Doushantuo Formation In South China Research Articles

A New Negative Carbon Isotope Interval Caused by Manganese Redox Cycling After the Shuram Excursion

AbstractSeveral negative C isotope excursions (CIEs) occurred at the end of the Neoproterozoic era which have been generally attributed to the oxidation of organic carbon using sulfate as the terminal electron acceptor and the subsequent release of 13C‐depleted dissolved inorganic C (DIC). Based on new analyses from the Doushantuo Formation in South China, we observe a negative C isotope excursion right after the well‐known Shuram excursion. This excursion is equivalent to the ∼550 Ma negative CIE which is globally expressed within several continental margins. However, the origins of this CIE in the termination of Ediacaran remain unresolved. Here, we hypothesize that this post‐Shuram negative CIE was caused by a localized manganese cycling that began with the oxidation of hydrothermal Mn(II) in a water column to insoluble Mn(IV)‐oxide, followed by accumulation of Mn(IV)‐oxide to the seafloor and its subsequent dissolution via Mn(IV) reduction leading to the release of dissolved Mn(II) and 13C‐depleted DIC into ambient seawaters. This ultimately led to the precipitation of particulate Mn(II)‐carbonate characterized by low δ13Ccarb values ranging from −11.1‰ to −2.8‰. The presence of microbial fabrics in association with the Mn(II)‐carbonate further suggests that Mn(II)‐carbonate precipitation took place at the seafloor in shallow sun‐lit waters rather than in the deeper sediment pile, which archived ambient seawater C isotopic signal. Although most Ediacaran negative CIEs were generally attributed to sulfate reduction, our findings suggest that at a local level, Mn cycling can also lead to negative CIE in the Neoproterozoic, and potentially at other times in Earth's history.

Recurrent photic zone euxinia limited ocean oxygenation and animal evolution during the Ediacaran

The Ediacaran Period (~635–539 Ma) is marked by the emergence and diversification of complex metazoans linked to ocean redox changes, but the processes and mechanism of the redox evolution in the Ediacaran ocean are intensely debated. Here we use mercury isotope compositions from multiple black shale sections of the Doushantuo Formation in South China to reconstruct Ediacaran oceanic redox conditions. Mercury isotopes show compelling evidence for recurrent and spatially dynamic photic zone euxinia (PZE) on the continental margin of South China during time intervals coincident with previously identified ocean oxygenation events. We suggest that PZE was driven by increased availability of sulfate and nutrients from a transiently oxygenated ocean, but PZE may have also initiated negative feedbacks that inhibited oxygen production by promoting anoxygenic photosynthesis and limiting the habitable space for eukaryotes, hence abating the long-term rise of oxygen and restricting the Ediacaran expansion of macroscopic oxygen-demanding animals.

Distinct REY sources recorded in the Doushantuo phosphorite

During the Ediacaran period, massive marine phosphorites were deposited worldwide, which could represent a global sink of rare earth elements and yttrium (REY) in oceans. In the Doushantuo Formation of South China, the REY source has been preliminarily constrained as the mixed sources of seawater and terrigenous matter in these phosphorites. However, the REY composition of both seawater and terrigenous endmembers is still unclear; therefore, it’s difficult to identify the contributions of seawater and terrigenous sourced REY. In this work, REY and other trace elements of bulk phosphorites, in situ carbonates, and apatite grains were analyzed from a drill core (Fangmashan) of the Doushantuo Formation in South China. Combined with mineralogical observations, the REY composition of seawater and terrigenous endmembers is well-constrained. Along the investigated Fangmashan drill core, all in situ carbonates (calcites and dolomites) show a modern seawater-like REY pattern, indicating that the REY characteristics of the Doushantuo seawater could be similar to those of modern oxic seawater without significant changes. Alternatively, apatites from the lower and upper phosphorites showed distinct REY patterns. One type of apatite in the upper phosphorites showed a modern seawater-like REY pattern, indicating authigenic REE enrichment from the seawater column. However, another type of apatite in the upper phosphorites with an REE pattern that deviated from seawater showed high ΣREY (∼691.16 ± 309.78) and low Y/Ho (∼40.52 ± 4.05), probably reflecting mixed REY sources and/or the effects of early diagenesis. It is noted that most apatites in the lower phosphorites are obviously enriched in light REY (LREY: La - Nd) compared to heavy REY (HREY: Ho - Lu and Y), which may represent a significant contribution of the terrestrial REY source. This study reveals that the REY composition of paleo-seawater could be similar to modern seawater as early as the Neoproterozoic and supports a significant contribution to understanding the difference in the REY composition of phosphorites in geological history.

