Ediacaran Doushantuo Formation Research Articles

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.

Tracing the evolution of dissolved organic carbon (DOC) pool in the Ediacaran ocean by Germanium/silica (Ge/Si) ratios of diagenetic chert nodules from the Doushantuo Formation, South China

The Ediacaran Period (ca. 635–538 Ma) was a critical interval in Earth’s history, bridging the Proterozoic and the Phanerozoic Earth systems. It witnessed the diversification of eukaryotic phytoplanktons in the early stage, the evolution of macroscopic multicellular lives in the late stage, and frequent oscillations of carbonate carbon isotopes of large magnitudes, presumably reflecting large perturbations of the global carbon cycle. It has been proposed that a large dissolved organic carbon (DOC) pool, hundreds to thousands times larger than the present one, was developed in the Ediacaran deep ocean. The wax and wane of the marine DOC pool might be responsible for the secular variation of carbon isotopes of marine dissolved inorganic carbon (DIC) pool, which was recorded in the carbonate carbon isotope chemostratigraphy. However, neither the extent nor the evolutionary history of marine DOC pool in the Ediacaran ocean has been well constrained. In this study, we use Germanium/silica (Ge/Si) ratios of chert nodules from the Ediacaran Doushantuo Formation in the Yangtze Gorges area, South China, to trace the evolution of marine DOC pool. These chert nodules yield abundant microfossils, i.e. acanthomorphic acritarchs, and were precipitated in the early diagenetic replacement of calcareous silty/muddy sediments. Most chert nodules show positive correlations between Al contents and Ge/Si ratios, which can be resolved by a binary mixing between a silica (quartz) endmember and an Al-rich silicate (clay) endmember. On the one hand, the Ge/Si ratios of silica component ((Ge/Si)SiO2) are comparable to the modern seawater composition, suggesting the normal seawater rather than hydrothermal fluids was the major source of Si. On the other, the Ge/Si ratios of the clay component ((Ge/Si)clay) are one to two orders of magnitudes higher than that of normal marine clays. The Ge-enrichment of the clay component could be attributed to the extensive chelation of Ge by organic ligands and massive formation of organic-Ge-Clay complex at high DOC concentration. This observation supports the presence of a large DOC pool in the Ediacaran ocean. In addition, there is an increase of (Ge/Si)clay from the Member II to Member III of the Doushantuo Formation, suggesting an increase of DOC concentration. The expansion of marine DOC pool is coincident with the reduction of the sizes of the upper acanthomorphic acritarch assemblage in the Member III. We suggest that the increase of marine DOC pool might be attributed to the reduction of sizes of particulate organic matter, which favored DOC generation and accumulation in the Ediacaran seawater.

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.

Extensive primary production promoted the recovery of the Ediacaran Shuram excursion

Member IV of the Ediacaran Doushantuo Formation records the recovery from the most negative carbon isotope excursion in Earth history. However, the main biogeochemical controls that ultimately drove this recovery have yet to be elucidated. Here, we report new carbon and nitrogen isotope and concentration data from the Nanhua Basin (South China), where δ13C values of carbonates (δ13Ccarb) rise from − 7‰ to −1‰ and δ15N values decrease from +5.4‰ to +2.3‰. These trends are proposed to arise from a new equilibrium in the C and N cycles where primary production overcomes secondary production as the main source of organic matter in sediments. The enhanced primary production is supported by the coexisting Raman spectral data, which reveal a systematic difference in kerogen structure between depositional environments. Our new observations point to the variable dominance of distinct microbial communities in the late Ediacaran ecosystems, and suggest that blooms of oxygenic phototrophs modulated the recovery from the most negative δ13Ccarb excursion in Earth history.

Diverse multicellular algae from the early Ediacaran Doushantuo chert nodules and their palaeoecological implications

Morphologically diverse multicellular algae preserved with anatomical details are recovered from the chert nodules in the member II of the early Ediacaran Doushantuo Formation in the Yangtze Gorges area, South China. They are taxonomically identified as Archaeophycus yunnanensis, Sarcinophycus papilloformis, Thallophyca ramosa, Thallophyca sp., Thallophycoides phloeatus, Wengania exquisita, W. globosa, W. minuta and two unnamed species. An individual growth of spheroidal thallus is evidenced by a series of specimens of Wengania minuta. Archaeophycus yunnanensis and Sarcinophycus papilloformis are possibly green algae, while the others are interpreted as red algae. The radiation of multicellular algae likely enhanced the efficiency of the biological pump, influencing the ocean ecology and environment during the early Ediacaran.

