2016 Vol. 27, No. 2
Phosphorite nodule beds are discovered in the black shale of basal Niutitang Formation throughout the Yangtze Platform in South China, recording an important phosphorite-generation event. Platform-wide phosphorite precipitation requires special oceanographic and geochemical conditions, thus the origin of the Niutitang phosphorite nodules may provide valuable information about the ocean chemistry in the Early Cambrian. In this study, we measured sulfur and oxygen isotopic compositions of sulfate extracted from phosphorite nodules collected from the basal Niutitang Formation. Phosphorite associated sulfate (PAS) is a trace amount of sulfate that incorporates into crystal lattice during phosphorite precipitation, accordingly PAS records the geochemical signals during phosphorite nodule formation. Sulfur isotopic composition of PAS (δ34SPAS) ranges from -1.16‰ to +24.48‰ (mean=+8.19‰, n=11), and oxygen isotopic value (δ18OPAS) varies between -5.3‰ and +26.3‰ (mean=+7.0‰, n=8). Most phosphorite nodules have low δ34SPAS and low δ18OPAS values, suggesting PAS mainly derived from anaerobic oxidation of H2S within suboxic sediment porewater. We propose that phosphate was delivered to the Yangtze Platform by a series of upwelling events, and was scavenged from seawater with the precipitation of FeOOH. The absorbed phosphate was released into suboxic porewater by the reduction of FeOOH at the oxic-suboxic redox boundary in sediments, and phosphorite nodule precipitated by the reaction of phosphate with Ca2+ diffused from the overlying seawater. The platform-wide deposition of phosphorite nodules in the basal Niutitang Formation implies the bottom water might be suboxic or even oxic, at least sporadically, in Early Cambrian. We speculate that the intensified ocean circulation as evident with frequent occurrences of upwelling events might be the primary reason for the episodic oxidation of the Yangtze Platform in Early Cambrian.
The earliest Cambrian acritarch 'Asteridium-Heliosphaeridium-Comasphaeridium' assemblage and the Early Cambrian ('Chiungchussuan') acritarch 'Skiagia ornate-Fimbriaglomerella membranacea' assemblage in South China can be correlated with assemblages from synchronous strata elsewhere in the world. Recent geochemical study and biomarker evidence further confirm a biostratigraphic change between Cambrian Series 2 and Series 3 and support the recognition of a major geological and biotic event during this time interval.
Hypoxic tolerance experiments may be helpful to constrain the oxygen requirement for animal evolution. Based on literature review, available data demonstrate that fishes are more sensitive to hypoxia than crustaceans and echinoderms, which in turn are more sensitive than annelids, whilst mollusks are the least sensitive. Mortalities occur where O2 concentrations are below 2.0 mg/L, equivalent to saturation with oxygen content about 25% PAL (present atmospheric level). Therefore, the minimal oxygen requirement for maintaining animal diversity since Cambrian is determined as 25% PAL. The traditional view is that a rise in atmospheric oxygen concentrations led to the oxygenation of the ocean, thus triggering the evolution of animals. Geological and geochemical studies suggest a constant increase of the oxygen level and a contraction of anoxic oceans during Ediacaran-Cambrian transition when the world oceans experienced a rapid diversification of metazoan lineages. However, fossil first appearances of animal phyla are obviously asynchronous and episodic, showing a sequence as: basal metazoans>lophotrochozoans>ecdysozoans and deuterostomes. According to hitherto known data of fossil record and hypoxic sensitivity of animals, the appearance sequence of different animals is broadly consistent with their hypoxic sensitivity: animals like molluscs and annelids that are less sensitive to hypoxia appeared earlier, while animals like echinoderms and fishes that are more sensitive to hypoxia came later. Therefore, it is very likely that the appearance order of animals is corresponding to the increasing oxygen level and/or the contraction of anoxic oceans during Ediacaran-Cambrian transition.
