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In the present study, we carried out trace element analyses of black shales of the Ediacaran Doushantou Formation from two sections (Jiulongwan, Baiguoyuan) in Hubei Province, South China. Mo-U characteristics of black shales from the two sections and compiled Mo-U data of Doushantuo black shales from sections of a variety of sedimentary facies described the temporal/spatial variability in the redox conditions of paleo-seawater during deposition of the Doushantuo Formation. Changes in Mo-U patterns of the Doushantuo Member II (DST2) shales of open marine environments are consistent with a shift from a predominately oxic to a predominately anoxic ocean during their deposition. Mo-U patterns of the DST2 black shales from intra-shelf sections reflect basin restriction may have happened in the intra-shelf basin and are compatible with the redox-stratified model of the intra-shelf basin. Mo-U patterns of black shales of the Doushantuo Member IV (DST4) reveal that the shales from intra-shelf sections have more pronounced Mo enrichment and more significant enrichment of Mo over U than the slope shales, indicating the operation of a Mn particulate shuttle in the intra-shelf basin. High Mo/TOC ratios of the DST4 at the intra-shelf sections, in combination with similar Mo-TOC patterns of the DST4 from both intra-shelf and slope sections, indicate the intrashelf basin was well connected to the open ocean during deposition of the DST4. [ABSTRACT FROM AUTHOR]

In order to acknowledge the enrichment mechanism of organic matter in the black shale of the Middle Ordovician Yanxi Formation in central and southern Hunan area, the shale samples of the Yanxi Formation in the Maduqiao, Jinweixiang, Hejiadong and Mianhuaping are selected to test abundance of organic matter, major, trace and rare earth elements. The results show that the average total organic carbon (TOC) of black shale in study area is 2.03%, indicating the high abundance of organic matter in the Yanxi Formation. The CIA values and w(Sr)/w(Cu) ratios show that the Yanxi Formation had a warm and humid climate. The concentrations of Zn, V, Ni and Cu imply a medium primary productivity in the Yanxi Formation, whereas they have weak correlations with TOC. The element concentrations of V, Cr, Ni, and Mo reveal that the black shales were deposited in anoxic-euxinic conditions. The accumulation of organic matter is jointly affected by paleoclimate, primary productivity, redox conditions, sea level change and terrigenous debris. The organic matter enrichment model of the Yanxi Formation shales is a 'deepwater retention basin' controlleded by anoxic conditions. [ABSTRACT FROM AUTHOR]

The basal unit of the Early Cambrian black shale sequence of South China hosts sulfide-rich polymetallic units, non-sulfidic vanadium-rich black shales, sapropelic alginite (combustible shale), barite, and phosphorite. This rock spectrum occurs in a paleoceanographic similar, and stratigraphically correlated, transgressive upwelling setting on the passive continental margin of the Neoproterozoic Yangtze Platform. Several centimeter-thick polymetallic sulfidic units (3–13 wt% Mo+Ni, 100–600 ppm U) have relatively light Mo (δ98/95Mo = 1.1 ± 0.2‰) and relatively heavy U isotope composition (δ238/235U = 0.2 ± 0.1‰). Several meter-thick V-rich shales with multiple ore-grade layers (0.1–0.8 wt% V, < 100 ppm U, Mo and Ni ~ 100 ppm) have isotopically lighter Mo (δ98/95Mo = 0.3 ± 0.4‰) and heavier U composition (δ238/235U = 0.4 ± 0.2‰ and up to 0.7‰). The inverse Mo versus U isotope correlation suggests that both metals were enriched by removal from anoxic to strongly euxinic bottom water in restricted basins along the rifted continental margin. Metal replenishment probably occurred via the cycling of Fe–Mn-oxyhydroxide particles across the redox boundary, with sorption/desorption of Mo (and likely Ni) in a stratified water column. In contrast, V enrichment with much lower Mo, Ni, and U contents, but more fractionated Mo and U isotope composition, reflects non-sulfidic anoxic depositional conditions in a partly open system with higher bottom water renewal rates. While Mo isotope fractionation likely occurred in the water column, U isotope fractionation may dominantly have occurred at the water-sediment interface, perhaps in a benthic organic flocculent layer. These findings indicate that local hydrodynamic control and stratified water column redox conditions may explain the observed variation of metal enrichment (Mo–Ni versus V) in the black shales. Furthermore, the high δ98/95Mo values up to 2.6‰ of the black shales studied and the correlated U and Mo isotope data suggest that Early Cambrian seawater was at least episodically broadly similar to modern seawater. [ABSTRACT FROM AUTHOR]

