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.

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.

Diagenetic and Catagenetic Transference of Noble Metal Elements in Lower Cambrian Black Rock Series, Southwest China

Some extraditional types—black rock series types of platinum group element (PGE), gold and silver mineralization occurrences were found in the Lower Cambrian in Guizhou and Hunan provinces of southwest China where PGE concentration reaches more than 800×10 -6. Sea floor hydrothermal fluid eruption was suggested to have been the main origin of the ore-forming materials. The whole process from the sedimentation to the redistribution of the ore-forming elements occurred on the conditions of intermediate to weak alkaline, weak reduction to weak oxidation. The temperature for the sedimentation and redistribution of the ore-forming elements was lower than 210 ℃. At such a low temperature, inert elements such as PGE, Au and Ag could quite easily be remobilized.

The Metallogenetic Processes and Environment of a Large Ag-V Deposit in Black Rock Series

Located in Western Hubei Province,this deposit is a large-scale Ag-V ore deposit,listed among the fifth type of silver deposit in China.1 Geological Characteristics It lies in the NE sector of the Yangtze flat of the Yangtze paraplatform.There are sporadically magmatic rocks and fold basement made up of upper Archaeozoicmiddle and lower Proterozoic strata.The sedimentary cover consists of Sinian-lower Paleozoic marine sediments,Mesozoic-Cenozoic intercalated marine and nonmarine sediments or nonmarine sediments.

Paleo-productivity evolution across the Permian-Triassic boundary and quantitative calculation of primary productivity of black rock series from the Dalong Formation, South China

The change of the primary productivity across the Permian-Triassic boundary （PTB） remains controversial. In this study, records from two deep-water sections in South China （Xiakou and Xinmin sections） show the primary productivity decreased gradually from the latest Permian to the earliest Triassic, and five evolutionary stages Increase-Decrease-Recovery-Recession- Stagnation） can be observed from Clarkina changxingensis-C, deflecta to Hindeodus parvus-lsarcicella isarcica zones. Pri- mary productivity decreased abruptly from the base of C. meishanensis zone. Besides, for adjusting to the deterioration of the oceanic environment, the primary producers in the oceanic surface had changed to acritarch and cyanobacteria, which were more tolerant of stressful environment. Then the producers were under huge stagnation in the H. parvus-L isarcica zone. The values of quantitative calculation of the primary productivity from the black rock series in the Dalong Formation were very high, corresponding to that of an upwelling area in modern ocean, which shows that the strata of the Dalong Formation in the study region are potential hydrocarbon source-rocks. This result may come from the fact that South China craton was located at the equatorial upwelling area during the Permian-Triassic transitions. But organic matter contents were different in various sections because they could be affected by redox conditions and diagenesis process after burial.

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.

Rare Earth Elements Compositions and Genesis of Xinhua Large-Scale Phosphorite Deposit in Western Guizhou, China

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.

Characteristics of Rare Earth and Trace Element Patterns in Bedded Cherts from the Bottom of the Lower Cambrian in the Northern Tarim Basin, Northwest China and Their Genetic Significance

The sedimentary sequence of the Lower Cambrian is a key interval to reveal the early evolution history of the Earth and there occur widespread cherts worldwide. These cherts possibly carry important information to decipher the breakup process of the Rodinia Continent. Black rock series at the bottom of the Lower Cambrian in the Northern Tarim Basin, China, is composed of black shales interbedded with thin-bedded cherts. Ten chert samples were systematically collected from two outcrops at Xiaoerbulak and Sogatbulak, 8.8 and 7.5 m thick respectively. The cherts were crushed, and were analyzed for trace element and rare earth concentrations. Trace elements such as V, Cu, Zn, U, Pb, Ba, Cd, Ag, Mo, As and Sb are highly enriched, and others such as Rb, Zr, Cs, Hf, Ta, W, Tl, Bi and Th are highly depleted in the cherts. These trace element patterns suggest that the cherts may be of deep crustal origin. The low ratios of Th/U and Rb/Sr further suggest that the cherts are of earth interior sources or received hydrothermal input during their deposition. Chondrite- normalized Eu/Eu* value markedly decreases upward in the section from 5.54 at the lowermost to 0.73 at the top, and NASC-normalized Eu/Eu* value decreases from 8.05 to 1.03. The relatively high Eu/Eu* ratio for the cherts from the northern Tarim Basin is most likely due to a hydrothermal input (e.g., Eu/Eu* ~10). The systematic decrease of Eu/Eu* ratio from the bottom to the top of the section reflects that the hydrothermal input is the largest in the lowermost portion of the section and gradually decreases upward. The chondrite-normalized Ce/Ce* ratio ranges from 0.42 to 0.83, with an average of 0.60. North American Shale Composite (NASC)-normalized Ce/Ce* ratio ranges from 0.42 to 0.79, with an average of 0.57. Negative Ce anomalies are distinct. ΣREEs in the cherts generally increase from 10.50 ppm at the bottom to 35.97 ppm at the top of the sampled section. NASC-normalized (La/Lu) N ratio decreases from 2.72 at the bottom to 0.67 at the top. NASC-normalized (La/Ce) N ratio increases from 1.36 at the bottom to 3.13 at the top. These REE patterns are very similar to those for the cherts deposited in the pelagic ocean-basin floor in the Franciscan Complex exposed at Marin Headlands, California (F-MH chert) (Murray et al., 1991). These geochemical signatures are inconsistent with our previous sedimentological data, which suggests a continental shelf setting. Based on multiple lines of evidence including high TOC content in the concomitant black shales, phosphorite at the bottom of black rock series, regional rise of sea level, and beginning of the southern Tianshan Ocean geotectonic cycle, the authors infer that the hydrothermal fluid was carried to the continental shelf by upwelling from a divergent pelagic ocean floor setting.

