Paleoceanographic Indicators for Early Cambrian Black Shales from the Yangtze Platform, South China: Evidence from Biomarkers and Carbon Isotopes

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.

The Trace Element Distribution Patterns of Ediacaran-Early Cambrian Black Shales and the Origin of Selenium in the Guangning Area, Western Guangdong Province, South China

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.

Sedimentary Environment and Mineralization of the Black Shale Polymetallic Layer in the Early Cambrian,SW China:Constraints from in situ LA-ICP-MS Analysis of Pyrite

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.

Carbon and sulfur isotopic compositions of Early Cambrian black shales, NW Hunan, China: Implications for the Paleoceanographic sedimentary environment

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.

Occurrence modes of silver in the Ni-Mo-PGE polymetallic layer of the Lower Cambrian black shales in Zunyi, Guizhou Province, South China

The Ni-Mo-PGE polymetallic mineralization of the Lower Cambrian black shales locate in Zunyi, South China and contain abundant noble metals such as Ag, Au and PGE, and especially Ag with average concentration of 64×10-6. The occurrence modes of Ag have been investigated using methods of selective chemical dissolution and transmission electron microscopy. The results demonstrate that the occurrence modes of Ag are complex and diversiform. It might be associated with clay minerals, organic matter, sulfides and also occurred as native silver and sulfides with nanometer in size. Combined with results of previous studies, we suggest that the sulfides, clay minerals and organic matter which hosted in the Ni-Mo-PGE polymetallic ores of black shales can play the roles of important reduction and adsorption geochemical barriers for the enrichment and distribution of silver. This study further implies that the selective chemical dissolution and transmission electron microscopy may pave the way to study the occurrence modes of other noble metals in black shales.

Formation,evolution,reconstruction of black shales and their influence on shale oil and gas resource

Black shales are important products of material cycling and energy exchange among the lithosphere,atmosphere,hydrosphere,and biosphere.They are widely distributed throughout geological history and provide essential energy and mineral resources for the development of human society.They also record the evolution process of the earth and improve the understanding of the earth.This review focuses on the diagenesis and formation mechanisms of black shales sedimentation,composition,evolution,and reconstruction,which have had a significant impact on the formation and enrichment of shale oil and gas.In terms of sedimentary environment,black shales can be classified into three types:Marine,terrestrial,and marine-terrestrial transitional facies.The formation processes include mechanisms such as eolian input,hypopycnal flow,gravity-driven and offshore bottom currents.From a geological perspective,the formation of black shales is often closely related to global or regional major geological events.The enrichment of organic matter is generally the result of the interaction and coupling of several factors such as primary productivity,water redox condition,and sedimentation rate.In terms of evolution,black shales have undergone diagenetic evolution of inorganic minerals,thermal evolution of organic matter and hydrocarbon generation,interactions between organic matter and inorganic minerals,and pore evolution.In terms of reconstruction,the effects of fold deformation,uplift and erosion,and fracturing have changed the stress state of black shale reservoirs,thereby having a significant impact on the pore structure.Fluid activity promotes the formation of veins,and have changed the material composition,stress structure,and reservoir properties of black shales.Regarding resource effects,the deposition of black shales is fundamental for shale oil and gas resources,the evolution of black shales promotes the shale oil and gas formation and storage,and the reconstruction of black shales would have caused the heterogeneous distribution of oil and gas in shales.Exploring the formation mechanisms and interactions of black shales at different scales is a key to in-depth research on shale formation and evolution,as well as the key to revealing the mechanism controlling shale oil and gas accumulation.The present records can reveal how these processes worked in geological history,and improve our understanding of the coupling mechanisms among regional geological events,black shales evolution,and shale oil and gas formation and enrichment.

Nitrogen isotope stratigraphy of the Early Cambrian successions in the Tarim Basin:Spatial variability of nitrogen cycling and its implication for paleo-oceanic redox conditions

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.

New Evidence for Hydrothermal Sedimentary Genesis of the Ni-Mo Deposits in Black Rock Series of the Basal Cambrian, Guizhou Province: Discovery of Coarse-Grained Limestones and its Geochemical Characteristics

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.

Controls on the organic carbon content of the lower Cambrian black shale in the southeastern margin of Upper Yangtze

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.

Study of Noble Metal Elements in Lower Cambrian Black Rock Series of Guizhou-Hunan Provinces, China

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.

Gas Occurrence and Accumulation Characteristics of Cambrian–Ordovician Shales in the Tarim Basin, Northwest China