The Devonian–Carboniferous transition marks a fundamental shift in the surface environment primarily related to changes in ocean–atmosphere oxidation states1,2, resulting from the continued proliferation of vascular land plants that stimulated the hydrological cycle and continental weathering3,4, glacioeustasy5,6, eutrophication and anoxic expansion in epicontinental seas3,4, and mass extinction events2,7,8. Here we present a comprehensive spatial and temporal compilation of geochemical data from 90 cores across the entire Bakken Shale (Williston Basin, North America). Our dataset allows for the detailed documentation of stepwise transgressions of toxic euxinic waters into the shallow oceans that drove a series of Late Devonian extinction events. Other Phanerozoic extinctions have also been related to the expansion of shallow-water euxinia, indicating that hydrogen sulfide toxicity was a key driver of Phanerozoic biodiversity.A spatial and temporal compilation of geochemical data documents a stepwise transgression of toxic euxinic waters into shallow oceans that drove a series of Late Devonian extinction events. [ABSTRACT FROM AUTHOR]

The Toarcian Oceanic Anoxic Event (T-OAE) and its corresponding Carbon Isotope Excursion (CIE) have been reported widely across the Tethyan region and globally. In Arabia, and based on ammonite dating, the time window of the T-OAE coincided with the deposition of the reddish siliciclastic unit of the Marrat Formation. However, no evidence of the T-OAE/CIE was ever reported from Arabia because these red beds were previously interpreted as continental deposits. Recently, these red beds have been recognized as shallow marine deposits which opened an opportunity to assess the occurrence and expression of T-OAE–CIE in Arabia. In this study, a multiproxy geochemical characterization was performed on the Toarcian Marrat Formation to infer the chemistry of the paleowater column and identify intervals of possible T-OAE/CIE in Arabia. While the low concentrations of redox-sensitive elements (Mo, U, V, Cr) may indicate a shallow oxic marine settings, the coupled negative δ13Corganic excursion and apparent increase in the chemical weathering suggests that the deposition of Marrat red beds coincided with the development of T-CIE and possibly time-equivalent to the T-OAE globally. The origin of reddening is interpreted to have occurred during the middle Marrat deposition due to the stabilization of unstable hydrous iron oxides to hematite under oxic marine conditions. The proposed model further indicates the possible development of source rocks in the deep, anoxic environment counterpart where the T-OAE may be expressed. Since our study documents the first record of the T-CIE and discuss the origin of shallow marine siliciclastic red beds in the Arabian Plate, this will have significant implications for the overall understanding of the T-CIE globally and for hydrocarbon exploration through realizations of potential new source rocks associated with the OAEs in the Toarcian and other time intervals. [ABSTRACT FROM AUTHOR]

Early Cambrian black shales on the Yangtze Platform host a regionally distributed highly metalliferous sulfide-rich carbonaceous unit which has been the subject of extensive debate. This marker unit, with a few centimeters or tens of centimeters in thickness, displays extreme enrichment in Mo and Ni (wt% range), and in a broad spectrum of other metals such as As, Au, PGE, Re, Cu, Zn, Cd, Ag, Sb, Se, Tl, and Hg, and occurs discontinuously along the western passive margin of the Yangtze Platform. It grades laterally in stratigraphically equivalent meter-thick vanadium-rich shale and tens-of-meter-thick sapropelite (combustible shale). New Cu and Zn isotope data, combined with existing Cd, Cr, Ni, Mo, Hg, and Se isotope and other chemical data, allow to attempt an integrated view on the formation of this intriguing unit of hyper-enriched metalliferous black shale. The authigenic Cu enrichment in the 1000-ppm range has produced no or little Cu isotope fractionation (0.03 ± 0.26 ‰ δ65Cu) beyond the lithogenic background. Heavy zinc and cadmium isotope enrichment in the sulfidic samples (1.11 ± 0.18 ‰ δ66Zn, 0.31 ± 0.10 ‰ δ114Cd) is controlled by sulfide fractionation and contrasts with V-rich and barren shale (0.60 ± 0.18 ‰ δ66Zn, 0.00 ± 0.14 ‰ δ114Cd). The distinctly negative Ni isotope composition of the metalliferous unit (−0.84 ± 0.05 ‰ δ60Ni) with Ni in the percent range has been interpreted as due to hydrothermal activity related to the leaching of mafic rocks and their sulfides. Sorption processes (Fe-oxyhydroxides) and redox cycling in the water column and the bottom sediment with microbial activity could be an alternative interpretation. The extreme metal enrichment can be understood as due to a process chain, from high biological productivity in the oxic photic zone to sulfate reduction in the deeper sulfidic water column and upper sediment layer. Key to the metal enrichment seems to be extremely low clastic sedimentation and advanced carbon destruction by anaerobic oxidation. Hydrothermal input of basinal brines along the rifted margin of the Yangtze Platform was likely a part of this scenario. [ABSTRACT FROM AUTHOR]