Authigenic clay mineral evidence for restricted, evaporitic conditions during the emergence of the Ediacaran Doushantuo Biota

The Ediacaran Period witnessed major environmental change and an expansion of eukaryotic life following the Marinoan glaciation. The Doushantuo Formation of south China has furnished much of our understanding of Earth System and biosphere evolution during this period, but its depositional setting–marine or non-marine–is still debated. Here we conduct mineralogical, petrographic and geochemical analyses of samples from the lower Doushantuo Formation in order to determine the origin of saponite clay minerals which are abundant in this interval. We find that the morphology and distribution of the saponite clays suggest they are of pre-compaction, authigenic origin. We infer that the lower Doushantuo sediments were deposited in a restricted, mildly evaporitic lagoonal basin, offering additional constraints on the environmental setting into which metazoan life emerged. Further, our findings confirm that Ediacaran seawater favored reverse weathering, with marine clay formation likely representing an important sink for various elements during the Precambrian.

An authigenic response to Ediacaran surface oxidation: Remarkable micron-scale isotopic heterogeneity revealed by SIMS

The Ediacaran Shuram excursion (SE) records a global decrease in carbonate carbon isotope (δ13Ccarb) values from +6‰ down to ca. –10‰, representing the largest δ13Ccarb negative anomaly in Earth history. While the SE is widely recorded in the upper Doushantuo Formation of South China, it shows highly variable δ13Ccarb profiles among correlative sections. This inconsistent expression of the SE challenges the conventional view of a homogeneous marine dissolved inorganic carbon (DIC) reservoir. A potential process that could explain δ13Ccarb variability is local mineralization of isotopically distinct authigenic carbonates near the sediment–water interface during early diagenesis. However, a direct test of such authigenic carbonates is still limited. Here, following a recent study on the SE in an intra-shelf environment, we revisited an outer-shelf section, identified and analyzed μm-scale, syn-depositional authigenic calcite cements via integrated cathodoluminescence (CL), micro-X-ray fluorescence (μXRF), scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), and secondary ion mass spectrometry (SIMS). Our new SIMS results reveal remarkable micron-scale heterogeneity of δ13Ccarb in authigenic calcite cements, including extremely negative values down to –37.5‰ (VPDB). We interpret these calcite cements as methane-derived authigenic calcite (MDAC) resulting from microbial sulfate reduction (MSR) and anaerobic oxidation of methane (AOM) during early diagenesis. Based on the new results, we propose that the heterogeneous SE in South China — manifest on micrometer, centimeter, and basinal scales — was modulated by methane oxidation under variable local redox and water depth conditions. The SE, therefore, was coupled with different degrees of methane oxidation in individual basins, and globally triggered by enhanced seawater sulfate during an atmospheric oxygenation event. In light of this study, the potential role of redox variability in methane oxidation during the SE may have been underestimated. Our study demonstrates that integrated SIMS-SEM analysis can distinguish different generations of isotopically distinct carbonates otherwise undetected by conventional analysis, and is thus an effective approach to assess the origin and diagenetic history of δ13Ccarb anomalies in the sedimentary record.

A microfossil assemblage from the Ediacaran Doushantuo Formation in the Shennongjia area (Hubei Province, South China): Filling critical paleoenvironmental and biostratigraphic gaps