The Tarim Basin is located in northwestern China and is the biggest basin in China with huge oil and gas resources. Especially the Lower to Middle Cambrian and Middle to Upper Ordovician possess the major marine source rocks in the Tarim Basin and have large shale gas resource potential. The Cambrian–Ordovician shales were mainly deposited in basin–slope facies with thicknesses between 30–180 m. For shales buried shallower than 4500 m, there is high organic matter abundance with TOC（total organic carbon） mainly between 1.0% and 6.0%, favorable organic matter of Type I and Type II, and high thermal maturity with RoE as 1.3%–2.75%. The mineral composition of these Cambrian–Ordovician shale samples is mainly quartz and carbonate minerals while the clay minerals content is mostly lower than 30%, because these samples include siliceous and calcareous shale and marlstone. The Cambrian and Ordovician shales are compacted with mean porosity of 4% and 3%, permeability of 0.0003×10^（-3）–0.09×10^（-3） μm^2 and 0.0002×10^（-3）–0.11×10^（-3） μm^2, and density of 2.30 g/m^3 and 2.55 g/m^3, respectively. The pores in the shale samples show good connectivity and are mainly mesopore in size. Different genetic types of pores can be observed such as intercrystal, intergranular, dissolved, organic matter and shrinkage joint. The reservoir bed properties are controlled by mineral composition and diagenesis. The maximum adsorption amount to methane of these shales is 1.15–7.36 cm^3/g, with main affecting factors being organic matter abundance, porosity and thermal maturity. The accumulation characteristics of natural gas within these shales are jointly controlled by sedimentation, diagenesis, hydrocarbon generation conditions, reservoir bed properties and the occurrence process of natural gas. The natural gas underwent short-distance migration and accumulation, in-place accumulation in the early stage, and adjustment and modification in the later stage. Finally, the Yulin（well Y1） and Tazhong（well T1） areas are identified as the targets for shale gas exploration in the Tarim Basin.

Biota and Organic Matter in the Late Sinian and EarlyCambrian Black Rock Series of West Hunan andIts Significance for Metallization

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.

Organic carbon isotopes of the Sinian and Early Cambrian black shales on Yangtze Platform,China

Organic matter of the Sinian and early Cambrian black shales on the Yangtze Platform belongs to the light carbon group of isotopes with the δ13C values from - 27 % to -35 % , which are lower than those of the contemporaneously deposited carbonates and phosphorites. A carbon isotope-stratified paleooceanographic model caused by upwelling is proposed, which can be used not only to interpret the characteristics 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.

Environmental Effects on Differential Organic Matter Enrichment of the Lower Cambrian Shale,Tarim Basin,NW China

Early Cambrian shale is an important petroleum source rock around the world.Because of little drilling data and poor seismic data,until recently,organic matter enrichment of the Lower Cambrian Yuertusi and Xishanbulake formations shale is still an enigma in the Tarim Basin,northwestern China.Total organic carbon(TOC),major and trace element data of Cambrian shale samples from five boreholes have been analyzed to decipher the mechanism of the organic matter enrichment.The results show that the shales deposited in the western restricted intraplatform have much higher TOC contents(3.2%-19.8%,on average 11.0%)than those from the eastern basin(2.2%-10.2%,on average 4.5%).The paleoproductivity proxies(Ba,Ba/Al,P/Al)in the western restricted platform are much higher than those in the eastern basin.The trace element indicators such as V/Cr,Ni/Co,Mo-TOC and Mo_(EF)-U_(EF)suggest an anoxic environment across the basin,but a more restricted environment in the western intraplatform.The paleoproductivity rather than anoxic condition and hydrothermal activity are concluded to have resulted in the differentiation of the organic matter enrichment from the western intraplatform to eastern basin in the early Cambrian shales;the restricted environment was favorable for paleoproductivity and preservation of organic matter.

Burial Records of Reactive Iron in Cretaceous Black Shales and Oceanic Red Beds from Southern Tibet

One of the new directions in the field of Cretaceous research is to elucidate the mechanism of the sedimentary transition from the Cretaceous black shales to oceanic red beds. A chemical sequential extraction method was applied to these two types of rocks from southern Tibet to investigate the burial records of reactive iron. Results indicate that carbonate-associated iron and pyrite are relatively enriched in the black shales, but depleted or absent in red beds. The main feature of the reactive iron in the red beds is relative enrichment of iron oxides （largely hematite）, which occurred during syn-depostion or early diagenesis. The ratio between iron oxides and the total iron indicates an oxygen-enriched environment for red bed deposition. A comparison between the reactive iron burial records and proxies of paleo-productivity suggests that paleo-productivity decreases when the ratio between iron oxides and the total iron increases in the red beds. This phenomenon could imply that the relationship between marine redox and productivity might be one of the reasons for the sedimentary transition from Cretaceous black shale to oceanic red bed deposition.

Response of Reactive Phosphorus Burial to the Sedimentary Transition from Cretaceous Black Shales to Oceanic Red Beds in Southern Tibet

The mechanism of sedimentary transition from the Cretaceous black shales to the oceanic red beds is a new and important direction of Cretaceous research. Chemical sequential extraction is applied to study the burial records of reactive phosphorus in the black shale of the Gyabula Formation and oceanic red beds of the Chuangde Formation, Southern Tibet. Results indicate that the principal reactive phosphorus species is the authigenic and carbonate-associated phosphorus （CAP） in the Gyabula Formation and iron oxides-associated phosphorus （FeP） in the Chuangde Formation which accounts for more than half of their own total phosphorus content. While the authigenic and carbonate-associated phosphorus （CAP） is almost equal in the two Formations; the iron oxidesassociated phosphorus is about 1.6 times higher in the Chuangde Formation than that in the Gyabula Formation resulting in a higher content of the total phosphorus in the Chuangde Formation. According to the observations on the marine phosphorus cyde in Modern Ocean, it is found that preferential burial and regeneration of reactive phosphorus corresponds to highly oxic and reducing conditions, respectively, leading to the different distribution of phosphorus in these two distinct type of marine sediments. It is the redox-sensitive behavior of phosphorus cycle to the different redox conditions in the ocean and the controlling effects of phosphorus to the marine production that stimulate the local sedimentary transition from the Cretaceous black shale to the oceanic red beds.