Barite in the Ediacaran Doushantuo Formation and its implications for marine carbon cycling during the largest negative carbon isotope excursion in Earth’s history

The Ediacaran Period (∼635–539 Ma) witnessed the largest negative inorganic carbon isotope (δ13Ccarb) excursion in Earth’s history (i.e., the Shuram Excursion), which is characterized by decoupling from the organic carbon isotope (δ13Corg) record. The cause(s) of this event remains highly debated. Here, we report a major (∼8–9-Myr-long) episode of strong barium (Ba) accumulation during the Shuram Excursion in the form of barite, as recorded in the Ediacaran Doushantuo Formation (∼635–551 Ma) of South China. The inner-shelf Zhangcunping section exhibits minimal Ba enrichment, while the slope Siduping section shows maximal Ba enrichment with the intrashelf basinal Jiulongwan section in the middle. The Siduping section contains ∼5 μm-diameter, ellipsoidal barite crystals of marine origin; and the Jiulongwan section contains large (>50 μm), euhedral barite crystals and cements that are partly replaced by pyrite, pointing to a diagenetic origin with barite formation within the sulfate-methane transition zone. The barite δ34S is ∼10‰ higher than δ34S of carbonate-associated sulfate at Jiulongwan in contrast to similar values of these two components at Siduping, suggesting a limited influence of methane oxidation, if any, on the formation of Shuram Excursion at Jiulongwan. The Ce/Ce* exhibits a lateral gradient among study sections which is reverse to the Ba enrichment, supporting the hypothesis that local surface-water productivity controlled dissolved oxygen levels in the Ediacaran surface ocean. Based on these findings, we attribute the highest Ba enrichment at Siduping to oceanic upwelling which enhanced local marine productivity. Furthermore, we propose that episodic oceanic upwelling in the Ediacaran shelf regions likely transported phosphorus and dissolved organic carbon (DOC) to shallow waters, increasing their productivity and facilitating the oxidation of DOC, contributing to the largest negative carbon isotope excursion in Earth’s history.

Insights into hydrothermal controls and processes leading to the formation of the Late Ediacaran Gaoyan stratiform manganese-carbonate deposit, Southwest China

The stratiform Mn-carbonate ore from the Gaoyan deposit occurs within terrigenous-sedimentary rocks of the upper part of the Ediacaran Doushantuo Formation and is characterized by rhodochrosite spherulites. Here we examine the effect of depositional environment and hydrothermal contribution based on new petrographical, mineralogical and geochemical data to shed light on major controls on formation of sedimentary Mn mineralization. The significant geochemical characteristics such as high Mn/Fe ratios (average 32.07), high Ba content (average 1940.9 ppm), positive Eu anomalies (average 1.38) and low REE contents (average 51 ppm) reveal a hydrothermal source. Meanwhile, 87Sr/86Sr ratios of Mn ores are substantially higher than those of carbonate wall rocks and contemporaneous seawater, indicating mixing of radiogenic Sr from the Mn-rich hydrothermal extraction from underlying sediments. This explanation is supported by a positive linear correlation between 87Sr/86Sr ratios and Eu anomalies. The slightly positive Ce anomaly of most Mn carbonate ore samples is mirrored in the negative Ce anomaly of black shale, while different Ce anomalies provide evidence that Mn redox cycling took place across a sub-oxic to anoxic/euxinic water interface. The euxinic conditions, as evidenced by the co-occurrence of fine-grained disseminated pyrite to framboidal aggregates (average diameters <5 μm) with rhodochrosite, can account for the high Mn/Fe ratios via ongoing Fe-sulfide precipitation. Calcite introduction to metal-rich hydrothermal waters with a lower pH relative to surface waters, together with Mn-oxide reduction and sulfate reduction, triggers substantial increases in rhodochrosite saturation and precipitation near the water–sediment interface. Subsequently, increasing Ca2+ in early diagenesis resulted in the precipitation of kutnohorite rims. Altogether, we develop a hydrothermal sedimentary model of the Gaoyan Mn mineralization with rhodochrosite spherulites as the hydrothermal sedimentary mineral phases, and kutnohorite forming during early diagenesis. Slightly light carbon isotope compositions (∼–6.1‰) of the manganese carbonate ores than those of normal dolostones (∼–4.8‰) suggest a limited carbon source from oxidation of organic material by methanogenesis processes during burial diagenesis. This model supports the model for direct Mn-carbonate precipitation from redox-stratified water columns and means that sedimentary Mn mineralization may be mainly controlled by hydrothermal contribution, rather than seawater redox conditions. This means exploration strategies that focus on oxic zone alone as an indication of prospectivity may be ineffective.

