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The Drewer quarry located in the Rhenish Massif is a well-studied outcrop that comprises Upper Devonian (Famennian) to Lower Carboniferous (Viséan) strata. Within the Drewer deposits two black shale intervals have been described that are linked to two global oceanic anoxic events, the Hangenberg Event and the Lower Alum Shale Event. The black shales associated with the Middle Tournaisian Lower Alum Shale Event contain abundant phosphatic concretions, which were investigated using thin section petrography, powder X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy. The concretions formed during several growth phases under anoxic and at least episodically sulphidic conditions within the sediment and served as a substrate for subsurface microbial mats that formed phosphatic microstromatolites. The microstromatolites occur either as partially branched columns of up to 600 µm in length attached to the phosphatic concretions or as smaller, bulbous aggregates surrounding the concretions. Element mapping identified the presence of pyrite and other metal sulphides within the phosphatic microstromatolites. The carbon and oxygen stable isotopic composition of phosphate-associated carbonate within the phosphatic microstromatolites suggests that the mat-forming microorganisms were probably anaerobic, chemotrophic microbial communities dwelling in the anoxic environment during the Lower Alum Shale Event. Such interpretation agrees with the deeper-water depositional setting of the Lower Alum Black Shale and its high content of organic matter, suggesting that chemotrophic microbial mats are potent agents of phosphogenesis in general, and of the formation of phosphatic stromatolites in particular.

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.

Animal experiments suggest that selenium (Se) may alleviate cadmium (Cd) toxicity in animal liver and kidneys, but its effect on human liver and kidneys remains uncertain. In China, areas with black shale have shown elevated levels of Se and Cd. According to the USEPA (U.S. Environmental Protection Agency) evaluation method, the soil and rice in these areas pose significant risks. In black shale regions such as Enshi and Zhuxi County, residents who long‐term consume local rice may surpass safe Se and Cd intake levels. Significantly high median blood Se (B‐Se) and urine selenium (U‐Se) levels were detected in these areas, measuring 416.977 μg/L and 352.690 μg/L and 104.527 μg/L and 51.820 μg/L, respectively. Additionally, the median blood Cd (B‐Cd) and urine Cd (U‐Cd) levels were markedly elevated at 4.821 μg/L and 3.848 μg/L and at 7.750 μg/L and 7.050 μg/L, respectively, indicating substantial Cd exposure. Nevertheless, sensitive liver and kidney biomarkers in these groups fall within healthy reference ranges, suggesting a potential antagonistic effect of Se on Cd in the human body. Therefore, the USEPA method may not accurately assess Cd risk in exposed black shale areas. However, within the healthy ranges, residents in the Enshi study area had significantly greater median levels of serum creatinine and cystatin C, measuring 67.3 μmol/L and 0.92 mg/L, respectively, than those in Zhuxi did (53.6 μmol/L and 0.86 mg/L). In cases of excessive Se and Cd exposure, high Se and Cd levels impact the filtration function of the human kidney to some extent. Plain Language Summary Se is an essential trace element for humans. However, excessive intake of Se can harm humans. Cd is a carcinogen and a chronic potent nephrotoxin that mostly accumulates in the human liver and kidneys. Animal experiments suggest that Se may alleviate Cd toxicity in animal liver and kidneys, but its effect on human liver and kidneys remains uncertain. In China, areas with black shale exposure have shown elevated levels of Se and Cd. According to the USEPA (U.S. Environmental Protection Agency) evaluation method, the soil and rice in these areas pose significant risks. Our results suggested that the exposed black shale areas are simultaneously enriched with Se and Cd. However, residents in these areas were exposed to excessive Se and Cd long‐term without significant damage to liver and kidney functions. Therefore, the USEPA method may not accurately assess Cd risk in exposed black shale areas. The risk assessment of heavy metals in high‐Se geological background areas cannot be separated from human health surveys. Our study provides evidence for the antagonistic effects of Se and Cd on the human body. Key Points Residents in exposed black shale areas consume excessive Se and Cd through local rice Human liver and kidney functions are not significantly damaged in exposed black shale areas The USEPA method may not accurately assess Cd risk in exposed black shale areas

