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Nitrogen isotope compositions (d15N) of sedimentary rocks are usually used to reconstruct the paleoenvironment and nitrogen (N) biogeochemical cycle. The d15N values of crude oils inherit the characteristics of relevant source rocks and can well reflect the information of hydrocarbon-forming organisms and environment in ancient water column. However, studies on the d15N of crude oils are limited due to the low N content. In this study, a new efficient method is applied to the marine oils from the Bashituo (BST) and Halahatang (HLHT) areas of the Tarim Basin to obtain the nitrogenous components (i.e., nonhydrocarbons and asphaltenes) for the achievement of N concentration. The carbon and nitrogen isotopes of these components and the biomarkers of oils were measured. The d15N values in asphaltenes (d15NAsp) are significantly heavier than those in nonhydrocarbons (d15NNSOs) in these oils, which are attributed to the potential directional N transfer and kinetic isotope fractionation during the thermal evolution of organic matters (OM). The d15NAsp values have significant correlations with OM origin associated parameters and weak correlations with environmental parameters, suggesting that the difference in d15NAsp values is mainly resulted from biological source rather than redox conditions. The d15NNSOs values have a closer relationship with the redox condition than biological characteristics, indicating that they have a good response to paleoenvironmental variation in the water column, which is not completely overprinted by the difference of OM origin. Different redox conditions give rise to distinct nitrogen cycles, resulting in various d15N values. Anammox occurs in the water column of the Early Cambrian dominated by physically stratified conditions with significant isotope fractionation, resulting in relatively heavier d15N of OM in the BST area. In the MiddleeLate Ordovician period, the limited suboxic zone leads to an insignificant positive bias of d15N caused by partial denitrification in the HLHT oils. The evaluation of d15N in nitrogenous fractions enables a more comprehensive reconstruction of N cycle for ancient oceans. [ABSTRACT FROM AUTHOR]

Background: Dark anaerobiosis promotes the acidification of the thylakoid lumen and a reduction in the plastoquinone (PQ) pool. The relationship between the reduction in the PQ pool in the dark and the induction of the xanthophyll cycle under high light stress was investigated in Chlamydomonas reinhardtii. Methods: To achieve a comprehensive oxidative/reductive (aerobic/anaerobic conditions) state of the PQ pool, cultures were bubbled with air or nitrogen for 4 h. To induce the xanthophyll cycle, the cultures were then irradiated with 1200 µmolphotons m−2 s−1 white light for 1 h. Results: The anaerobic cultures exhibited a stronger induction of the xanthophyll cycle with a 3.4-fold higher de-epoxidation state than the aerobic cultures. Chlorophyll fluorescence measurements showed that this response was influenced by the previous redox state of the PQ pool, and that dark anaerobiosis triggers physiological responses, such as exposure to high light. Thus, the photosynthetic apparatus in anaerobic cultures was already alerted, at the moment of high light exposure, to give an appropriate response to the stress with a stronger induction of the xanthophyll cycle than in aerobic cultures. Conclusions: Our results provide new information on the importance of the redox signaling pathway and highlight the importance of the reductive conditions of the PQ pool in regulating the physiological responses of photosynthetic organisms to stress. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hydrological circulations of Early Cambrian intrashelf basins are restricted. • Hydrodynamic processes affected the Early Cambrian marine redox environment. • High primary productivity and sluggish oceanic circulation enriched organic matter. • Enrichment mechanisms of redox-sensitive trace elements vary temporally. There was a strong relationship between paleo-oceanic conditions and organic matter accumulation during the critical period of the Early Cambrian. The Yangtze Platform in South China provides an opportunity to study this relationship, but the basin architecture and paleo-hydrographic dynamics remain poorly understood, which hinders one's understanding of the evolution in oceanic redox state and its relationship to organic matter accumulation. To fill the knowledge gap, a newly obtained data set from the Lower Cambrian Niutitang Formation shales (Late Cambrian Stage 2-Stage 3) of the intrashelf basin is used. Results show that the molybdenum–uranium covariation, along with the abnormally low Mo contents and Mo/TOC ratios in the anoxic (ferruginous and euxinic) Niutitang shales of the intrashelf basin, indicate a hydrographic circulation that is moderately to strongly restricted. The hydrographic evolution at different stages, influencing redox conditions to a certain extent, in conjunction with variations in primary productivity, controls the enrichment of organic matter. In particular, the relatively low sea level during Interval I (Late Stage 2) resulted in weak connectivity between the intrashelf basin and open ocean; this, coupled with high primary productivity and enhanced chemical weathering, formed stable stratified water (euxinic bottom-water) conditions that were favorable for organic matter enrichment. In contrast, Interval II (Early–Middle Stage 3) and Interval III (Late Stage 3) involved less organic matter enrichment due to weakened restricted hydrographic circulation (Interval II) and oxic bottom-water conditions (Interval III). This study highlights how hydrodynamic processes affected the marine environment during the Early Cambrian and reveals that sluggish oceanic circulation combined with high primary productivity led to anomalous enrichment of organic matter. This may be a common feature of basins with restricted hydrographic circulation in deep time. [ABSTRACT FROM AUTHOR]