Accumulation Conditions of Organic Matter during the Deposition of Black Shales of the Buxin Formation (Early Paleogene) in the Sanshui Basin, South China

Analyses of organic carbon, nitrogen, sulfur and iron have been performed in order to understand sources and preservation of organic matter in black shale of the Buxin Formation (Early Paleogene) from the Sanshui Basin. The C/N ratios show that the organic matter is characterized by a mixture of terrestrial and phytoplanktonic contributions. The relative importance of different sources depend on climate conditions and most of organic matter is of terrestrial origin. The relationships between C, S and Fe indicate that the brackish environment with alternation of anoxia and low-O2 developed in the bottom waters during the deposition of these organic-rich sediments as a result of a mixed setting of thermal stratification and salinity stratification, the latter being the consequence of intermittent sea water incursion. Bacterial sulfate reduction is the most effective early diagenesis affecting the preservation of organic matter. The intensity of sulfate reduction is related to the relative proportion of metabolizable organic matter supplied to sediments.

Jurassic Black Shales Facies from Qiangtang Basin (Northern Tibet): Rare Earth and Trace Elements for Paleoceanographic Implications

The Biluo Co and Amdo 114 station, northern Tibet, cropping out the Early Toarcian and Middle-Late Tithonian （Jurassic） organic-rich black shales, have been a focus to petroleum geologists in discussing their oil-producing potential. This paper first reports the trace elements and rare earth elements to discuss the paleoenvironments, redox conditions and sedimentary mechanisms of those black shales. Both sections exhibit variation in trace element abundances with concentrations 〈0.1 ppm to 760 ppm, mostly enriched in V, Cr, Ni, Cu, Zn, Mo, Ba and U. Element ratios of Ni/Co, V/Cr, U/Th and V/（V＋Ni） plus U were used to identify redox conditions. The shale-normalized rare earth element （REE） patterns are characterized by the flat-shale type with instable Ce anomalies and very weekly positive Eu anomalies. Positive Ceanom values are significant with values varying between - 0.064 and 0.029 in Biluo Co, which may be interpreted as release of REE and input of riverine terrestrial matter with rich Ce （resulting in pH change） during the anoxic conditions. In the middle parts of Amdo 114 station, distinct negative Ceanom values are observed （-0.238 to -0.111） and associated surface water warming were interpreted as being related to a major sea level rise. In contrast, the formation of the black shales in the lower and upper part of the studied succession took place during a cooler （Ceanom values 〉-0.10）, lower surface water productivity, and lower sea-level stage. Thus, we emphasize the role of different factors that control the formation of local and regional black shales. The most important factors are sea-level fluctuations and increasing productivity.

Preliminary Estimation of Paleoproductivity via TOC and Habitat Types:Which Method Is More Reliable?—A Case Study on the Ordovician-Silurian Transitional Black Shales of the Upper Yangtze Platform, South China

New total organic carbon （TOC） data from the two Ordovician-Silurian transitional graptolite-bearing black shale intervals, the Wufeng （五峰） Formation and the Longmaxi （龙马溪） Formation in Central Guizhou （贵州） and West Hubei （湖北）, respectively, as well as previously reported TOC data from the same intervals in other places on the Yangtze platform of South China, have been used to produce an initial estimate of the primary paleoproductivity via a conventional inverse method （i.e., Rpp.inverse）. The values of the Rpp.inverse are estimated to be 32 （43-21） gC/（m^2·a）（Wufeng Formation） and 21 （27-16） gC/（m^2·a） （Longmaxi Formation）. Also, simultaneously, the habitat types （i.e., HT; cf., BA： benthic assemblage） and their temporal and spatial changes have been documented from the same succession, and an initial estimate of the primary paleoproductivity has been produced using a forward method （i.e., Rpp-forward） Beingbounded mainly by the peritidal to inner-shelf environment shelly-facies or mixed-facies successions with BA1 to BA3 faunas both at the top and the base, which indicates the habitat types from HT Ⅱ to HT Ⅲ2, the biohabitat type of the two graptolite-bearing black shale intervals can be limited to HT III to HT IV, corresponding to the inner shelf to the outer shelf, with depths from roughly 60 m to 200-300 m. Based on the current data from the South China Sea and the southern part of the East China Sea, values of Rpp-forward should be about 100 to 400 gC/（m^2·a）. The difference in the results via the two methods suggests that paleoproductivity estimates from the geological strata need to be made cautiously, with particular attention paid to the paleogeographic setting, oxic-anoxic conditions, as also the preservation factor of organic carbon.

Simulating experiment on the enrichment of precious metals in Lower Cambrian black shale series of Hunan and Guizhou provinces

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.