Microfossils of the Ediacaran Doushantuo Formation in South China provide an important window onto the rapid diversification of marine eukaryotes after the terminal Cryogenian global glaciation. They also offer key data in the biostratigraphic subdivision and correlation of the lower–middle Ediacaran System. Previously published Doushantuo microfossils in South China were mostly from intra-shelf facies in the Yangtze Gorges area, shelf margin facies in the Weng’an area, and upper slope facies in the Zhangjiajie area, whereas paleontological data from shallow-water inner shelf facies have been rarely documented. In addition, previous data from South China leave a “barren zone” associated with the negative δ13Ccarb excursion EN2 that impedes biostratigraphic correlation. To address these environmental and stratigraphic gaps, we conducted an integrated chemostratigraphic and biostratigraphic analysis of the Doushantuo Formation at the inner shelf Lianhuacun section in the eastern Shennongjia area of Hubei Provence, South China. The Lianhuacun fossils are preserved in chert nodules/bands of the lower Doushantuo Formation, precisely in a chemostratigraphic interval identified as EN2, indicating that the so-called “barren zone” is likely a taphonomic artifact. A total of 33 genera and 82 species are identified, including a new genus (Duospinosphaera gen. nov.) and seven new species (Duospinosphaera shennongjiaensis sp. nov., D. biformis sp. nov., Jixiania retorta sp. nov., Mengeosphaera mamma sp. nov., Sinosphaera exilis sp. nov., Tanarium columnatum sp. nov., and Weissiella concentrica sp. nov.). The Lianhuacun acanthomorphic acritarchs can be broadly assigned to the third microfossil assemblage zone (i.e., the Tanarium conoideum – Cavaspina basiconica Assemblage Zone) recognized on the basis of the Weng’an biota that is correlated with upper Member II of Doushantuo Formation in the Yangtze Gorges area, consistent with chemostratigraphic correlation between the Shennongjia and Yangtze Gorges areas. Thus, the so-called “barren zone” may be a poorly preserved part of the third microfossil assemblage zone. Alternatively, it may represent a new and yet unnamed microfossil assemblage zone between the third and the overlying Tanarium pycnacanthum – Ceratosphaeridium glaberosum Assemblage Zone. Regardless, the new data presented here fill important gaps in the geographical, paleoenvironmental, and stratigraphic distributions of Ediacaran acanthomorphic acritarchs in South China. As such, they facilitate integrative chemostratigraphic and biostratigraphic correlation of Ediacaran strata at regional and global scales.

Integrated study of the Doushantuo Formation in northwestern Hunan Province: Implications for Ediacaran chemostratigraphy and biostratigraphy in South China

The Ediacaran Doushantuo Formation in South China documents profound biological and environmental changes after the Neoproterozoic global glaciations. However, since the geological records of these changes are scattered in various lithofacies, the establishment of the co-evolutionary pattern of life and environment largely relies on regional stratigraphic correlation. A negative δ13C excursion in the upper Doushantuo Formation in the shelf-margin facies has been correlated with different δ13C chemostratigraphic features in the Doushantuo Formation in the shelf-lagoon facies: either with EN3 (widely regarded as equivalent to the Shuram excursion in Oman) or with EN2, which occur respectively in the upper and middle Doushantuo Formation in the Yangtze Gorges area of South China. Here we report new litho-, chemo-, and biostratigraphic data of the Douoshantuo Formation at the Caojunba section in shelf-margin facies, where the lithostratigraphic sequence and carbon isotopic profile resemble those at other shelf-margin sections, e.g., the Yangjiaping and Zhongling sections. Diverse microfossils including nine genera and eighteen species of acanthomorphic acritarchs are found from the upper Doushantuo Formation at Caojunba, which represent to date the first report of the upper Doushantuo acritarch assemblage from the shelf-margin facies in South China. The newly recovered microfossil assemblage includes Hocosphaeridium anozos, H. scaberfacium, Tanarium conoideum, and clustered leiospheres, and these taxa support the stratigraphic correlation of upper Doushantuo Formation between shelf-margin and shelf-lagoon facies. This correlation indicates that the interval with negative δ13C values in the upper Doushantuo Formation of shelf-margin facies is likely equivalent to EN3. This correlation also suggests that the δ13C profiles of the EN3/Shuram excursion interval in different facies in South China have various expressions (e.g., stratigraphic range, magnitude), making its regional and continental correlations more challenging. On the other hand, the discovery of acritarch assemblage characteristic of the upper Doushantuo Formation in the Yangtze Gorges area from shelf-margin facies confirms their potential as an independent stratigraphic tool in the subdivision and correlation of Ediacaran strata.

Geochronological and geochemical constraints on the origin of highly 13Ccarb-depleted calcite in basal Ediacaran cap carbonate

AbstractEdiacaran cap dolostone atop Marinoan glacial deposits contains complex sedimentary structures with extremely negative δ13Ccarb values in close association with oscillations in palaeoclimatic and oceanographic proxy records. However, the precise geological, geochronological and geochemical context of the cap dolostone is not clarified, which hampers us from correctly interpreting the extremely negative δ13Ccarb values and their causal relationships with the Snowball Earth hypothesis. In this study, we conducted detailed in situ geochronological and geochemical analyses on the calcite within the cap dolostone from the Ediacaran Doushantuo Formation in South China in order to define its formation and relationship to the Snowball Earth hypothesis. Petrographic observations show that formation of dolomite pre-dates precipitation of calcite and pyrite, which pre-dates quartz cementation in the basal cap carbonate. Calcite cement within the cap dolostone yielded a U–Pb age of 636.5 ± 7.4/17.8 Ma (2σ, MSWD = 1.6, n = 36/40), which is within uncertainty of a published dolomite U–Pb age of 632 ± 17 Ma (recalculated as 629.3 ± 16.7/22.9 Ma). These age constraints negate the possibility that the calcite cement was formed by late Ediacaran or Cambrian hydrothermal activity. The rare earth element distribution patterns suggest a dominant seawater origin overprinted by subsequent early Ediacaran hydrothermal activity. The combined age, petrographic and geochemical data suggest oxidization of methane clathrates in response to complicated interplay between eustasy and isostatic rebound and hydrothermal fluids.