Over 1.3 million Californians rely on unmonitored domestic wells. Existing probability estimates of groundwater Mn concentrations, population estimates, and sociodemographic data were integrated with spatial data delineating domestic well communities (DWCs) to predict the probability of high Mn concentrations in extracted groundwater within DWCs in California's Central Valley. Additional Mn concentration data of water delivered by community water systems (CWSs) were used to estimate Mn in public water supply. We estimate that 0.4% of the DWC population (2342 users) rely on groundwater with predicted Mn > 300 μg L-1. In CWSs, 2.4% of the population (904 users) served by small CWSs and 0.4% of the population (3072 users) served by medium CWS relied on drinking water with mean point-of-entry Mn concentration >300 μg L-1. Small CWSs were less likely to report Mn concentrations relative to large CWSs, yet a higher percentage of small CWSs exceed regulatory standards relative to larger systems. Modeled calculations do not reveal differences in estimated Mn concentration between groundwater from current regional domestic well depth and 33 m deeper. These analyses demonstrate the need for additional well-monitoring programs that evaluate Mn and increased access to point-of-use treatment for domestic well users disproportionately burdened by associated costs of water treatment.

Microbial communities are fundamental components driving critical biogeochemical carbon (C), nitrogen (N) and sulfur (S) cycles in groundwater ecosystems. The reduction–oxidation (redox) potential is one important environmental factor influencing the microbial community composition. Here, we developed a bio-trap method using in-situ sediment as a matrix to collect aquifer sediment samples and evaluate the response of microbial composition and C/N/S cycling functions to redox variations created by providing sole O2, joint O2 and H2, and sole H2 to three wells. Illumina sequencing analyses showed that the microbial communities in the bio-trap sediment could respond quickly to redox changes in the wells, demonstrating that this bio-trap method is promising for detecting microbial variation in the aquifer sediment. The microbial metabolic functions related to C, N and S cyclings and organic pollutants degradation were predicted by the Kyoto Encyclopedia of Genes and Genomes (KEGG) approach. It was found that the joint O2 and H2 injection produced medium oxidation–reduction potential (ORP −346 and −614 mV) and enhanced more microbial functions than sole O2 or H2, which mainly include oxidative phosphorylation, most carbon source metabolism, various pollutants degradation, and nitrogen and sulfur metabolism. Moreover, the functional genes encoding phenol monooxygenase, dioxygenase, nitrogen fixation, nitrification, aerobic and anaerobic nitrate reductase, nitrite reductase, nitric oxide reductase, and sulfur oxidation increased. These findings tell us the contaminant bioremediation and N, S metabolism can be promoted by adjusting ORP realised by injecting joint O2 and H2. [ABSTRACT FROM AUTHOR]