Manganese carbonate stromatolites of the Ediacaran Doushantuo Formation in Chengkou, northern Yangtze Craton, China

The origin process of manganese ores remains unsolved worldwide. Exploring the origins of stromatolites that contain manganese may be a key to deciphering the sedimentary environments and metallogenic processes of these deposits. However, only a few manganese stromatolites have been discovered and described until now. Microbialites are well developed in the manganese deposits, located near the top of the Ediacaran Doushantuo Formation in Chengkou area of Chongqing, northern Yangtze Craton, but has not been explicitly studied; and whether they are true stromatolites or Epiphyton microbialites remains controversial. Based on field and core observations and thin section microscopy, the characteristics of five types of manganese stromatolites and their growth modes are described in detail in this study. The results show that these stromatolites grew in a biostrome in shoal and lagoon environments and were syngenetic with oncolites and oolites on a carbonate ramp behind the shoal. Manganese stromatolites can be categorized into three forms: (1) stratiform; (2) columnar, which includes branched and columnar types; and (3) stratiform-columnar, which is a transitional type. Based on a criterion that the diameter is less than or greater than 1 mm, columnar stromatolites are further divided into micro-columnar (< 1 mm) and columnar (> 1 mm) columns, which display synchronous growth and are similar to Pseudogymnosolenaceae. Their shapes are mainly controlled by water depths and hydrodynamic strengths. The greater the water depth, the more columnar the columns tend to be. Excessively strong hydrodynamic conditions decrease the growth rate of stromatolites, and they even stopped growth due to wave damage. Furthermore, pillared laminar textures (not Epiphyton), which consist of dendritic, micro-branched and micro-columnar stromatolites, are a common feature of the larger stratiform, stratiform-columnar and columnar stromatolites. The alternations of laminae with different internal textures record subtle fluctuations in water depths and hydrodynamic strengths, which indicate that stromatolite growth is controlled by tidal cycles at the lamina level. Therefore, it is possible that the vertical evolution of the stromatolites could reveal the changing characteristics of both local and regional sedimentary environments, i.e., stromatolite shape changes from columnar to stratiform can represent the onset of shallower environments with weak hydrodynamic conditions. In addition, as important reef builders in shallow carbonate ramps, microstromatolites accelerate the development from ramp to platform. Indicators of microbial control on stromatolite shapes and manganese sedimentation processes include the fabric of stromatolite laminae, organic rhodochrosite with a micritic texture that is usually clotted, spherical, tubular, fibrous or dendritic, which suggests that the laminae resulted from microbially induced in situ precipitation.

Silicified Polybessurus from the Ediacaran Doushantuo Formation records microbial activities within marine sediments

Polybessurus, as a common element of the late Mesoproterozoic to early Neoproterozoic microfossil assemblages, has yet no confirmed record from post-Cryogenian strata. In this study, we report Polybessurus sp. from the Ediacaran Doushantuo Formation chert nodules in western Hubei Province, South China. Polybessurus specimens from the Doushantuo Formation are identical to their pre-Cryogenian counterparts in morphology (stacked concave lamellae), composition (organic matter), and preservational mode (silicification). The Doushantuo specimens generally have large tubes (average diameter ~157 μm, maximum diameter ~450 μm), and are often preserved separately and parallel to the bedding plane, whereas the pre-Cryogenian specimens have relatively small tubes (mostly thinner than 100 μm in diameter), and are often preserved gregariously and perpendicular to the bedding plane. Polybessurus may be formed by a variety of benthic micro-organisms, mainly cyanobacteria, e.g., stalk forming taxa like Cyanostylon and endolithic taxa like Solentia, that are capable of secreting EPS (extracellular polymeric substance) unidirectionally to push itself forward in the sediment. The producers of Polybessurus may have played a role in the benthic microbial community by making microburrows, affecting textures and microenvironments of inshore sediments. As the first unambiguous record of Polybessurus from Ediacaran strata, our new findings extend its distribution from the late Mesoproterozoic–early Neoproterozoic to the late Neoproterozoic.