The Arabian Sea encompasses oxygen minimum zone with denitrifying conditions. For the present study, sediments were collected across three transects off Goa transect (GT), Mangalore transect (MT) and Kochi transect (KT) in contact with water column dissolved oxygen (DO) range of 1.4–118.0 µM. Sediments were investigated for texture, clay mineralogy, total organic carbon (Corg), total nitrogen, CaCO3, δ15N, δ13C, metal content to infer their distribution with changing DO and their use as possible palaeo-proxies. The Corg (0.9–8.6%) is largely marine and δ15N from GT and MT preserves signatures of higher water column denitrification. Al normalised ratios of Cu, Ni, Zn, V and Mo are GT > MT > KT. Nickel could be a productivity proxy for DO <80 µM; Cr, U could be a redox proxy for DO <20 µM; Co and Mn could be a better proxy for DO <80 µM; U/Mo vs. DO could separate sediments with DO less than and >80 µM. We observed that eastern Arabian Sea dataset does not always fall within the defined proxies of the other anoxic basins. The metal concentrations in modern day sediments from the eastern Arabian Sea may be used as a proxy to infer the ancient sediment redox conditions. Highlights: Organic carbon distribution in anoxic sediments. Provenance of sediments. Nitrogen isotopes and geochemistry as palaeo-proxy for anoxic basins. [ABSTRACT FROM AUTHOR]

The Lower Member of the Longmaxi Formation is generally dominated by siliceous shale, but recently we found some siltstone-mudstone rhythm sections developed in the Lower Member of the Longmaxi Formation. The study of formation mechanism of siltstone-mudstone rhythmic sedimentary sections may provide new insights into the shale sedimentary environment. Therefore, we studied the characteristics and formation mechanism of siltstone-mudstone rhythmic sedimentary sections in the Lower Member of the Longmaxi Formation in the Changning area based on core observation, thin section identification, major elements and trace elements analysis. The results show the following: 1) Two siltstone-mudstone rhythmic sedimentary sections are characterized by frequent interbed between black or gray-black shale and light gray siltstone, abundant argillaceous laminas and silty laminas, with obvious lithological boundaries having developed. Horizontal laminas and rhythmic laminas are well-developed in the shale layer, while the wavy laminas are well-developed in the siltstone layer. 2) The major compositional elements are SiO2, Al2O3 and CaO, followed by Fe2O3, MgO, K2O and Na2O. 3) Compared with the world average shale, these siltstone-mudstone rhythmic sedimentary sections are rich in Mo, U and Ba, but less in V, Co, Ni, Cu. Compared with the shale layer, the siltstone layer has lower contents of V, Co and Ni. 4). The geochemical redox indices, Mo-U and CIA values suggest the formation of the siltstone-mudstone rhythmic sedimentary sections are related to influences from bottom currents in an oxic condition with a warm and humid paleoclimate. [ABSTRACT FROM AUTHOR]

The continuous and well-accessible Devonian-Carboniferous boundary successions of the Czech Republic are part of the Brunovistulian Unit, which belongs to the Variscan Rhenohercynian Zone of the Bohemian Massif. The well-studied sections, with almost continuous carbonate sedimentation, crop out in the Moravian Karst area and are characterised by carbonate turbidites (Lesní lom) and hemipelagic successions (Křtiny). In the Lesní lom quarry, a complete succession of conodont zones of the Devonian-Carboniferous boundary interval (Upper expansa, praesulcata, costatus-kockeli, kockeli, sulcata/kuehni, bransoni, duplicata zones) was documented in calciturbidites and can be correlated with coeval foraminiferal zones (Quasiendothyra kobeitusana, Quasiendothyra konensis and Tournayellina pseudobeata zones). The Hangenberg Crisis and its three phases can be well recognised both with lithological, biostratigraphical and geochemical approaches in the Lesní lom section. At Křtiny, the nodular limestones yielded conodonts of the Devonian-Carboniferous boundary interval, but missing protognathodid fauna hampered identification of the kockeli Zone. A stratigraphic gap covering the basal part of the sulcata/kuehni Zone or strong condensation can be inferred from the occurrence of the transitional morphotype Si. sulcata-bransoni at the base of this zone. The tested "Montpellier criterion" for the Devonian-Carboniferous boundary redefinition can be used only in the Lesní lom section, where the first Protognathodus kockeli occurs above the regressive Hangenberg Sandstone Event deposits. [ABSTRACT FROM AUTHOR]