The stepwise oxygenation of Earth's surficial environment is thought to have shaped the evolutionary history of life. Microfossil records and molecular clocks suggest eukaryotes appeared during the Paleoproterozoic, perhaps shortly after the Great Oxidation Episode at ca. 2.43 Ga. The mildly oxygenated atmosphere and surface oceans likely contributed to the early evolution of eukaryotes. However, the principal trigger for the eukaryote appearance and a potential factor for their delayed expansion (i.e., intermediate ocean redox conditions until the Neoproterozoic) remain poorly understood, largely owing to a lack of constraints on marine and terrestrial nutrient cycling. Here, we analyzed redox‐sensitive element contents and organic carbon and nitrogen isotope compositions of relatively low metamorphic‐grade (greenschist facies) black shales preserved in the Flin Flon Belt of central Canada to examine open‐marine redox conditions and biological activity around the ca. 1.9 Ga Flin Flon oceanic island arc. The black shale samples were collected from the Reed Lake area in the eastern part of the Flin Flon Belt, and the depositional site was likely distal from the Archean cratons. The black shales have low Al/Ti ratios and are slightly depleted in light rare‐earth elements relative to the post‐Archean average shale, which is consistent with a limited contribution from felsic igneous rocks in Archean upper continental crust. Redox conditions have likely varied between suboxic and euxinic at the depositional site of the studied section, as suggested by variable U/Al and Mo/Al ratios. Organic carbon and nitrogen isotope compositions of the black shales are approximately −23‰ and +13.7‰, respectively, and these values are systematically higher than those of broadly coeval continental margin deposits (approximately −30‰ for δ13Corg and +5‰ for δ15Nbulk). These elevated values are indicative of high productivity that led to enhanced denitrification (i.e., a high denitrification rate relative to nitrogen influx at the depositional site). Similar geochemical patterns have also been observed in the modern Peruvian oxygen minimum zone where dissolved nitrogen compounds are actively lost from the reservoir via denitrification and anammox, but the large nitrate reservoir of the deep ocean prevents exhaustion of the surface nitrate pool. Nitrogen must have been widely bioavailable in the ca. 1.9 Ga oceans, and its supply to upwelling zones must have supported habitable environments for eukaryotes, even in the middle of oceans around island arcs. [ABSTRACT FROM AUTHOR]

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[Objective] The Lower Cambrian Shuijingtuo Formation black shale is an important source rock and shale gas exploration target in the Sichuan Basin. However, the enrichment mechanism of organic matter in this series of black shale is still unclear. [Methods] Here, we reported total organic carbon (TOC) contents, sedimentary microfacies, major and trace elements, and pyritic framboid size distributions in the lower part of Shuijingtuo Formation in the Chengkou area, northeastern Sichuan Basin on the Upper Yangtze Platform, providing new evidence for reconstructing the paleogeography, paleoenvironment, and main controlling factors of organic matter enrichment. The results show that the black shale succession in the Shuijingtuo Formation developed five sedimentary microfacies which related to the deep-water shelf slope environment. Productivity index (BaXS, P/Ti) and continental input index Ti, Al indicate that the sedimentary environment of black shale in the Shuijingtuo Formation is at a low level of paleoproductivity, and the continental input is relatively stable and has no obvious correlation with TOC. Therefore, paleoproductivity and continental input are not the main controlling factors of organic matter enrichment in the black shale of the Shuijingtuo Formation. The redox-sensitive element index (U/Th, UEF, MoEF ) and pyrite framboid size distributions show that the organic matter content is positively correlated with the redox index, indicating that the organic matter enrichment in Shuijingtuo Formation is mainly controlled by the change of redox conditions of the water column. [Conclusions] Based on the above understanding, it can be inferred that the organic matter enrichment of the black shale of the Shuijingtuo Formation was controlled by the fluctuation of redox conditions of the bottom water caused by the large-scale transgression event during the stage 2 to stage 3 Cambrian (529-514 Ma), and the organic matter enrichment model was proposed here. [ABSTRACT FROM AUTHOR]

