Jing-Hong Yang

Early Cambrian ocean anoxia in South China

Arising from: M. Wille, T. F. Nägler, B. Lehmann, S. Schröder & J. D. Kramers 453, 767–769 (2008)10.1038/nature07072; Wille et al. replyThe cause of the most marked changes in the evolution of life, which define the first-order stratigraphic boundary between the Precambrian and the Phanerozoic eon, remains enigmatic and a highly topical subject of debate. A global ocean anoxic event, triggered by large-scale hydrogen sulphide (H2S) release to surface waters, has been suggested by Wille et al., on the basis of two data sets from South China and Oman, to explain the fundamental biological changes across the Precambrian/Cambrian (PC/C) boundary. Here we report a new precise SHRIMP U–Pb zircon age of 532.3 ± 0.7 million years (Myr) ago (Fig. 1) for a volcanic ash bed in the critical unit that reflects the ocean anoxic event, the lowermost black shale sequence of the Niutitang Formation in the Guizhou Province, South China. This age is significantly younger than the precise PC/C boundary age of 542.0 ± 0.3 Myr ago, approximately 10 Myr younger than the extinction of the Ediacaran fauna, and thus challenging the view of a major ocean anoxic event having been responsible for the major changes in the direction of evolution at the PC/C boundary.

Re-Os isotopes and PGE geochemistry of black shales and intercalated Ni-Mo polymetallic sulfide bed from the Lower Cambrian Niutitang Formation, South China

The Lower Cambrian Niutitang Formation consists of a thick black shale sequence with a regionally distributed conformable Ni Mo polymetallic sulfide horizon and a chert bed at its basal strata on theYangtze Platform, South China. In this paper, we discuss all available data on Re Os isotopes and Platinum Group Element (PGE) distribution pattern of the Ni Mo polymetallic sulfide ore and its host rocks (black shales, cherts, and phosphorites) from Guizhou and Hunan provinces. Our results show that the black shales and the Ni Mo sulfide ore have a high initial 187 Os/ 188 Os ratio of 0.78～0.86, indicating that the Early Cambrian ocean across the Yangtze Platform had a highly radiogenic Os value. This ratio is slightly lower than but still similar to present day seawater, possibly as a result of high continental weathering at that time. The Ni Mo sulfide ore yields a Re Os isochron of 537±10 Ma (MSWD=11.9), possibly representing the depositional age of the Niutitang Formation. The chondrite normalized PGE pattern, Pt anomaly (Pt/Pt *), Pt/Pd, Ir/Pd, Au/Ir and Re/Mo ratios of the Ni Mo sulfide ore and its host rocks from South China indicate a varying source contribution of the PGE and other metals for different rocks. It is suggested that the cherts and Ni Mo sulfide ore may have a significant proportion of PGE and probably other metals deriving from submarine hydrothermal fluids with a mantle signature.

Paleoceangraphic significance of redox-sensitive metals of black shales in the basal Lower Cambrian Niutitang Formation in Guizhou Province, South China

Abstract Black shales of the Lower Cambrian Niutitang Formation occurwidely on the Yangtze Platform. In this study, we analyzed black shales from two sections (Zhongnan and Zhijin) in Guizhou Province. The redox-sensitive metal concentration and distribution of black shales from the two sections provide good evidence for the anoxic conditions of the basal Cambrian ocean on the Yangtze Platform. Our geochemical data suggest that the black shales from the Zhongnan section may have deposited in a more strongly anoxic environment than the black shales in the Zhijin section.

An improved procedure for separation/purification of boron from complex matrices and high-precision measurement of boron isotopes by positive thermal ionization and multicollector inductively coupled plasma mass spectrometry

In order to eliminate boron loss and potential isotopic fractionation during chemical pretreatment of natural samples with complex matrices, a three-column ion-exchange separation/purification procedure has been modified, which ensures more than 98% recovery of boron from each step for a wide range of sample matrices, and is applicable for boron isotope analysis by both TIMS and MC-ICP-MS. The PTIMS-Cs2BO2(+)-static double collection method was developed, ensuring simultaneous collection of (133)Cs2(11)B(16)O2(+)(m/z 309) and (133)Cs2(10)B(16)O2(+) (m/z 308) ions in adjacent H3-H4 Faraday cups with typical zoom optics parameters (Focus Quad: 15 V, Dispersion Quad: -85 V). The external reproducibilities of the measured (11)B/(10)B ratios of the NIST 951 boron standard solutions of 1000 ng, 100 ng and 10 ng of boron by PTIMS method are ±0.06‰, ±0.16‰ and ±0.25‰, respectively, which indicates excellent precision can be achieved for boron isotope measurement at nanogram level boron in natural samples. An on-peak zero blank correction procedure was employed to correct the residual boron signals effect in MC-ICP-MS, which gives consistent δ(11)B values with a mean of 39.66±0.35‰ for seawater in the whole range of boron content from 5 ppb to 200 ppb, ensuring accurate boron isotope analysis in few ppb boron. With the improved protocol, consistent results between TIMS and MC-ICP-MS data were obtained in typical geological materials within a wide span of δ(11)B values ranging from -25‰ to +40‰.

Pb-Pb isotope dating of black shales from the Lower Cambrian Niutitang Formation, Guizhou Province, South China

Abstract The Lower Cambrian black shales of the Niutitang Formation and their lateral equivalents occur widely on the Yangtze Platform. South China. In this study, we examine two sections of the Niutitang Formation in Guizhou Province. We employ a stepwise acid-leaching technique to obtain Pb-isotope compositions of the black shales. At the Zhongnan section, the black shales display large Pb isotope variations, with 206Pb/204Pb of 20.5396–33.5709, and 207Pb/204Pb of 15.8407–16.5782. In contrast, Pb isotope data show a relatively limited range in 206Pb/204Pb (18.2797–18.5972) and 207Pb/204Pb (15.6813–15.7159) at the Zhijin section. Data for all acid-leached black shale samples from the two sections yield a Pb-Pb isochron age of 531 ± 24 Ma. This age may represent the sedimentary age of the black shales. The initial Pb-isotope composition of the black shales fallsnear the upper-crust evolution curve in a Zartman Pb-Pb evolution diagram. Hence, it is likely that the Pb in the black shales may have been deriv...