Discovery of Precambrian thick black mudstones and its implication for hydrocarbon exploration in the southwest Tarim Basin

Due to deep burial of Precambrian in Tarim Basin,no breakthrough in the hydrocarbon exploration has been achieved from these strata,and development of high-quality source rocks is also uncertain.More than 30 exploratory wells have been drilled in the southwest Tarim Basin and the pediment region of Kunlun Mountains with a total area of more than 100
103 km2.Though some marine oil/gas fields such as Hetianhe,Bashituopu,Yubei and Luosi 2 have been discovered,the Cambrian or Ordovician source rocks have not been drilled,and hydrocarbon source still remain controversial.Recently,a set of thick black shales and mudstones has been found in the southwest Tarim Basin.The total thickness of mudstones is more than 140 m,and the total organic carbon mainly ranges from 0.6%to 1.9%with an average of 1.0%.Tmax is from 490C to 520C,equivalent to Ro from 1.99%to 2.99%.Pyrites are very rich in mudstone.According to stratigraphic contact relationship and isotopic chronology,this mudstone may have the age of more than 517 Ma,and is tentatively named as the“Western Kunlun black rock series”.Through the plate tectonic analysis,this set of thick black mudstones is possibly distributed widely in the southwest Tarim Basin,and its formation may be controlled by the aulacogen.This set of black mudstones may be an important source rocks in the southwest Tarim Basin,which suggest that the Precambrian-Cambrian strata in Tarim Basin has geological conditions for hydrocarbon accumulations.This discovery of the black thick mudstones in the southwest Tarim Basin will promote hydrocarbon exploration in the deep and ultra-deep strata of the Tarim Basin.

Discovery of anomalous gallium enriched in stone coal: Significance, provenance and recommendations

Gallium(Ga)is a critical mineral that plays an irreplaceable role in consumer electronics,clean energy technologies and the aerospace industry.Nowadays competition for gallium resources at the national strategic level has begun to emerge,but gallium resources are unevenly distributed globally,and their presence is not guaranteed.New discoveries revealed an average gallium concentration of thirty-one samples from M_(1),M_(2),M_(3) and M_(4) stone coal-bearing seams of the Cambrian strata on South Qinling Orogenic Belt in central China is 157 mg/kg(9.98–747 mg/kg),which is 27.6-fold higher than the global hard coal average,as well as the existing association of Mo–V–U–Cd–Zn–Ba–Se–Mg–Ni–Cu enrichment.Ga average of these coal seams are 344 mg/kg(M_(3),44.5–747 mg/kg,n=11),270 mg/kg(M_(4),14.3–270 mg/kg,n=5),53.8 mg/kg(M_(2),22.6–75.4 mg/kg,n=8)and 19.8 mg/kg(M_(1),9.98–34.9 mg/kg,n=7)respectively,as well as the thickness of approximately 6,12,8,and 20 m,which be close to or exceed to the boundary grade standard(30 mg/kg)and minimum recoverable thickness(0.7 m)of gal-lium resources exploration.These findings indicate that the Cambrian stone coal deposits,especially in the middle and late Cambrian period,should be considered as promising alternative sources of gallium.The anomalous gallium-enriched sediments originated from a complex combination of hydrothermal flu-ids,original biomass and terrigenous materials.For the M_(1) stone coal-bearing seams,gallium most likely occurred in the mode of GaAs,Ga_(x)In_(1-x)As and GaO(OH),while modes of gallium in the M_(2) to M_(4) seams is interrelated with the organic affinity and clay minerals.The crude reserve estimate of gallium resources in central China is approximately 10.06?104 tons,corresponding to a super-large coal-hosted gallium ore deposit.The unique paleogeographic location and geological structure in central China resulted that this newly discovered deposit is a unique type of gallium-enriched deposit that has been discovered worldwide.These discoveries will provide the critical parameters when developing distinctive benefici-ation processes and appropriate extraction procedures,as well as guidance and effective for future prospecting regions of gallium resources around the globe,involving a combination consider the distri-bution of regional deep–large fault zones and the middle to late Cambrian black rock series deposits.