The second pulse of the Late Ordovician mass extinction occurred around the Hirnantian-Rhuddanian boundary (~444 Ma) and has been correlated with expanded marine anoxia lasting into the earliest Silurian. Characterization of the Hirnantian ocean anoxic event has focused on the onset of anoxia, with global reconstructions based on carbonate δ238U modeling. However, there have been limited attempts to quantify uncertainty in metal isotope mass balance approaches. Here, we probabilistically evaluate coupled metal isotopes and sedimentary archives to increase constraint. We present iron speciation, metal concentration, δ98Mo and δ238U measurements of Rhuddanian black shales from the Murzuq Basin, Libya. We evaluate these data (and published carbonate δ238U data) with a coupled stochastic mass balance model. Combined statistical analysis of metal isotopes and sedimentary sinks provides uncertainty-bounded constraints on the intensity of Hirnantian-Rhuddanian euxinia. This work extends the duration of anoxia to >3 Myrs – notably longer than well-studied Mesozoic ocean anoxic events. The Late Ordovician mass extinction has been attributed to extended marine anoxia. Here, the authors use a metal isotope mass balance model and find the marine anoxic event lasted over 3 million years, notably longer than the anoxic event associated with the Permian-Triassic extinction and Cretaceous ocean anoxic events. [ABSTRACT FROM AUTHOR]

We present δ60Ni values for black shales, determined by double-spike MC-ICP-MS. The samples comprise Paleoproterozoic Talvivaara Ni–Zn–Co–Cu black shales from Finland, Neoproterozoic black shales from the Teplá-Barrandian Unit, Czech Republic, Early Cambrian Ni–Mo-rich black shales from the Yangtze Craton, and Devonian Ni–Zn–PGE black shales from Yukon, Canada. In addition, the sample set includes a black smoker sample from the Logatchev hydrothermal field, Mid-Atlantic Ridge. The δ60Ni values vary from − 0.84 ± 0.09 to + 0.62 ± 0.04‰ (2SD) with a median of − 0.10‰ (n = 28). Ni isotopic compositions were predominantly lighter than those of abiotic terrestrial and extraterrestrial samples (0.15 and 0.27‰), mantle (0.23‰, Gall et al. 2017), present-day seawater (1.44‰, Cameron and Vance 2014), dissolved Ni from riverine input (0.84‰, Cameron and Vance 2014), ferromanganese crusts (0.9–2.5‰, Gall et al. 2013), Devonian/Mississippian organic-rich marine sediments, lower Jurassic organic-rich marine sediments (0.2–2.5‰, average 0.92‰, n = 18, Porter et al. 2014), and euxinic sediments of the Black Sea (0.14–0.51‰, Vance et al. 2016). However, the range of δ60Ni values in our black shale samples was close to that of the weathering products of mafic/ultramafic rocks (ore and soil samples) ranging from − 0.60 to + 0.30‰ (Ratié et al. 2015; Spivak-Birndorf et al. 2018), Ni-sulfide ores hosted by Archean komatiites from Australia and Canada (− 0.10 to − 1.03‰, average − 0.70‰, n = 8, Gueguen et al. 2013), and Archean Ni-rich magmatic sulfides from Zimbabwe (− 0.28 to − 0.47‰, n = 6, Hoffman et al. 2014). Based on our observations and considering the extremely low contribution of direct biological uptake of Ni, and a dominant Ni residence in early Fe/Ni-sulfides, we suggest that our mostly light Ni isotopic compositions in metal-rich black shales result from sulfidization of organic matter and Ni removal into sulfides. [ABSTRACT FROM AUTHOR]

The lowermost Famennian deposits of the Kowala quarry (Holy Cross Mountains, Poland) are becoming famous for their rich fossil content such as their abundant phosphatized arthropod remains (mostly thylacocephalans). Here, for the first time, palaeontological and geochemical data were integrated to document abundance and diversity patterns in the context of palaeoenvironmental changes. During deposition, the generally oxic to suboxic conditions were interrupted at least twice by the onset of photic zone euxinia (PZE). Previously, PZE was considered as essential in preserving phosphatised fossils from, e.g., the famous Gogo Formation, Australia. Here, we show, however, that during PZE, the abundance of arthropods drastically dropped. The phosphorous content during PZE was also very low in comparison to that from oxic-suboxic intervals where arthropods are the most abundant. As phosphorous is essential for phosphatisation but also tends to flux off the sediment during bottom water anoxia, we propose that the PZE in such a case does not promote the fossilisation of the arthropods but instead leads to their impoverishment and non-preservation. Thus, the PZE conditions with anoxic bottom waters cannot be presumed as universal for exceptional fossil preservation by phosphatisation, and caution must be paid when interpreting the fossil abundance on the background of redox conditions. [ABSTRACT FROM AUTHOR]