In order to develop glass-ceramics containing ions of variable valence in lower oxidation states, it is important to know how changing the redox conditions of glass melting affects structure and properties of glass-ceramics. The zinc aluminosilicate glass nucleated by TiO 2 was melted with and without addition of As 2 O 3 and heat-treated from 720° to 1350°C to obtain gahnite-based glass-ceramics. DSC, XRD analysis, Raman spectroscopy and TEM studies revealed that variation of glass melting redox conditions affects kinetics of liquid phase separation and rutile crystallization, composition and structure of gahnite and rutile, crystallization of the residual glass, and does not affect kinetics of gahnite crystallization, gahnite and rutile fractions and structure of glass-ceramics. In glass-ceramics prepared from glasses melted without As 2 O 3 , absorption in the visible and near-IR spectral ranges is due to octahedrally coordinated Ti3+ ions in gahnite nanocrystals. The study is important for development of rare-earth-free phosphors. • Zinc aluminosilicate glass nucleated by TiO 2 was melted with and without As 2 O 3. • Variation of redox conditions does not change the structure of glass-ceramics. • Variation of redox conditions changes the Ti3+/Ti4+ distribution between the phases. • Distribution of Ti3+ and Ti4+ ions between the phases determines optical properties. • Absorption spectra reveal Ti3+ absorption in octahedral sites in gahnite crystals. [ABSTRACT FROM AUTHOR]

Theoretical issues of joint underground storage of hydrogen with methane are poorly studied, and practical examples are rare. Therefore, it is extremely important to analyze the mutual influence of hydrogen-methane mixtures and the host geological environment. This article presents material that makes it possible to substantiate the most significant hydrochemical processes that affect the transformation of cap rocks. For this purpose, the results of our own experiments, as well as published data on the study of the influence of hydrochemical conditions on the diffusion loss of hydrogen, its interaction with rock-forming minerals, organic matter, and pore waters were used. A quantitative assessment of the decrease in the moisture saturation of clay-rocks samples and, as a consequence, the loss of the mass content of mineral and organic substances is given. It was found that the cyclic change of thermobaric effects leads to a change in the redox conditions in the system “rock ↔ pore water” and is accompanied by an increase in the reactivity of calcium, magnesium, sulfur, iron. The saturation indices of pore water with carbonate and sulfate calcium salts were calculated under the conditions of their precipitation, dissolution, and removal from solution. The interpretation of the experimental data made it possible to substantiate the most probable transformations in clayey cap rocks, which affect their screening capabilities. It is recommended to take into account, when designing and operating storage facilities for hydrogen-methane mixtures, the variety of accompanying hydrochemical and microbiological processes that affect the change in the filtration properties of cap rocks.

The Jurassic Period was a significant phase of variable organic matter accumulation in paleo-shelf areas of the southern Tethys (Egypt). Reconstructing the paleoredox conditions, paleoclimate, and weathering intensity, along with the role of terrigenous sediment flux and mineralogical maturity, is important for understanding basin infill history and prevalent paleoenvironmental conditions. Here, inorganic geochemical data are presented from the Middle Jurassic Khatatba Formation and two samples from the underlying Ras Qattara and the overlying Masajid formations in the Jana-1x well, Shushan Basin, Western Desert. Twenty-four (24) whole-rock samples were analyzed for their major and trace element composition and carbonate content. The Khatatba Formation represents one of the major hydrocarbon source rocks in the North Western Desert, Egypt. Redox conditions were assessed based on enrichment factors of redox-sensitive elements Mo, V, U, and Co. Results revealed that the Khatatba Formation was deposited under predominant anoxic bottom and pore water conditions, in contrast to the oxic settings that were prevalent during the deposition of the Ras Qattara and Masajid formations. Continental weathering intensity and paleoclimate were reconstructed based on several proxies, such as the chemical index of alteration (CIA), K2O/Rb, Rb/Sr, Ln(Al2O3/Na2O), and Al/K ratios, indicating that the studied succession was deposited during alternating phases between weak and moderate weathering intensity under arid and warm-humid climates, respectively. Periods of enhanced continental weathering were associated with high values of clastic ratios such as Si/Al, Ti/Al, and Zr/Al, suggesting increased terrigenous sediment supply during intensified hydrological cycling. These ratios further provided inferences about the changes in sediment grain size, such as a change from shale to coarse silt- and sand-size fractions. [ABSTRACT FROM AUTHOR]

