarly Cambrian of the Yangtze platform. With its emphasis on pyrite and organosulfur, this paper discusses their distribution and formation. The research shows that sulfur phases take regular variations laterally as well as vertically in the research areas. In western researched profile with high terrigenous supply at the time it formed, there exists a larger amount of pyrite and less organosulfur, and pyrite amount declines while organosulfur content increases upwards along the profile. This black shale profile is characterized by relatively light sulfur isotope composition with evolution trend of becoming heavier both for pyrite and organosulfur from bottom to top along the profile. Opposite situation occurs in eastern profiles which were located farther away from terrigenous land. Here pyrite amount obviously decreases and organic matter has combined more sulfur, although these two kinds of sulfur species take similar trend in content variation along profiles to that for western profile. At the same time more 34S is accumulated in sulfur species of black shale samples from eastern profile, and sulfur isotope composition gradually turns lighter from bottom to top. In combination with other information of iron, organic carbon contents and petrographic features, it can be established that sea-level change, supply of terrigenous matters, tectonic background and natures of paleoceanic chemistry have exerted great influence on the distribution of sulfur species in these black shales.