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.

Geochemistry of Platinum Group and Rare Earth Elements of the Polymetallic Layer in the Lower Cambrian,Weng'an,Guizhou Province

The black shales of the Lower Cambrian Niutitang Formation in Weng＇an, on the Yangtze platform of south China, contain voluminous polymetallic sulfide deposits. A comprehensive geochemical investigation of trace, rare earth, and platinum group elements （PGE） has been undertaken in order to discuss its ore genesis and correlation with the tectono-depositional setting. The ore-bearing layers enrich molybdenum （Mo）, nickel （Ni）, vanadium （V）, lead （Pb）, strontium （Sr）, barium （Ba）, uranium （U）, arsenic （As）, and rare earth elements （REE） in abundance. High uranium/ thorium （U/Th） ratios （U/Th〉I） indicated that mineralization was mainly influenced by the hydrothermal process. The 8U value was above 1.9, showing a reducing sedimentary condition. The REE patterns showed high enrichment in light rare earth elements （LREE） （heavy rare earth elements （HREE） （LREE/HREE=5-17）, slightly negative europium （Eu） and cerium （Ce） anomalies （δEu=0.81- 0.93）, and positive Ce anomalies （δCe=0.76-1.12）. PGE abundance was characterized by the PGE-type distribution patterns, enriching platinum （Pt）, palladium （Pd）, ruthenium （Ru） and osmium （Os）. The Pt/Pd ratio was 0.8, which is close to the ratios of seawater and ultramafic rocks. All of these geochemical features suggest that the mineralization was triggered by hydrothermal activity in an extensional setting in the context of break-up of the Rodinian supercontinent.

Catalytic hydrogenolysis of organosolv lignin: Cleaving C–O bonds over CuMgAlO_(x)-layered porous metal oxide catalysts for oriented monophenols production

To understand the catalytic conversion of lignin into high-value products,lignin depolymerization was performed using a layered polymetallic oxide(CuMgAlO_(x))catalyst.The effects of the conversion temperature,hydrogen pressure,and reaction time were studied,and the ability of CuMgAlO_(x)to break the C–O bond was evaluated.The CuMgAlO_(x)(Mg/Al=3:1)catalyst contained acidic sites and had a relatively homogeneous elemental distribution with a high pore size and specific surface area.Theβ-O-4 was almost completely converted by disassociating the C–O bond,resulting in yields of 14.74%ethylbenzene,47.58%α-methylphenyl ethanol,and 36.43%phenol.The highest yield of lignin-derived monophenols was 85.16%under reaction conditions of 280℃ and 3 Mpa for 4 h.As the reaction progressed,depolymerization and condensation reactions occurred simultaneously.Higher temperatures(>280℃)and pressures(>3 Mpa)tended to produce solid char.This study establishes guidelines for the high-value application of industrial lignin in the catalytic conversion of polymetallic oxides.

New Re-Os Isotopic Constrains on the Formation of the Metalliferous Deposits of the Lower Cambrian Niutitang Formation

The Terreneuvian Epoch（541-521 Ma）is also an important period for metallogenesis in South China, as was represented by the widespread occurrences of Ni-Mo polymetallic layers on the antecedent shallow platform margin and the V-enriched black shales in deeper slope-basin settings. In this study, we have measured Re-Os isochron ages of Ni-Mo polymetallic layers（Songlin, Niuchang, Sancha, Chuanpengwan）, V-rich black shales（Bahuang）, and non-metalliferous black shales（Shuidong） in the basal Niutitang Formation in Guizhou and Hunan province, South China. The Ni-Mo polymetallic layers and V-enriched black shales have similar Re-Os isochron ages, suggesting concurrent deposition of these two types of metalliferous ores. This suggestion is consistent with the traditional stratigraphic correlation by using the nodular phosphorite bed directly underlying these metalliferous layers as a stratigraphic marker. Furthermore, the metalliferous ores and non-metalliferous black shales have similar initial ^（187）Os/^（188） Os ratios of 0.8-0.9, arguing for a dominant seawater origin with minor contribution of hydrothermal activity. Furthermore, Re-Os isotopic data also imply that Ni-Mo and V ore might have derived from the same source. We suggest that the spatial distribution of metalliferous ores can be explained by the development of non-sulfidic anoxic-suboxic wedge（NSASW） in the slope-basin and sulfidic wedge in the previous platform margin. Upwelling of deep water first transects the mildly reduced, organic rich NSASW, in which V（V） is reduced to V（IV）, and is preferentially removed from seawater by organometallic complex formation. As a result, V-rich black shale deposits in the slope-basin of Yangtze Platform. Further movement of deep water into the sulfidic platform margin results in Ni-Mo polymetallic layer formation.

SHRIMP zircon age for a K-bentonite in the top of the Laobao Formation at the Pingyin section,Guizhou,South China

The Lower Cambrian on the Yangtze Platform in South China （internationally equivalent to the Nerreneuvian and 2nd series of the Cambrian） is valuable for understanding the early evolution of life, the global biogeochemical circles, and the major changes of the ocean. In particular, a precise radiometric calibration of the Lower Cambrian of this region is a critical realm in its multidisciplinary studies. A SHRIMP U-Pb geochronology study of the K-bentonite in the topmost Laobao Formation at the Pingyin section, Guizhou, South China yielded an age of 536±5 Ma （MSWD -- 0.75）, suggesting that the K-bentonite here can be correlated with the intensely studied K-bentonite within the middle Zhongyicun Member （Bed 5） of the Zhujiaqing For- mation at the Meishucun section in Yunnan. Such a regional correlation result reveals that the Bed 5 K-bentonite also extends into deeper-water environments rather than being deposited merely in the shallow platform interior of the Yangtze Platform. The age of the K-bentonite at the Pingyin section also implies that its overlying polymetallic Ni-Mo layer should be younger than 536e5 Ma. Hence the previous placement of the Precambrian/Cambrian boundary at this layer is inappropriate. Combined with the results of stratigraphic correlations, it is suggested that the K-bentonites in the middle Zhongyicun Member of the Zhujiaqing Formation （or the equivalents） and the base of the Shiyantou Formation （or its equivalents）, together with the polymetallic Ni-Mo layer, serve as three important marker beds. Their self-consistent radiometric ages have established an im- proved geochronologic framework for the Lower Cambrian in South China.