Non-metazoan affinity of embryo-like Megasphaera fossils from the Ediacaran Zhenba microfossil assemblage

The Ediacaran Doushantuo Formation of South China yields diverse phosphatised embryo-like fossils, among which the taxon Megasphaera stands out for its astonishing abundance and strong resemblance to extant invertebrate embryos. Our knowledge of Megasphaera has been increasing since their discovery in 1986. However, the controversy surrounding its biological affinity remains unresolved. Previous investigations have almost all been based on specimens from the Weng’an biota; here, however, we show new fossil material from the Zhenba microfossil assemblage, a possibly younger phosphatised fossil deposit from the base of the late Ediacaran Dengying Formation. The new material not only contains common specimens seen in the Weng’an biota but also provides single-celled specimens with a broader size range and Megaclonophycus-stage specimens with remarkably tiny daughter cells comparable to the smallest single-celled specimen in size as well as structure, and hence, allows a more complete reconstruction of the life cycle. Multiple methods analyses reveal a conspicuous volume increase during the vegetative stage, a ceaseless cell division without germ-layer or tissue-organ differentiation, and a probable phenomenon of encystment. These features are inconsistent with the embryogenesis of living animals, and therefore do not support the metazoan-embryo interpretation. In contrast, a more complete life cycle based on new specimens supports an encysting-protist affinity as the interpretation of the Ediacaran Megasphaera fossils.

Spatial distribution of organic functional groups in Ediacaran acritarchs from the Doushantuo Formation in South China as revealed by micro-FTIR spectroscopy

Raman and Fourier-transform infrared (FTIR) microspectroscopic analyses were performed to examine the chemical signatures and their spatial distribution of organic-walled microfossils together with organic matter (OM) in a black chert nodule from the Ediacaran (635–551 Ma) Doushantuo Formation in China. Raman spectral parameters (I-1350/1600 values) reveal that the acritarchs, bundled filaments, and OM have different degrees of structural order, and that there is no significant difference in I-1350/1600 values among the different portions of individual acritarchs (i.e., inner structure, inner membrane, and outer wall). The IR mapping reveals portion-specific chemical signatures within the individual acritarch specimens. The inner membrane of Tianzhushania contains aliphatic C-H bonds. The acritarchs, including Tianzhushania, show chemically four types of inner structures: (1) aromatic C-H-rich type, (2) aliphatic C-H-rich type, (3) aromatic/aliphatic C-H-poor type, or (4) heterogeneous. All of the examined acritarchs have aromatic C-H rich outer wall, irrespective of the presence/absence of processes. These features support a eukaryotic cyst origin, although it is difficult to determine whether the acritarchs correspond to the cysts of Protista or Metazoa. The bundled filaments also consist of an aromatic C-H bond, but its origin is uncertain. The OM shows a high degree of variation in Raman spectral I-1350/1600 values, as does the IR spectral intensity ratio of asymmetric aliphatic CH3/CH2, alongside a heterogeneous spatial distribution of aromatic and aliphatic C-H bands. This suggests the contribution of various precursors derived from dead microbial cell debris and extracellular organic compounds. Overall, these results confirm the presence of diverse microorganisms in the Doushantuo microbiota. Furthermore, the spatial distribution of organic functional groups in individual microfossils could provide clues about the taxonomy of microfossils of unknown origin.