Various isotopic and palynological indicators have shown interspersed periods of aridity and humidity for the late Paleocene to early Eocene in central China, so the paleoclimate conditions remain unclear. This research investigates the environmental characteristics of a saline lake in the Jiangling depression, southwestern Jianghan Basin, from the Paleocene to the Eocene, using bulk-rock geochemistry in a 1280 m sediment core. The ratios of FeO/MnO, Al2O3/MgO, and C-value indicate a semi-humid to semi-arid climate in the early–middle Paleocene. There was a rapid shift to a humid climate during the late Paleocene to early Eocene, following a short time of intense dryness. The Eocene climate was arid, but experienced intermittent humidity. The variation trend of the CIA, CIW and PIA was similar to that of FeO/MnO, Al2O3/MgO, and the C-value, so chemical weathering of the surrounding rocks was controlled by climate change. The lake redox conditions in the Jiangling depression from the Paleocene to the Eocene were reconstructed using the ratios of U/Th, Ni/Co, and V/Cr. During humidity and alternations of aridity and humidity, the lake water received external water input, resulting in weak stratification, so the sediments were in oxidizing conditions. During aridity, lakes become endorheic, leading to sediments forming in reduced conditions. The salinity of the lake in the Jiangling depression from the Paleocene to the Eocene was determined through analysis of sedimentary sequences and the trend of the Sr/Ba ratio. In the early–middle Paleocene, lake salinity varied greatly. From the late Paleocene to the early Eocene, lake salinity decreased. In the Eocene, lake salinity increased and halite precipitated, but lake salinity finally decreased due to a humid climate. During the late Paleocene–early Eocene, the occurrence of multiple humid climates in the Jiangling depression were not merely regional effects. The most significant humidity was caused by a global hyperthermal (PETM), which caused a huge increase in precipitation in the whole of East Asia and even in low latitudes around the world. [ABSTRACT FROM AUTHOR]

Ediacaran to Early Cambrian sequences are well preserved in several synclines within the Lesser Himalaya. We have conducted multi-proxy geochemical and stable isotopic studies on carbonaceous sediments of the basal Tal Group to decipher redox conditions of the Earliest Cambrian Ocean. Organic matter is immature, predominantly aliphatic and likely derived from marine phytoplankton. The S/C(organic) ratios above 0.4; strong enrichment of redox-sensitive trace elements V, Mo, U and Cd; higher DOPT, U/Th, V/Sc, Mo/Sc and V/(V+Ni) ratios; V/Al–U/Al–Mo/Al systematics and U–Mo enrichment factors indicate anoxic to euxinic conditions of deposition. Large variations (5–7‰) in δ13C likely reflect spatial heterogeneity or vertical gradient in DIC compositions of the Early Cambrian Ocean, and possibly capture the part of Basal Cambrian negative Carbon isotope Excursion (BACE). Finely disseminated texture of pyrite framboids with sizes mostly below 10 µm suggest sulfide reduction within the water column in an open system. Isotopically heavy δ34S values (+4.5 to +22.8‰) overlap with the δ34Ssulfate of contemporary Fortunian ocean (+10 to +40‰), suggesting sulfidic conditions and small size of the sulfate reservoir. Whereas the REE+Y proxies of the same set of samples show seawater-like patterns, with strong HREE enrichment, positive Y and La anomalies and negative Ce anomaly (avg. Ce/Ce* = 0.78), indicating REE uptake by phytoplankton from an oxidized-euphotic surface zone. The combined geochemical and isotopic data suggest a strongly stratified ocean with sulfidic bottom water and oxidized surface water. Episodic shoaling of anoxic deep water onto the surface possibly caused the extinction of benthic Ediacaran fauna, and the surface oxidized zone likely provided the niche for further metazoan radiation. [ABSTRACT FROM AUTHOR]

The Upper Cretaceous carbonate successions of the Sarvak Formation host giant oil reservoirs in the Persian Gulf. In this research, a total of 28 oil samples from nine oilfields located in the western, central and eastern parts of the Persian Gulf region were studied to determine the genetic relationships of oils, depositional setting of possible source rocks, thermal maturity, and source-rock ages in the Persian Gulf basin. According to the measured geochemical data, the source rocks facies vary from marine carbonates and marl/carbonates in the central and eastern oilfields to shale/carbonates in the western oilfields. The Pr/Ph ratio, steranes and terpanes suggest anoxic to dysoxic conditions of the depositional environments. The depositional environments experienced both low water stratification/low salinity and normal salinity/unstratified conditions. Evaluation of the saturated and aromatic biomarkers shows that all oil samples are mature and most of the source rocks lie within the beginning of the oil-generation window. The thermal maturity of the central oilfields is higher than that of the other samples, and has gone beyond the oil-generation stage. The C28/C29 steranes ratio suggest that the central oilfields of the Persian Gulf have Paleozoic and Jurassic source rocks, whereas the Sarvak reservoir in other parts of this region is sourced from Cretaceous carbonate rocks.