Cryptic terrestrial fungus-like fossils of the early Ediacaran Period

The colonization of land by fungi had a significant impact on the terrestrial ecosystem and biogeochemical cycles on Earth surface systems. Although fungi may have diverged ~1500–900 million years ago (Ma) or even as early as 2400 Ma, it is uncertain when fungi first colonized the land. Here we report pyritized fungus-like microfossils preserved in the basal Ediacaran Doushantuo Formation (~635 Ma) in South China. These micro-organisms colonized and were preserved in cryptic karstic cavities formed via meteoric water dissolution related to deglacial isostatic rebound after the terminal Cryogenian snowball Earth event. They are interpreted as eukaryotes and probable fungi, thus providing direct fossil evidence for the colonization of land by fungi and offering a key constraint on fungal terrestrialization.

Distribution of Ediacaran acanthomorphic acritarchs in the lower Doushantuo Formation of the Yangtze Gorges area, South China: Evolutionary and stratigraphic implications

As part of the most common eukaryotic fossils in early Ediacaran strata, acanthomorphic acritarchs are crucial for understanding the biostratigraphy and evolutionary dynamics of marine eukaryotes after the Marinoan global glaciation. Abundant and diverse acanthomorphic acritarchs have been reported from the Ediacaran Doushantuo Formation in the Yangtze Gorges area, South China, and different biozonation schemes have been proposed. However, these previously published biozones were based on biostratigraphic data compiled from different stratigraphic sections, with little effort to test whether these biozones can be consistently recognized at different sections, despite the fact that regional consistency is critical to a robust biostratigraphic framework. Also, the evolutionary pattern of the Doushantuo acritarchs has not been documented in detail, especially for acritarchs from the lowermost Doushantuo Formation, largely due to the perceived low taxonomic richness after the Marinoan global glaciation.In this study, we report silicified acanthomorphic acritarchs and other eukaryotic microfossils from chert nodules in the lower part (Member II) of the Doushantuo Formation at the Jiulongwan, Jinguadun, and Wuzhishan sections in the Yangtze Gorges area. From a total of 1547 acanthomorphic acritarch specimens found, 24 genera and 69 species have been identified, including two new genera (Annularidens gen. nov. and Crassimembrana gen. nov.), six new species (Annularidens inconditus gen. et sp. nov., Bispinosphaera vacua sp. nov., Crassimembrana crispans gen. et sp. nov., C. multitunica gen. et sp. nov., Distosphaera jinguadunensis sp. nov., and Mengeosphaera matryoshkaformis sp. nov.), five unnamed species (Annularidens sp., Mengeosphaera sp. 1, Mengeosphaera sp. 2, Sinosphaera sp., and Variomargosphaeridium sp.), and three possible new forms tentatively placed in open nomenclatures (Crassimembrana cf. C. crispans, Tanarium cf. T. conoideum, and Weissiella cf. W. grandistella). The high-resolution fossil occurrence and abundance data from the three sections reveal both spatial variations in acritarch composition, and stratigraphic similarities in acanthomorph range and abundance, indicating that acanthomorph taxa can be applied to biostratigraphic subdivision and correlation only if their stratigraphic records are thoroughly investigated at least at the regional scale. The FADs (first appearance data) of acanthomorph species such as Appendisphaera grandis, Appendisphaera heliaca n. comb., Ericiasphaera fibrilla, and Tianzhushania spinosa, as well as the relative abundance variations of certain taxa, are recognized as promising biostratigraphic markers in lower Doushantuo Formation. The new data also reveal a rapid diversification of marine eukaryotes, with taxonomic richness of acanthomorphs increasing to notable levels within probably ten million years after the termination of the Marinoan glaciation, followed by continuing increase in both taxonomic richness and evenness afterwards.

Tracking the evolution of seawater Mo isotopes through the Ediacaran–Cambrian transition

The rapid increase in animal diversity and abundance over the Ediacaran–Cambrian boundary has been attributed to, among other parameters, pronounced Earth surface oxygenation at that time. However, whether atmospheric oxygen elevated to modern levels, or whether the extent was smaller and oxygen remained relatively muted until the late Paleozoic is currently debated. Here, we present new Mo isotope datasets of drill core material for two key black shale units (the Ediacaran Doushantuo Formation and the lower Cambrian Jiumenchong Formation), located on the Yangtze Block. These data capture a 0.7‰ isotope fractionation between sediments experiencing quantitative and non-quantitative Mo removal. By identifying this offset, we provide integrated estimates for global seawater Mo isotope compositions during the deposition of these two formations (~1.2–1.4‰ and ~1.8–2‰, respectively). When paired with a mass balance model, our results indicate that a large proportion of the early Cambrian ocean was bathed under oxic waters. We also discuss how recent discoveries have provided insights into the geochemical processes underpinning the oxygenation of the oceans.