Biomineralization may have an extremely long evolutionary history since the Paleoarchean, while the widespread biomineralization among metazoan lineages started at the earliest Cambrian. However, the primary mineralogy of Anabarites shell remains controversial. Optical microscopic observations combined with the Back-Scattered Electron (BSE) and Energy-Dispersive X-ray Spectroscopy (EDS) analyses are used to study the shell of the fossil Anabarites from the Kuanchuanpu fauna in southern Shaanxi Province in China, which is correlated to the Cambrian Fortunian Stage. The EDS analysis shows that the phosphorus-rich layer closely adjacent to the calcified layer exhibits a Ca: P: C ratio compositionally similar to the mineral fluorapatite (Ca5(PO4, CO3)3(F, CO3). The result that the calcified layer and the phosphorus-rich layer have different chemical compositions is consistent with the optical observation that there is an obvious gap between these two layers and the phosphorus-rich layer can extend to the phosphatic material inside of the tube, suggesting the phosphorus-rich layer doesn't belong to the original shell. We suggest that the phosphorous-rich layer is diagenetic in origin, precipitated as a result of phosphorus release during the decay of organic matter by microbes. Considering the outermost shell layer (OMS, biologically controlled carbonate shell layer) should display different isotopic information from the carbonate matrix (i.e., OMS is 12C concentrated due to the biogenic organic matter template is readily rich in 12C), NanoSIMS was used to map ion distributions of C and N in the shell of Anabarites and matrix. However, ion images show that the concentration differences of 12C, 13C and 26CN among the OMS and the matrix are unclear, while 12C and 26CN are supposed to be enriched in the OMS. Therefore, the minor isotopic differences between the shell and the matrix is hard to be detected by NanoSIMS, at least in our sample, probably due to alteration of the 12C-rich characteristic of the Anabarites OMS during the late diagenesis.
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.
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 8.10×103 kg/km2·yr-1, especially the organic carbon sink fluxes in depth between 3 385 and 3 470 m range from 3.80 to 8.10×103 kg/km2·yr-1, with an average of ~6.03×103 kg/km2·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 21.61×103 kg/km2·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.
The Dajiangbian Formation in South China is a siliciclastic-dominated sedimentary succession with low-grade metamorphism deposited on the western margin of the Cathaysia Block, and is capped by a glaciogenic diamictite (the Sizhoushan Formation). The Sizhoushan glaciogenic strata can be attributed to the Jiangkou glacial (Sturtian glacial) episode as they share stratigraphic and lithological similarities with Jiangkou strata in South China. Some carbonate, chert and shale units throughout the upper part of the Dajiangbian Formation were sampled for carbonate carbon isotope (δ13Ccarb) and organic carbon isotope (δ13Corg) analyses. A range of geochemical indices including oxygen isotopes (δ18O) and Mn/Sr (Fe/Sr) ratios suggest that primary carbon isotope values were preserved in the upper Dajiangbian Formation. The upper Dajiangbian Formation shows δ13Ccarb of -0.1‰, upward decreasing towards to -5.4‰. We suggest that the negative δ13C excursion beneath the Sizhoushan diamictite is correlative with the Pre-Sturtian Islay δ13Ccarb anomaly and allows correlation with the global Neoproterozoic isotope stratigraphy. We find that carbonate and organic carbon isotope data of the upper Dajiangbian Formation are coupled, consistent with the δ13Ccarb-δ13Corg pattern observed on multiple continents.