ABSTRACTSeagrasses can enhance nutrient mobilization in their rhizosphere via complex interactions with sediment redox conditions and microbial populations. Yet, limited knowledge exists on how seagrass-derived rhizosphere dynamics affect nitrogen cycling. Using optode and gel-sampler-based chemical imaging, we show that radial O2 loss (ROL) from rhizomes and roots leads to the formation of redox gradients around below-ground tissues of seagrass (Zostera marina), which are co-localized with regions of high ammonium concentrations in the rhizosphere. Combining such chemical imaging with fine-scale sampling for microbial community and gene expression analyses indicated that multiple biogeochemical pathways and microbial players can lead to high ammonium concentration within the oxidized regions of the seagrass rhizosphere. Symbiotic N2-fixing bacteria (Bradyrhizobium) were particularly abundant and expressed the diazotroph functional marker gene nifH in Z. marina rhizosphere areas with high ammonium concentrations. Such an association between Z. marina and Bradyrhizobium can facilitate ammonium mobilization, the preferred nitrogen source for seagrasses, enhancing seagrass productivity within nitrogen-limited environments. ROL also caused strong gradients of sulfide at anoxic/oxic interfaces in rhizosphere areas, where we found enhanced nifH transcription by sulfate-reducing bacteria. Furthermore, we found a high abundance of methylotrophic and sulfide-oxidizing bacteria in rhizosphere areas, where O2 was released from seagrass rhizomes and roots. These bacteria could play a beneficial role for the plants in terms of their methane and sulfide oxidation, as well as their formation of growth factors and phytohormones. ROL from below-ground tissues of seagrass, thus, seems crucial for ammonium production in the rhizosphere via stimulation of multiple diazotrophic associations.IMPORTANCESeagrasses are important marine habitats providing several ecosystem services in coastal waters worldwide, such as enhancing marine biodiversity and mitigating climate change through efficient carbon sequestration. Notably, the fitness of seagrasses is affected by plant–microbe interactions. However, these microscale interactions are challenging to study and large knowledge gaps prevail. Our study shows that redox microgradients in the rhizosphere of seagrass select for a unique microbial community that can enhance the ammonium availability for seagrass. We provide first experimental evidence that Rhizobia, including the symbiotic N2-fixing bacteria Bradyrhizobium, can contribute to the bacterial ammonium production in the seagrass rhizosphere. The release of O2 from rhizomes and roots also caused gradients of sulfide in rhizosphere areas with enhanced nifH transcription by sulfate-reducing bacteria. O2 release from seagrass root systems thus seems crucial for ammonium production in the rhizosphere via stimulation of multiple diazotrophic associations.