Estimating ancient seawater isotope compositions and global ocean redox conditions by coupling the molybdenum and uranium isotope systems of euxinic organic-rich mudrocks

The sedimentary Mo and U isotope systems have been commonly used as novel global ocean redox tracers due to their long oceanic residence times and redox-sensitive behavior. However, local sedimentary environments and global ocean redox conditions both influence the Mo and U isotope compositions of euxinic organic-rich mudrocks (ORM). Here, we further develop the coupled use of Mo and U isotope data from euxinic ORM to more robustly infer coeval global ocean redox conditions. We measured δ238U from eight late Neoproterozoic to middle Paleozoic ORM units that have previously reported Mo isotope and Fe speciation data. Integration of our new data with previously published Proterozoic and Phanerozoic Mo and U isotope data reveals that there is no overall correlation between the Mo and U isotope compositions of euxinic ORM. This observation confirms that the extent to which local versus global environments influenced the preserved Mo and U isotope compositions in ORM was variable. Individual ORM units can have negative, positive, or no correlation between δ98Mo and δ238U. A negative correlation between δ98Mo and δ238U in the Upper Devonian Kettle Point Formation is similar to the observations from modern euxinic basins, reflecting a major control on the Mo-U isotope systematics by changes in the local depositional environment, such as bottom-water sulfide concentrations. A positive correlation between δ98Mo and δ238U observed in the Upper Ordovician Fjäcka Shale is best explained by changes in global ocean redox conditions that simultaneously shifted the Mo and U isotope compositions of the global seawater and the Fjäcka Shale ORMs in the same direction. No correlations between δ98Mo and δ238U for euxinic ORM may be caused by specific local depositional changes, a lack of or a combination of local and global environmental changes, and/or is an artifact of limited data. For example, a vertical trend (variable δ98Mo but similar δ238U) is shown by most samples from Member IV of the Ediacaran Doushantuo Formation, implying a strong influence on the Mo isotope data by an Fe-Mn particulate shuttle. A horizontal trend (similar δ98Mo but variable δ238U) is observed from the Paleoproterozoic Zaonega Formation, implying that relatively constant bottom water sulfide concentrations caused similar magnitudes of Mo isotope fractionations whereas other factors (e.g., U reduction pathways, aqueous U species, productivity) were responsible for variable U isotope fractionations. Relatively constant elemental concentrations and isotope compositions from the Tanezzuft Formation are indicative of stable conditions at local and global scales. We further propose a method to estimate the coeval seawater Mo and U isotope compositions based on a coupled Mo-U isotope mass balance model and the observations from modern euxinic basins. The coupled Mo-U isotope data from euxinic ORMs provide more insights on the local and global environmental controls on the preservation of both isotope systems than previously realized. Our study highlights the importance of examining the local depositional environment and using large datasets of coupled Mo-U isotope compositions from euxinic ORM intervals to reconstruct paleocean redox conditions.

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.

Surface ocean nitrate-limitation in the aftermath of Marinoan snowball Earth: Evidence from the Ediacaran Doushantuo Formation in the western margin of the Yangtze Block, South China

Geochemical and paleontological studies suggest that a rapid rise in atmospheric O2 level in the termination of the Marinoan global glaciation (635 Ma) might have triggered the diversification of eukaryotes and caused the deep ocean oxygenation. It is proposed that the Earth’s surface redox condition was directly linked to the marine primary productivity, which represented the only major O2 source before the evolution of land plants. The marine primary productivity was mainly controlled by the bioavailability of macronutrients, phosphorus (P) and nitrogen (N). Thus, reconstruction of ancient P and N cycles can provide direct constraints on marine organic matter production and the redox landscape of the ocean. Previous studies of the Ediacaran Doushantuo Formation in the Yangtze Block, South China, suggested that the Ediacaran marine N cycle was highly dynamic and was characterized by dramatic fluctuations in the intensity of denitrification. However, these studies were mainly focused on sections deposited in the offshore marine environment, and little is known about the N cycle in the nearshore regions. In this study, we report high-resolution organic carbon (δ13Corg) and nitrogen (δ15NTN) isotopes of the Doushantuo Formation at the E-Shan section in the western margin of the Yangtze Block. The Doushantuo Formation at the E-Shan section is composed of alternating deposition of thin bedded sandstone and mudstone, and was deposited in a nearshore delta environment. The δ13Corg profile displays two prominent negative excursions, which are coincident with two positive excursions in δ15NTN. The positive excursion in δ15NTN implies the enhanced denitrification, resulting in the loss of N (nitrate and ammonium). In addition, there are negative correlations between δ15NTN and TOC content and between δ15NTN and δ13Corg. Such relationships suggest that the reduction of N supply would lower primary productivity and accordingly decrease the carbon isotope of dissolved inorganic carbon (δ13CDIC) in the surface ocean. In addition, this interpretation also implies that N-fixation was not active in the nearshore region. We speculate that the muted N-fixation in the nearshore regions could be attributed to the Fe limitation in oxic shallow seawater and general Mo deficiency of the Ediacaran ocean. Thus, our study indicates that the surface ocean productivity and marine redox landscape were coupled in the Ediacaran ocean.