Chromium isotope evidence for oxygenation events in the Ediacaran ocean

Pulses of the Ediacaran ocean oxygenation were inferred from strong enrichments of redox-sensitive elements (RSEs; particularly Mo, V, U, Re) and negative pyrite sulfur isotopes (δ34Spy) in black shales of the Doushantuo Formation in South China. These oceanic oxygenation events (OOEs) have been challenged by the lack of comparable RSE enrichments in correlative strata of northwestern Canada. Here we report four positive chromium isotope (δ53Cr) excursions with peak values (+0.79 ± 0.03‰ to +1.45 ± 0.06‰; 2SD) close to the average δ53Cr value of the modern ocean (+1.0 ± 0.3‰) at the intervals of OOEs, which are separated by low δ53Cr values close to that of the bulk silicate Earth (BSE, −0.124 ± 0.101‰). The positive δ53Cr excursions could be explained by episodic input of oxygenated water from the open ocean to the restricted Nanhua basin, or pulses of ocean oxygenation during the Ediacaran-early Cambrian. The two interpretations can explain the majority of the geochemical data available from the Wuhe section, but both have limitations. The first interpretation implies that the open ocean was more oxygenated than the Nanhua basin during the entire Ediacaran-early Cambrian period, which is not supported by the currently available data from other Ediacaran successions. The second interpretation has difficulties to explain the thallium isotope (ε205Tl) data from the same section, pending confirmation of the OOEs from other successions globally. The data from the Wuhe section highlight the complexity of interpreting the redox history of the global ocean from geochemical results of a single section. Nonetheless, the synchronous changes of multiproxy records—including positive δ53Cr excursions, RSE peaks, negative δ34Spy and molybdenum isotope (δ98Mo) excursions—at the same stratigraphic intervals do support a more oxygenated ocean at ~635 Ma, ~580 Ma, ~560 Ma, and early Cambrian, regardless of the degree of restriction of the Nanhua basin from the open ocean.

Deposition or diagenesis? Probing the Ediacaran Shuram excursion in South China by SIMS

The Ediacaran Period (ca. 635–541 Ma) witnessed the earliest paleontological evidence for macroscopic animals (i.e., Ediacara biota) and geochemical observations of the largest carbon cycle anomaly in Earth history (i.e., Shuram Excursion, SE). Numerous hypotheses have been proposed for the origins of the SE, ranging from primary seawater anomaly to syn- or post-depositional diagenesis. Despite intensive geochemical and theoretical work published in the past decade, empirical evidence that is strictly based on fundamental petrographic results at the micrometer scale is still limited. To evaluate depositional compositions and diagenetic effects on samples from the SE, we investigated the EN3 interval in the Doushantuo Formation of South China via integrated cathodoluminescence (CL), secondary ion mass spectrometry (SIMS), and scanning electron microscope (SEM). Detailed petrographic observations reveal that the EN3 limestone is dominated by calcite microspar, with minor but variable amounts of disseminated zoned dolomite crystals. The former likely formed via neomorphism of depositional micrite, while the latter was the result of progressive post-depositional dolomitization. The mean values of paired SIMS δ13Ccalcite and δ13Cdolomite compositions are indistinguishable in each sample and consistent with published micro-drilled bulk-powder δ13C values, which we interpret to represent depositional “background” signals of seawater dissolved inorganic carbon (DIC). We also observed μm-scale variability of SIMS δ13C data that may reflect a variable diagenetic overprint after deposition. Our integrated petrographic and geochemical results are consistent with a depositional origin of the SE and provide little evidence for the hypothesized isotope alteration by meteoric and mixing-zone diagenesis or late burial diagenesis. In light of this study, we propose that the SE indeed represents a marine carbon cycle anomaly that bears a close temporal link to the Ediacaran surface environment.

Iron phosphate in the Ediacaran Doushantuo Formation of South China: A previously undocumented marine phosphate sink

Ediacaran phosphorites capture the dynamics of the ultimate biolimiting nutrient, phosphorus, during perhaps the most critical transition of Earth's climatic and ecological history. Concomitant with the Neoproterozoic Oxygenation Event was the deposition of the first extensive phosphorites across marine shelves, typically interpreted as a basinward shift in the locus of phosphogenesis facilitated by deep-ocean oxygenation. Petrographic and spectroscopic analyses of proximal phosphorites from the Ediacaran Doushantuo Formation near the Yangtze Gorges area of South China reveal the presence of interlaminated pristine, muddy, and granular phosphorites that were cemented by early diagenetic iron phosphate, an additional, previously undocumented seafloor P sink. Transmitted- and reflected-light microscopy, cathodoluminescence microscopy, and back-scattered electron scanning electron microscopy were used to reconstruct the paragenesis of phosphorites at the Wanjiagou section near Zhangcunping (Hubei Province) and demonstrate that pristine phosphorite precipitated authigenically as francolite via microbially-mediated phosphogenesis as evidenced by preserved microbial laminations along with filamentous and coccoidal microfossils. Subsequent tidal reworking of pristine hardgrounds and phosphatic mudstones produced minimally-coated intraclasts and peloidal phosphatic grains that were cemented by iron phosphate soon after deposition but before compaction. Raman spectroscopy, bulk-sample and micro-X-ray diffractometry indicate the iron phosphate cement is composed of phosphosiderite/strengite (Fe+3PO4•2H2O). The presence of phosphosiderite can be attributed to either syndepositional oxidation of phosphorites or thermal stabilization of vivianite (Fe2+3(PO4)2•8H2O). In both cases, the occurrence of phosphosiderite represents the first direct evidence for iron phosphate minerals as a P sink during the Ediacaran and suggests phosphogenesis may have partially proceeded in ferruginous porewaters in contrast to the redox-independent process of francolite precipitation. Integration of petrographic and geochemical techniques, such as those employed in this study, offers the ability to corroborate P speciation analyses and provides an independent determination of P phase partitioning. Ultimately, this approach is paramount in testing hypotheses that suggest ferrous iron phosphate minerals played a regulatory role in global Proterozoic oxygenation.

Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the “dolomite problem”

Paleozoic and Precambrian sedimentary successions frequently contain massive dolomicrite [CaMg(CO3)2] units despite kinetic inhibitions to nucleation and precipitation of dolomite at Earth surface temperatures (<60 °C). This paradoxical observation is known as the "dolomite problem." Accordingly, the genesis of these dolostones is usually attributed to burial-hydrothermal dolomitization of primary limestones (CaCO3) at temperatures of >100 °C, thus raising doubt about the validity of these deposits as archives of Earth surface environments. We present a high-resolution, >63-My-long clumped-isotope temperature (TΔ47) record of shallow-marine dolomicrites from two drillcores of the Ediacaran (635 to 541 Ma) Doushantuo Formation in South China. Our T∆47 record indicates that a majority (87%) of these dolostones formed at temperatures of <100 °C. When considering the regional thermal history, modeling of the influence of solid-state reordering on our TΔ47 record further suggests that most of the studied dolostones formed at temperatures of <60 °C, providing direct evidence of a low-temperature origin of these dolostones. Furthermore, calculated δ18O values of diagenetic fluids, rare earth element plus yttrium compositions, and petrographic observations of these dolostones are consistent with an early diagenetic origin in a rock-buffered environment. We thus propose that a precursor precipitate from seawater was subsequently dolomitized during early diagenesis in a near-surface setting to produce the large volume of dolostones in the Doushantuo Formation. Our findings suggest that the preponderance of dolomite in Paleozoic and Precambrian deposits likely reflects oceanic conditions specific to those eras and that dolostones can be faithful recorders of environmental conditions in the early oceans.

Comparison of Ediacaran platform and slope δ238U records in South China: Implications for global-ocean oxygenation and the origin of the Shuram Excursion

The Ediacaran Shuram negative carbon isotope excursion (SE) records major paleoceanographic changes during the late Neoproterozoic, possibly linked to a global oceanic oxygenation event, yet its cause(s) remain uncertain. Earlier studies of the upper Ediacaran Doushantuo Formation in South China based on local redox proxies have documented strong spatial redox heterogeneity along shelf-to-basin transects, but variations of δ238U (a global redox proxy) have not yet been examined in deep-water SE carbonates. In this study, we examined δ238U variations through the SE in the upper slope Siduping section. Similar to platform SE sections, Siduping exhibits a shift toward higher δ238U values correlative with the peak of the SE (i.e., maximum negative δ13Ccarb), confirming inferences of global ocean oxygenation during the SE. This raises an apparent paradox, because a global negative carbon isotope excursion implies net oxidant consumption, requiring an ocean-based oxygenation mechanism. We hypothesize that an increase in the efficiency of phosphorus burial due to a plankton-driven shift from dominantly dissolved organic matter (DOM) cycling to greater particulate organic matter (POM) export depleted the ocean of nutrient phosphorus. By producing a steep redox gradient close to the sediment-water interface, we suggest that ocean oxygenation also triggered a globally simultaneous diagenetic event in which isotopically light δ13Ccarb was precipitated in authigenic carbonate minerals. This scenario can account for δ238U differences between shallow-water and deep-water carbonates, which reflect precipitation of relatively larger amounts of authigenic carbonate minerals in shallow-water settings, generating both a larger negative δ13Ccarb shift and a larger early diagenetic δ238U offset.