The geochemistry of major and trace elements (including heavy metals and rare earth elements) of the fresh and weathered black shales, and the soils derived from black shales in the Ganziping mine area in western Hunan province (China) were studied using the following techniques: X-ray fluorescence (XRF), inductively coupled plasma mass spectrometer (ICP-MS) and X-ray diffraction (XRD). The results show that the black-shale soils are significantly enriched with Al₂O₃ and Fe₂O₃, and depleted of mobile elements CaO, Na₂O and K₂O. The soils are also highly enriched with heavy metals U, V, Ni, Ba, Cu, Zn and Pb, that may cause potential heavy-metal contamination of the soils. Composition of the soils is homogeneous compared to the weathered black shales, for which the concentrations of major elements except CaO and Na₂O, and trace elements except heavy metals (U, V, Ni, Ba, Cu, Zn and Pb) as well as the mobile Sr, show lower variations than in the weathered black shales. Ratios of Zr/Hf, Ta/Nb, Y/Ho, Nd/Sm, and Ti/(Ti + Zr), of the soils are also less variable, with values constantly similar to that of the fresh and weathered black shales correspondingly. Thus, components of the soils are believed to be contributed from the parent black shales through weathering and pedogenesis. It is concluded that the soils were formed by at least two stages of geochemical processes: the early stage of chemical differentiation and the later stage of chemical homogenization. The chemical differentiation that was taken during black-shale weathering might have caused the depletion of CaO and Na₂O, and the enrichment of Al₂O₃ and Fe₂O₃; while the chemical homogenization that was taken during pedogenesis led to the depletion of SiO₂ and K₂O, and to the further enrichment of Al₂O₃ and Fe₂O₃. The heavy-metal enrichment (contamination) of the soils was then genetically related to the enrichment of Al₂O₃ and Fe₂O₃ in the soils.

Current chemostratigraphical studies of the Jurassic System primarily involve the use of one sedimentary component (marine organic carbon), one divalent transition metal substituted in carbonate (manganese), and two isotopic tracers: strontium-isotope ratios (87Sr/86Sr) and carbon-isotope ratios (δ13Ccarb and δ13Corg) in carbonate and in organic matter. Other parameters such as Mg/Ca and Sr/Ca ratios in calcite, oxygen-isotope ratios (δ18O) in carbonate, sulphur-isotope ratios (δ34S) in carbonate-hosted sulphate, nitrogen-isotope ratios (δ15Norg) in organic matter, osmium-isotope ratios (187Os/188Os) in black shales and neodymium-isotope ratios (143Nd/144Nd) in various mineral phases are also useful but at present give poor resolution because the database is incomplete or compromised by various factors. Stratigraphical patterns in total organic carbon (TOC) can be of either local or regional significance, depending on the lateral extent of the former nutrient-rich and productive water mass. Divalent manganese follows a similar pattern, being concentrated, most probably as a very early diagenetic phase, only in oxygen-depleted waters that typically underlie zones of elevated organic productivity. Shifts in Mg/Ca and Sr/Ca ratios on the time scale of ammonite subzones seem largely to reflect temperature changes. Strontium-isotope ratios from pristine skeletal calcite provide a global signal; δ13C values from carbonates with minimal diagenetic overprint potentially do the same, although small spatial differences in palaeo-water-mass composition may have been locally significant. Oxygen-isotope determinations on carbonate rocks and fossils generally yield values that are too scattered to be stratigraphically useful, because they reflect palaeotemperature, the evaporation-precipitation balance in sea water and the impact of any diagenesis involving an aqueous phase. Nitrogen-isotope ratios in organic matter reflect the chemistry of ancient water masses as affected by nitrate utilization and denitrification, and the stratigraphical pattern of this parameter is more likely to correlate only on a regional basis. Neodymium-isotope ratios in sea water are also water mass dependent and greatly affected by regional sources and oceanic current systems. Preliminary data on sulphur-isotope ratios in carbonates and osmium-isotope ratios in organic-rich shales, both potentially offering global correlation, indicate that these tracers may be valuable, although the records at present are not sufficiently well established to allow high-resolution regional correlation. In all cases, biostratigraphically well-dated reference sections, against which the relevant geochemical data have been calibrated, are required in the first instance. To date, studies on the stratigraphical distribution of organic carbon have been principally carried out in both northern (Boreal) and southern (Tethyan) Europe; carbon-isotope stratigraphy has been undertaken primarily, but not exclusively, on bulk pelagic sediments from the Alpine-Mediterranean or Tethyan domain; and strontium-isotope stratigraphy has been undertaken largely on calcitic skeletal material (belemnites and oysters) from northern and southern Europe. In many sections, including those containing ammonites, multi-parameter chemostratigraphy can give resolution that exceeds that attainable by classic biostratigraphical means. Strontium-isotope ratios in skeletal calcite are a particularly powerful tool for illustrating changes in sedimentary rate and revealing gaps in the stratigraphical record.