The Venetian Plain is known for areas with high concentrations of arsenic (As) in groundwater (up to more than 400 μg/L; exceptionally 647 μg/L, in selected areas). A study area was chosen, north of Padua, which exhibits typical residential, industrial, and agricultural characteristics similar to most Western countries and lacks hydrothermal, volcanic, or anthropogenic sources of arsenic. The pilot area was the focus of several studies which are reviewed in this note. The objectives of the studies were to verify the distribution of As concentrations in groundwater and sediments (mineralogical and geochemical analysis of groundwater sediments and of filtered and unfiltered groundwater) and to model the mobility of arsenic arising from water-rock interaction. The grain size of aquifer reservoirs includes gravel, sand, silt, and clay. The amount of organic matter in the aquifer sediments of the study area seems peculiar (higher) compared to other plains in the world; it influences the redox potential and the relative concentration of As in groundwater. Arsenic contamination in groundwater and redox conditions varied greatly in the area. Groundwater under oxidizing and highly reducing conditions had much lower arsenic concentrations compared to groundwater under intermediate reducing conditions. Arsenic minerals (such as realgar-pararealgar) occur in aquifer sediments and they were documented in the studied materials by different analytical techniques for the first time in the context of the Italian plains. Since these minerals are rare throughout the world in plain sediments not affected by volcanic or hydrothermal activity, their occurrence is a distinctive feature of the Venetian Plain aquifer. These arsenic minerals were found in peat sediments of the study area, consistent with geochemical modeling results, which require highly reducing conditions for their precipitation from groundwater. Modeling suggests that under oxidizing and up to slightly reducing conditions (from 200 mV to -50 mV), arsenic is adsorbed on solid phases, but a further decrease in redox potential leads arsenic desorption from solids and consequent groundwater contamination (from -50 mV to -250 mV). If the redox potential becomes even more negative (below -250 mV), geochemical conditions are favorable to the formation of arsenic sulfides. The precipitation of the realgar-pararealgar phases, predicted by the geochemical model, proceeds by extracting arsenic from the groundwater and quantitatively accounts for the lower arsenic concentration measured in the highly reducing groundwater of the study area.

The Eocene Kopili Formation in the Assam foreland basin records sediment sources, tectonic activity and depositional environments following the India-Eurasia collision. Mineralogical and geochemical analysis of these shales exposed near Garampani, Assam, NE India was conducted to study the diagenesis, palaeoweathering, palaeosalinity, redox conditions, tectonic settings and provenance. The Kopili Formation is composed of mainly shale with thin beds of limestone, black shale and sandstone and these units overlie the Upper Sylhet Limestone. The presence of goethite-rich phosphatic nodules, secondary precipitation within the fissile planes of shale and the occurrence of anatase, talc, smectite and chlorite suggest diagenesis. The prevalence of kaolinite and mean Chemical Index of Alteration (CIA), Chemical Index of Weathering (CIW), Al2O3/MgO and Rb/Sr values of 86.73, 97.26, 16.36 and 1.32, respectively indicates extensive source rock weathering in humid tropical climate. The Index of Compositional Variation (ICV) values ranging between 0.47 and 2.38 also signify high weathering and tectonically active basin. The Sr/Ba ratio 0.34 ± 0.27 (mean±2σ) suggest overall freshwater basin. The Ni/Co (2.84 ± 2.29), V/Cr (1.65 ± 0.45) and Ce/Ce∗ (0.97 ± 0.63) suggest fluctuating redox environment. The samples predominantly cluster in continental island arc domain on the Th-Sc-Zr/10, La-Th-Sc and Th-Co-Zr/10 discriminant diagrams. Elemental ratios of Th/Sc, La/Sc, Cr/Th with average 0.91, 3.18, 10.13 respectively and La/Th-Hf plot suggest a felsic source rock. The Kopili shale was deposited in freshwater, continental island arc basin with fluctuating redox conditions, receiving sediments from weathered Himalayan granites and gneisses under a warm and humid climate. Subsequently, they underwent diagenetic alteration by low-pH fluid(s).

The black shales of the Saergan Formation, which represent one of the main hydrocarbon source rocks in the Tarim Basin, witnessed a time span of organic matter enrichment by profound changes in the Earth System. A multi-proxy geochemistry study was carried out on the samples of the Saergan Formation to reconstruct the depositional environment and to explore the mechanism of organic matter enrichment of the unit at the Yingshanbeipo section, Keping area, northwest Tarim. Elemental and TOC data are suggestive of an upwelling setting, with a less pronounced oxygen minimum zone (OMZ) compared to the highly productive Peru and Namibian margins. Ferruginous anoxic bottom water conditions prevailed during most time of the deposition, with suboxic conditions dominating the basal and the top parts of the studied unit. As a whole, primary productivity seems to be the dominating factor that controlled the micronutrients and OM accumulations in the Saergan Formation whereas the role of benthic redox conditions may have been subordinate. The variations in primary productivity and bottom water redox conditions were resulted by the multiple, interacting environmental factors including nutrient supply regulated by oceanic circulation and climate changes, and relative sea-level fluctuations.