Rare earth element geochemistry of phosphatic rocks in Neoproterozoic Ediacaran Doushantuo Formation in Hushan Section from the Yangtze Gorges Area, South China

Phosphatic rocks are widely distributed in Neoproterozoic Ediacaran Doushantuo Formation in Yangtze Gorges Area, South China. In this study, rare earth element geochemistry of eight phosphatic rock samples from the Hushan Section has been studied. All the samples display typical hat-shaped REE patterns, moderate negative Ce anomalies (Ce/Ce*=0.55 to 0.67), slightly positive Eu anomalies (Eu/Eu*=1.05 to 1.22) and low Y/Ho ratios (38.2±5.6). The hat-shaped REE patterns indicate diagenetic alteration of the primary REE signatures, which coincides with detrital siliciclastic sources of REE based on the Y/Ho ratios. The degree of Negative Ce anomalies and positive Eu anomalies may have recorded the redox features of diagenetic fluids, suggesting an anoxic environment during the phosphogenesis processes in Neoproterozoic Ediacaran Doushantuo Formation, South China. The geochemical comparison between the Lower Phosphorite Layer and Upper Phosphorite Layer at Hushan indicates a greater degree of diagenesis occurred in the Upper Layer than the Lower one. Besides the terrigenous sources of REE, organic materials could have also played a role on the REE characteristics.

Improvements on high-precision measurement of bromine isotope ratios by multicollector inductively coupled plasma mass spectrometry.

A new, feasible procedure for high-precision bromine isotope analysis using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is described. With a combination of HR mass resolution mode and accurate optimization of the Zoom Optics parameters (Focus Quad: -1.30; Zoom Quad: 0.00), the challenging problem of the isobaric interferences ((40)Ar(38)ArH(+) and (40)Ar(40)ArH(+)) in the measurement of bromine isotopes ((79)Br(+), (81)Br(+)) has been effectively solved. The external reproducibility of the measured (81)Br/(79)Br ratios in the selected standard reference materials ranged from ±0.03‰ to ±0.14‰, which is superior to or equivalent to the best results from previous contributions. The effect of counter cations on the Br(+) signal intensity and the instrumental-induced mass bias was evaluated as the loss of HBr aerosol in nebulizer and potential diffusive isotope fractionations.

δ13Ccarb and Ceanom excursions in the post-glacial Neoproterozoic and Early Cambrian interval in Guizhou, South China

Abstract Secular δ13Ccarb and Ceanom profiles in the post-glacial Neoproterozoic and Early Cambrian interval are reported from Guizhou on the southeasten border of the Yangtze platform. South China. Overall, the δ13Ccarb profile drifts to negative values in the postglacial Nantuo and lower to middle Doushantuo Formations, and then to positive values in the upper Doushantuo and Dengying Formations of Neoproterozoic, followed by negative values in the Lower Cambrian Gezhongwu and Niutitang Formations. A detailed investigation of the relationship between the δ 13Ccarb and Ceanom profiles reveals that the main anoxic and oxic episodes are coupled with negative and positive δ 13Ccarbvalues, respectively. This may suggest a control of alternation between ocean stratification and mixing on variations in 13C abundance in the ancient ocean of the investigated areas.

Effect of metasilicate matrices on boron purification by Amberlite IRA 743 boron specific resin and isotope analysis by MC-ICP-MS

The selective adsorption of metasilicate species by N-methyl D-glucamine functional groups in Amberlite IRA 743 resin was observed, which is clarified as the formation of sugar-metasilicate complexes and possible physical adsorptions. The existence of metasilicate matrices causes obvious discrepancies in the δ11B values of silicate materials. It opens the possibility for exploring relevant procedures for the separation/purification of silicon from geological samples.

Emission mechanism of polyatomic ions Cs2Cl+ and Cs2BO2(+) in thermal ionization mass spectrometry with various carbon materials.

The emission behavior of polyatomic ions Cs(2)Cl(+) and Cs(2)BO(2)(+) in the presence of various carbon materials (Graphite, Carbon, SWNTs, and Fullerenes) in the ionization source of thermal ionization mass spectrometry (TIMS) has been investigated. The emission capacity of various carbon materials are remarkably different as evidenced by the obvious discrepancy in signal intensity of polyatomic ions and accuracy/precision of boron and chlorine isotopic composition determined using Cs(2)Cl(+)-graphite-PTIMS/Cs(2)BO(2)(+)-graphite-PTIMS methods. Combined with morphology and microstructure properties of four selected carbon materials, it could be concluded that the emission behavior of the polyatomic ions strongly depends on the microstructure of the carbon materials used. A surface-induced collision mechanism for formation of such kinds of polyatomic ions in the ionization source of TIMS has been proposed based on the optimized configuration of Cs(2)BO(2)(+) and Cs(2)Cl(+) ions in the gas phase using a molecular dynamics method. The combination of the geometry of the selected carbon materials with the configuration of two polyatomic ions explains the structure effect of carbon materials on the emission behavior of polyatomic ions, where graphite samples with perfect parallels and equidistant layers ensure the capacity of emission to the maximum extent, and fullerenes worsen the emission of polyatomic ions by blocking their pathway.