Transient and stepwise ocean oxygenation during the late Ediacaran Shuram Excursion: Insights from carbonate δ238U of northwestern Mexico

The Ediacaran Shuram Excursion (SE) was a key episode in the history of atmospheric and oceanic oxygenation that has also been linked to contemporaneous bioevolutionary events. However, key aspects of the redox state of Ediacaran oceans during the SE remain in doubt. Here, the uranium isotope compositions (δ238U) of marine carbonates from Sonora, northwestern Mexico were measured to investigate ocean oxygenation during the SE. We found that the SE in Sonora is characterized by a shift toward higher δ238U values (from −0.7‰ to −0.3‰), consistent with a major oxygenation event that has now been documented in widely separated coeval upper Ediacaran sections including the Doushantuo Formation in South China, the Bol'shoy Patom Formation in Siberia, and the Johnnie Formation in California. In the Sonora Succession, this δ238U shift exhibits a ~0.8-Myr lag relative to the δ13Ccarb excursion that defines the SE. To account for these observations, we propose a two-step oceanic oxygenation model for the SE: (1) initial oxidation of an aqueous reductant (e.g., dissolved organic carbon) that resulted only in a shift of δ13Ccarb (from +5‰ to −3‰); and (2) subsequent oxidation of methane or particulate organic matter that caused a continuation of the negative shift in δ13Ccarb (from −3‰ to −12‰) as well as a positive excursion of δ238U due to progressive oceanic oxygenation. This transient period of enhanced oceanic oxygenation of the late Ediacaran ocean, which may have promoted the evolution of early metazoans, terminated after ~5.0 to 6.5 Myr.

Using SIMS to decode noisy stratigraphic δ13C variations in Ediacaran carbonates

Carbonate carbon isotope (δ13Ccarb) chemostratigraphy is a valuable tool in Precambrian stratigraphic correlation. The effectiveness of this tool rests on the assumption that δ13Ccarb data record global seawater signals. However, in some cases δ13Ccarb data exhibit rapid and noisy stratigraphic variations that may have been influenced by authigenic or diagenetic carbonate minerals. To assess the contribution of non-primary minerals towards bulk carbonate carbon isotope values, we acquired SIMS (secondary ion mass spectrometry) δ13Ccarb data, electron microscopic data, and CL (cathodoluminescence) microscopic data from two Ediacaran successions—the lower Member II of the Doushantuo Formation in South China and the Mooifontein Member of the Zaris Formation in southern Namibia. The Doushantuo samples came from a stratigraphic interval with noisy meter-scale δ13Ccarb variations of up to 10‰, whereas the Mooifontein Member is characterized by consistent δ13Ccarb values with limited meter-scale variations of less than ~4‰. Our data show that the meter-scale stratigraphic variations in δ13Ccarb are also mirrored in the SIMS data at μm-mm scales in both Doushantuo and Mooifontein samples. In the Doushantuo samples, SIMS δ13Ccarb values of authigenic calcite vary by up to 10‰ over μm-mm scales and can be either higher or lower than those of the co-existing dolomite matrix, which also appears to be affected by authigenic carbonate on the basis of petrographic observation. Bulk-sample δ13Ccarb values measured on powders microdrilled from the same SIMS specimens are within the range of SIMS δ13Ccarb values. Thus, we infer that bulk-sample δ13Ccarb values of Doushantuo samples represent mixtures of different carbonate components. The Doushantuo and Mooifontein SIMS δ13Ccarb data validate the traditional method of using chemostratigraphic consistency to evaluate authigenic/diagenetic alteration, but given that secondary phases may be 13C-enriched relative to matrix carbonate, caution is warranted when taking maximum values to approximate primary chemostratigraphic trends.

Sedimentological and geochemical evolution of an Ediacaran mixed carbonate-siliciclastic continental slope system, Windermere Supergroup, southern Canadian Cordillera, British Columbia, Canada