Cryogenian Datangpo Formation was deposited during the interglacial time between the Sturtian and Marinoan ice ages. We studied nitrogen isotope compositions and contents of Mo of the black shales from the basal Datangpo Formation in northeastern Guizhou, South China, for an attempt to reconstruct the marine redox change and nitrogen cycle during the interglacial time. Based on lithostratigraphy as well as geochemical profiles, the basal black shales can be divided into four intervals: Interval 1 has the lowest δ15N value (+5.0‰); in interval 2, δ15N values vary between +6.4‰ and +7.4‰ (the first peak); interval 3 records stable values of δ15N around +6‰; and interval 4 is characterized by its higher δ15N values, between +6.7‰ and +7.8‰ (the second peak). The values of enrichment factor of Mo decrease from 56.8 to 2.6 with the ascending stratigraphic trend. It indicated that immediately after the Sturtian glaciations, the marine seawater above the transitional zone between the shelf to slope of the southern margin of the Yangtze Platform was stratified, with shallow seawater being oxic but deep water being sulfidic. Subsequently, high denitrification rates prevailed in expanded suboxic areas in spite of a short emergence of an oxic condition in the surface seawater, and the deep seawaters were still anoxic or even euxinic.
Global occurrences of Steptoean Positive Carbon Isotope Excursion (SPICE) during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon (δ13C) and organic carbon (δ13Corg) isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate (CAS, δ34SCAS) and pyrite (δ34Spyrite), unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰ increase in δ13Ccarb of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions in δ34SCAS and δ34Spyrite have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound (VOSC, such as methanethiol and dimethyl sulfide) formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of 32S from continental margins to open oceans, elevating δ34S of seawater sulfate in continental margins. A simple box model indicates that about 35% to 75% of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.
Well-exposed Lijiatuo Section was chosen to explore the temporal evolution and controls of the oceanic redox state, primary productivity and seawater sulfate levels during the Cambrian Series 1-2, South China. This section consists of Xiaoyanxi Formation (Fm.) mudstones and Liuchapo Fm. cherts that deposited in the slope and basin environment. Five oxic-anoxic cycles were identified based on V/Sc, Th/U and the enrichment factors of Mo, U, V, Ni and Cu. The Middle-Upper Liuchapo Fm. and the Middle Xiaoyanxi Fm. were deposited under oxic-suboxic conditions, and the rest of the strata were under anoxic conditions. The Re/Mo ratio demonstrated that the oxic-suboxic conditions in the Middle Xiaoyanxi Fm. were accompanied by transient sulfidic conditions, and the rest of the section was underanoxic and non-sulfidic conditions. All the TOC and the enrichment factors of Ba, Ni, Cu, Zn and Cd demonstrated that both the sinking and burial flux of organic matter (OM) in Liuchapo Fm. were lower than that in the overlying Xiaoyanxi Fm. The highest sinking and burial flux of OM in the Xiaoyanxi Fm. appeared at its lower parts; however, the lowest sinking and burial flux of OM in the Xiaoyanxi Fm. appeared in its middle parts. TOC/TS, TS and the vertical trend of δ34Spy demonstrated that the seawater was dominated by low oceanic sulfate levels, which resulted in the absence of free H2S. The rise of the atmospheric oxygen content may be the principal driver for the associated, transient suboxic-oxic and nearly sulfidic environment in the middle Xiaoyanxi Fm.
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 187Os/188Os 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.
It is generally considered that a significant change in oceanic redox conditions occurred during the Ediacaran-Cambrian transition. However, there are currently two major conflicting views on the degree of oxygenation of deep water (oxic vs. ferruginous) during this interval. To date, the oxygenation conditions of the Early Cambrian ocean have not been well constrained. The oxygenation magnitude and mechanism of the Early Cambrian ocean could be critical to the significant biological evolution of the "Cambrian Explosion". To constrain the Early Cambrian oceanic redox environment, we conducted an integrated study on iron and sulfur isotopes and redox-sensitive elements (Mo, U, and V) of Lower Cambrian phosphorite deposits from two shallow sections (Meishucun and Gezhongwu) and a deeper water section (Zunyi) from the Yangtze Platform, South China. The near zero δ56Fe values from the two shallow sections studied here reflect oxic conditions in the lower phosphorite deposition. An obvious positive shift in δ56Fe and redox-sensitive element content was observed in the middle parts of the two shallow water sections, which might reflect loss of light iron by dissimilatory iron reduction during early diagenesis under suboxic shallow water in the platform. However, the highly positive δ56Fe values in the deep section could reflect a lower oxidation degree of dissolved Fe(Ⅱ) under anoxic deep water. The data suggest redox-stratified oceanic conditions during the Early Cambrian, in which completely oxygenated shallow water (platform) coexisted with anoxic deep water (slope). We propose that prolonged upwelling of dissolved organic carbon (DOC)-, Fe(Ⅱ)- and phosphorus-rich anoxic deep water in a redox-stratified ocean could have increased exchange with the open ocean, resulting in major phosphorite deposition in oxic-suboxic conditions. The progressive oxygenation of the ocean may have facilitated the Early Cambrian biotic diversification.