Silicate minerals enriched in V, Cr and Mn including garnets and epidote-supergroup members, in association with amphiboles, albite, hyalophane, titanite, chamosite, sulfides and other minerals occur in Devonian black shales near Cierna Lehota in the Strazovske vrchy Mountains, Slovakia. The garnets have high concentrations of V, Cr and Mn (up to 17 wt.% V2O3, ≤11 wt.% Cr2O3 and ≤ 21 wt.% MnO) and several compositional types. Vanadian-chromian grossular (Grs 1) usually preserves primary metamorphic oscillatory zoning, whereas solid solutions between goldmanite (Gld 2A,B), V- and Cr-rich grossular and spessartine (Grs 2A,B, Sps 2) form irregular domains or crystals with variable zoning. Dominant substitutions in the garnets include CaMn-1 and (V,Cr)Al-1, resulting in coupled Ca(V,Cr)Mn-1Al-1. Epidote-supergroup minerals occur as abundant anhedral crystals with variable compositional zoning. Nearly all crystals have a complete zoning sequence beginning with REE-rich allanite-(La), followed by mukhinite and by V- and Cr-rich clinozoisite to mukhinite and V- and Cr-poor clinozoisite. In common with garnets, the epidote-supergroup minerals are enriched in V, Cr and Mn (<7 wt.% V2O3, <5 wt.% Cr2O3 and <3 wt.% MnO). Lanthanum is the dominant REE (up to 11.5 wt.% La2O3) in allanite-(La). The composition of epidote-supergroup minerals is controlled by REEFe2+(CaAl)-1, REEMg(CaAl)-1, REEMn2+(CaAl)-1 and REEFe2+(CaFe3+)-1 substitutions introducing REE, together with VAl-1 and CrAl-1 substitutions. The negative Ce and slightly positive Eu anomalies displayed in chondrite-normalized patterns and enrichment in V, Cr and Mn are ascribed to the geochemical properties of the protolith. The minerals investigated exhibit multi-stage evolution: (1) presumed low-grade greenschist-facies metamorphism; and (2) development of V- and Cr-rich zones in both garnet- and epidote-supergroup minerals which result from late-Variscan contact metamorphism due to granitic intrusion of the Suchy Massif. Decreased temperature following the metamorphic peak probably resulted in the formation of REE-, V- and Cr-poor clinozoisite and secondary garnet.

The failure characteristics and the various induced fractures of shale are investigated in this paper. Brazilian tests were conducted for different inclination angles of the weak planes of shale (θ  = 0, 15, 30, 45, 60, 75, 90°). Different loading rates were applied (V  = 0.005 kN/s, 0.02 kN/s, 0.1 kN/s, and 0.5 kN/s). The results show that there is an increase in the Brazilian split strength (BSS) with the increase in the inclination angle from 0° to 90°, with possibly a local dip for 45°. When θ  = 45°, both the split modulus (Es) and the absorbed energy (U) had the minimum values, whereas the fracture maximum deviation distance (L′max) had the maximum value. The geometrical trajectory of the fracture in shale samples can be classified into three types, namely the through fracture, the non-through fracture, and the multiple fracture. The BSS, Es, and U of shale gradually increased with the increase in loading rate. Additionally, the fracture is more close to the center. This is because, as the loading rate increases, the time for the propagation and evolution of internal damage of shale decreases.