In this study a 165–265 m-thick siliciclastic-carbonate (mixed) base-of-slope succession within the Ediacaran Isaac Formation (hereafter termed FIC) in the deep-marine Windermere Supergroup (WSG), southern Canadian Cordillera was analyzed. Excellent outcrop exposure at three study areas (Castle Creek, Hill Section and Milk River), spaced over a distance of 20 km parallel to depositional dip provided the opportunity to observe the stratigraphic and inorganic carbon (δ13Ccarb) isotopic evolution of an ancient mixed, passive margin deep-water system. Based on detailed sedimentological analysis six stratal elements make-up the FIC (channel complexes, levees, siliciclastic-to-carbonate tripartite deposits, scour dominated units, debrites and slides). Within these strata the most voluminous carbonate phase (C1) represents neomorphism of primary aragonite on the slope and during early burial, and thus preserves the primary shallow-marine isotopic signature even after downslope transport. At the base of the FIC δ13Ccarb is negative (−5.2‰) and then progressively increases to 2–3‰ in the middle of the succession, after which it plateaus for about 65 m before declining to a nadir of −6.3‰ at its top. Coincident with these isotopic changes are systematic changes in the architecture and mineralogical composition of the component stratal elements that makeup the FIC, which collectively suggest long-term transgressive followed by regressive conditions that quite possibly are tied to rising and then falling sea-level, and accordingly the state of the continental shelf carbonate factory. Additionally, the upward change in δ13Ccarb closely resembles the trend reported in the upper June beds-Gametrail Formation of the WSG in the northern Canadian Cordillera, but the interpreted association of the latter with the Shuram-Wonoka anomaly (570–551 Ma) makes its correlation with the FIC unlikely. Instead, the FIC excursion potentially correlates with the EN2 excursion in the Doushantuo Formation of South China (and its potential global correlatives), which has been interpreted to be associated with the Gaskiers glaciation (580 Ma). This suggests that the FIC might be a stratigraphic and δ13Ccarb record of conditions that prevailed in the deep sea preceding the Gaskiers, which previously has been unreported from strata of the WSG.

Zn-Sr isotope records of the Ediacaran Doushantuo Formation in South China: diagenesis assessment and implications

Recent studies show that zinc isotopes could provide valuable clues to environmental change and biogeochemical cycle of the past oceans. This study reports a modified procedure for leaching the carbonate fractions in sedimentary rocks, a thorough evaluation of diagenetic effects, and systematic variations of Zn and Sr isotope ratios in lower part of the Ediacaran stratigraphic unit deposited in the aftermath of the Marinoan glaciation in South China. The influence of post-depositional diagenesis on Zn isotope compositions of the studied samples is assessed by comparing δ66Zn to other geochemical indexes (87Sr/86Sr, δ13C, δ18O and Mn/Sr ratios). In the five studied cap carbonate sections (Member I of the Doushantuo Formation), dolostones from four sections have δ66Zn values positively correlated with δ18O values and negatively correlated with 87Sr/86Sr ratios (0.7081–0.7204). These correlations suggest that these cap dolostone samples have been modified by post-depositional diagenesis. The light δ66Zn value (−0.02‰) suggests that initial Zn isotope ratios of cap dolostones could have been reset by hydrothermal fluids with relatively high Zn concentration and low δ66Zn values.By contrast, carbonates from Member II of the Doushantuo Formation above cap dolostones are relatively pristine based on their low 87Sr/86Sr ratios (0.7079–0.7086) being indistinct from the proposed early Ediacaran seawater 87Sr/86Sr values. Chemical and isotopic variations in these samples are interpreted to reflect primary signals that record paleo-environmental changes of the early Ediacaran ocean. A rapid increase of δ66Zn from ∼0.3‰ to 1.1‰ occurs in the middle part of Member II, accompanying by relatively invariant 87Sr/86Sr ratios that imply insignificant changes in input from continental weathering. Considering the limited change in atmospheric oxygen during this period, the rapid δ66Zn raise indicates an increase in buried organic matters, which is consistent with the coupled positive shift of δ13Ccarb, as well as the fossil records found in the same strata. These results provide insights into Zn cycling in the post-Marinoan oceans and facilitate the application of Zn isotopes in carbonates as a proxy for the fate of marine organic matter.

Research of Precambrian silicified spheroidal fossils’ preservation mechanism: Fish egg silicified simulation experimental taphonomy

Silicified spheroidal fossils have been found in the Ediacaran Doushantuo Formation in South China. Their organic material was exceptionally well-preserved, thus important to understanding early biological evolution. But the preservation mechanism of the silicified spheroidal fossils was unclear. As a result, research on the preservation mechanism at primal mineralization process was necessary. For this paper, Megalobrama amlycephala eggs were inserted into jars with different silicified concentration solutions. The eggs were immersed in the concentrated solutions for a period of two weeks and were removed afterwards for observation. Once extracted, the fish eggs were found to be separated into various shapes and sizes and rapidly preserved. The experiment showed that the metasomatism and coating were two different kinds of preservation. Upon closer examination of the fish eggs, not all the nuclei were silicified. Additionally, the surface of these eggs was covered by specks of tiny mineral crystals, particularly a tiny mineral that grew vertically in a special form of special biological texture. These tiny minerals helped protect the egg framework and preserved the delicate surface ornamentation. The taphonomy experiment had an important impact and was beneficial to learn more about silicified spheroidal fossils.