The Lomagundi-Jatuli Event (LJE) is one of the largest and earliest positive carbon isotope excursions preserving δ13Ccarb values between +5 and +16‰ in Paleoproterozoic carbonates worldwide. However, the duration, amplitude and patterns of these excursions remain poorly constrained. The 2.14-1.83 Ga Hutuo Group in the North China Craton is a > 10 km thick volcano-sedimentary sequence, including > 5 km thick well-preserved carbonates that were deposited in supra-tidal to sub-tidal environments. C-O isotopic and elemental analyses of 152 least altered samples of the carbonates revealed a three-stage δ13C evolution. It began with an exclusively positive δ13Ccarb (+1.3 to + 3.4‰) stage in the ~2.1 Ga carbonate in the Dashiling and Qingshicun Formations, followed by a transition from positive values to oscillating positive and negative values in ~3 000 m thick carbonates of the Wenshan, Hebiancun, Jianancun, and Daguandong Formations, and end with exclusively negative δ13Ccarb values preserved in > 500 m thick dolostones of the Huaiyincun and Beidaxing Formations. It appears that much of the LJE, particularly those extremely positive δ13Ccarb signals, was not recorded in the Hutuo carbonates. The exclusively positive δ13Ccarb values (+1.3 to + 3.4‰) preserved in the lower formations likely correspond to the end of the LJE, whereas the subsequent two stages reflect the aftermath of the LJE and the onset of Shunga-Francevillian event (SFE). The present data point to an increased influence of oxygen on the carbon cycle from the Doucun to the Dongye Subgroups and demonstrate that the termination of the LJE in the North China Craton is nearly simultaneous with those in Fennoscandia and South Africa.
Three positive carbon isotope excursions are reported from Middle–Upper Ordovician in Tahe oil-gas field, northern Tarim Basin. Based on conodont biostratigraphy, the Middle Darriwilian Isotope Carbon Excursion (MDICE) and the Guttenberg Carbon Isotope Excursion (GICE) are identified from Darriwilian to Early Katian by the aid of whole-rock carbon isotope data from two well cores. Positive excursion within conodont Pygodus anserinus zone is developed in Early Sandbian, and the fluctuation range is no less than MDICE. Because the range of this excursion in the generalized global carbon isotope curve is short, previous studies paid little attention to it, and named Early Sandbian Isotope Carbon Excursion (ESICE) in this paper. Furthermore, these positive excursions are not directly related to sea level fluctuations and the MDICE and GICE identified in northern Tarim can be globally correlated to that in southern China, North America, South America, and Europe. The Saergan Fm. source rocks of Middle-Upper Ordovician in Kalpin Dawangou outcrop are in accord with the geologic time of MDICE and ESICE, and GICE have strong ties to the source rock of Lianglitag Fm. in basin. Abundant organic carbon burial is an important factor in genesis of positive isotope carbon excursions. Positive oxygen isotope excursion, conodont fauna turnover, decreased conodont total diversity, and the change of sedimentary facies indicated that dramatic changes of paleoceanographic environment of Early-Middle Ordovician in Tarim Basin started from the end of Darriwillian, and an obvious icehouse climate of Late Ordovician occurred in ESICE.