Apatite-glaucony association in the Ediacaran Doushantuo Formation, South China and implications for marine redox conditions

Major phosphogenic events took place in the late Paleoproterozoic and the Ediacaran, both of which followed an episode of atmospheric oxygenation. These apparent coincidences have led to suggestions that the Precambrian phosphorus cycle was partly regulated by oceanic redox conditions, although direct evidence is lacking. In this paper, we report the discovery of glaucony in drill cores from the phosphorite-rich Ediacaran Doushantuo Formation at Weng'an, South China, which provides new insights into redox conditions and geochemical cycles during the deposition and early diagenesis of the lower Doushantuo Formation. The presence of flaser and lenticular bedding in the sandstones suggests deposition in a tidally-influenced shallow water environment. Apatite is present as millimeter-scale flasers in sandstones, but more commonly as intraclastic grains. Glaucony typically occurs as interstitial aggregates cementing and replacing detrital minerals and phosphatic grains, with an upsection decrease in abundance. The Doushantuo glauconies have consistently high K2O (7.5–9.6 wt%). In particular, phosphorite-hosted glaucony has generally higher total iron (TFe2O3) than sandstone-hosted glaucony, consistent with Al3+–Fe3+ substitution in the octahedral site, as supported by Raman peaks slightly shifted towards lower wavenumbers for higher Fe content. A decrease in detrital input probably resulted in limited Al availability during early diagenesis, which in turn led to the waning of glaucony upsection. The phosphate grains do not show any negative Ce anomalies, consistent with precipitation of authigenic apatite in suboxic environments with insignificant preferential remobilisation of Ce during deposition and early diagenesis. REE + Y features show variable diagenetic REE enrichment in phosphorites, but identical concave-down patterns. The wide occurrence of glaucony cement further documents the presence of a generally suboxic early diagenetic environment on the seafloor, which was in active exchange with bottom seawater. Slight fluctuations of redox states in the porewater and bottom water would have promoted the cycling of Fe, enrichment of phosphate and REE, and extensive glaucony authigenesis. Therefore, the glaucony-bearing phosphorites in the Doushantuo Formation are a direct result of Fe-redox driven diagenesis. Apatite-glaucony association likely forms in suboxic environments and is considered as a useful mineralogical proxy for paleoredox conditions on the Precambrian ocean floors.

Variation of chemical index of alteration (CIA) in the Ediacaran Doushantuo Formation and its environmental implications

The Ediacaran Period (635–541 Ma) witnessed rapid turnovers of marine organisms that eventually led to the early Cambrian radiation. The Ediacaran Doushantuo Formation (ca. 635–551 Ma) serves as one of the most important and intensively studied stratigraphic units for understanding the co-evolution of life and environment during this critical time interval. To better understand the early-middle Ediacaran climate change, we reconstruct a temporal variation curve of chemical index of alteration (CIA) from a drill core and an outcrop of the Doushantuo Formation, in combination with previously published CIA data from segments of time-equivalent strata. The results show three distinct decreases in CIA values that correlate well with the positive carbon isotope (δ13C) excursion at the low Doushantuo Formation (EP1) and the negative δ13C excursion at the middle (EN2) and upper (EN3) Doushantuo Formation. The decline of CIA in EP1 is consistent with occurrence of glendonites at the same stratigraphic interval that suggests a cooling event. The low CIA values in EN2 and EN3 also suggest relatively colder periods that are consistent with evidence from strontium isotope (87Sr/86Sr) and oxygen isotope (δ18O) data. With existing bio- and chemostratigraphic constraints, the cooling event associated with EN2 might be synchronous with the Gaskiers glaciation. The other two cold periods associated with EP1 and EN3, however, have not been documented from other successions globally, which needs to be tested in future studies.

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.