Heat-assisted development of shale oil and gas is recognized as a vital technique for the efficient extraction of shale gas; however, there is a need for comprehensive investigation regarding radon release during the extraction process. The aim of this study was to investigate the pore structure and radon release characteristics of heat-treated black shale using low-temperature nitrogen adsorption (LTNA) and radon (Rn-222) measurement equipment. The findings reveal that temperature initially enhances radon release, which subsequently decreases. The maximum radon release occurs at 500 °C, reaching 1.46 times the initial stage. The radon release rate is positively correlated with the volume of micropores (< 2 nm) in the shale. Organic pores within the shale serve as the primary storage spaces for radon, and the intricate pore structure of organic matter provides an optimal environment for radon gas retention. These results contribute to elucidating the mechanisms behind the impact of thermal treatment on shale’s radon release rate, which is crucial for guiding radon radiation evaluation in thermal treatment processes.

Lower Jurassic marine basins across the northwest European epicontinental shelf were commonly marked by deposition of organic-rich black shales. Organic-carbon burial was particularly widespread during the Toarcian Oceanic Anoxic Event (T-OAE: also known as the Jenkyns Event) with its accompanying negative carbon-isotope excursion (nCIE). Lower Toarcian black shales in central and southern Germany are known as the Posidonia Shale Formation (Posidonienschiefer) and are thought to have formed during the T-OAE nCIE. Here, we present stratigraphic (carbon-isotope, Rock–Eval, calcareous nannofossil) data from the upper Pliensbachian and lower Toarcian strata from a core drilled on the northern flank of the Lower Saxony Basin, north–west Germany. The bio- and chemostratigraphic framework presented demonstrates that (i) the rock record of the T-OAE at the studied locality registered highly condensed sedimentation and/or multiple hiatuses and (ii) the deposition of organic-rich black shale extended significantly beyond the level of the T-OAE, thereby contrasting with well-studied sections of the Posidonia Shale in southern Germany but showing similarities with geographically nearby basins such as the Paris Basin (France). Prolonged and enhanced organic-carbon burial represents a negative feedback mechanism in the Earth system, with locally continued environmental perturbance accelerating the recovery of the global climate from T-OAE-associated hyperthermal conditions, whilst also accelerating a return to more positive δ 13 C values in global exogenic carbon pools. Graphical abstract

Climate changes are known to have been a key regulator of the biodiversity in Earth's history. However, the dry‐humid degrees and alternating patterns throughout the Phanerozoic remain largely unconstrained. In this study, we report high contents (2.4 ± 3.8 mg N kg−1) and 17O anomalies (11.0 ± 7.4‰) of nitrate (NO3−) in the early Cambrian black shale from South China, likely caused by atmospheric NO3− intrusion under dry climates that followed tectonic uplift. By developing new methods to quantify aridity indices (AI, 0.06 ± 0.08) in combination with observational data with paleoclimate models, we reconstructed the historical AI variations. Our analyses revealed three significant dry‐to‐humid transitions which include Cambrian‐Ordovician to Silurian‐Permian, Permian‐Triassic boundary to middle Triassic‐early Jurassic, and Jurassic‐Paleogene to Neogene. This study quantitatively unlocked the Phanerozoic climate changes in South China, offering important evidence for understanding the co‐evolution of ecological and climatic systems in Earth's history. Plain Language Summary Climate changes have played a critical role in shaping the biological evolution during the Phanerozoic, but the precise degree of dry‐humid fluctuations and their patterns remain unclear. This study observed high contents and 17O anomalies of nitrate in Cambrian black shale from South China, attributed to atmospheric deposition during dry periods following tectonic uplift. By integrating isotopic and sedimentological data with climate models, we quantified historical aridity and reconstructed its variations in South China. We identified three major dry‐to‐humid transitions in the Phanerozoic. These findings improve our understanding of how climate dynamics interacted with biological and geological changes. Key Points High 17O anomaly (11.0 ± 7.4‰) of NO3− in Cambrian black shale was not explained by early diagenesis and modern surface processes A new framework using the ∆17O of sedimentary NO3− to quantify the deep‐time aridity was developed The data suggest three alternations of dry‐humid climates in the Phanerozoic were recorded by sedimentary geochemistry in South China