Microbial processes can influence the complex geochemical behaviour of the toxic metalloid antimony (Sb) in mining environments. The present study is aimed to evaluate the influence of microbial communities on the mobility of Sb from solid phases to water in different compartments and redox conditions of a mining site in southwest (SW) Spain. Samples of surface materials presenting high Sb concentrations, from two weathered mining waste dumps, and an aquatic sediment were incubated in slurries comparing oxic and anoxic conditions. The initial microbial communities of the three materials strongly differed. Incubations induced an increase of microbial biomass and an evolution of the microbial communities' structures and compositions, which diverged in different redox conditions. The presence of active bacteria always influenced the mobility of Sb, except in the neutral pH waste incubated in oxic conditions. The effect of active microbial activities in oxic conditions was dependent on the material: Sb oxic release was biologically amplified with the acidic waste, but attenuated with the sediment. Different bacterial genera involved in Sb, Fe and S oxidation or reduction were present and/or grew during incubation of each material. The results highlighted the wide diversity of microbial communities and metabolisms at the small geographic scale of a mining site and their strong implication in Sb mobility. [ABSTRACT FROM AUTHOR]

Studying the accumulation rules of organic matter (OM) in paleo-ocean sediments can not only enhance our understanding of how OM becomes enriched in ancient oceans but also provide guidance for the exploration of shale gas in unconventional shale strata. A breakthrough has been made in shale gas exploration in the early Cambrian Qiongzhusi Formation in South China. However, less attention has been paid to the intraplatform basin of the Yangtze Platform, and the factors controlling organic matter enrichment in this special region remain unclear. This study focuses on a continuous drilling core across the full well section of the Qiongzhusi Formation in the intraplatform basin of the Yangtze Platform. Through the comprehensive analysis of total organic carbon (TOC), major and trace elements, and Mo isotopes, this study investigates the controlling factors for OM enrichment with δ98/95Mo ratios utilized to identify the existence of euxinic bottom water. The examined 240 m long core can be divided into four units, where the TOC values of the lower Units 1 and 2 (0.2–5.0 wt.%) average higher than the upper Units 3 and 4 (0.2–2.5 wt.%). Redox indicators (U/Th, Ni/Co, EF(Mo)—EF(U)) indicate an increasing oxidation of bottom waters from the bottom upwards. δ98/95Mo data further confirm the presence of weakly euxinic conditions in Units 1 and 2, addressing the ongoing controversy surrounding bottom water redox environments. Primary productivity indicators (Ni/Al, Cu/Al) suggest a relatively low average productivity level within the intraplatform basin. The upwelling indicators EF(Co) * EF(Mn) of different profiles in the Yangtze Platform suggest that low productivity within the intraplatform basin can be mainly attributed to the absence of upwelling. Consequently, this study proposes an organic matter enrichment mechanism for the Qiongzhusi Formation in the intraplatform basin, which emphasizes the significance of the redox environment in the formation of high-quality hydrocarbon source rocks in restricted environments that lack upwelling, setting it apart from the deep ocean. These findings have the potential to provide valuable insights for the exploration of high-quality hydrocarbon source rocks in other similar regions. [ABSTRACT FROM AUTHOR]

Abstract—This paper presents numerous new data on the geochemical composition of olivine, clinopyroxene, and leucite phenocrysts, as well as spinel inclusions in olivine and quench glass from lamproites of Gaussberg volcano (East Antarctica). Most of the olivine phenocrysts in the Gaussberg lamproites are high Mg varieties (Fo89–91) with elevated Ni contents (up to 4900 ppm) and high Ni/Co ratios. According to data of about 320 clinopyroxene analyses, two groups of diopsidic phenocrysts have been established. Group I consists mainly of high-Mg varieties (Mg#>80), while group II clinopyroxenes are less magnesian (Mg# 52–80). The main difference between the clinopyroxenes of the two groups is the elevated contents of Al2O3, FeO and reduced TiO2, Cr2O3, and NiO in the compositions of group II compared to group I, as well as different contents of trace elements, which may reflect their crystallization from different types of primary melts. According to the study of ~550 grains of leucite phenocrysts in the Gaussberg lamproites, it was shown that they correspond to the ideal stoichiometry of leucite K[AlSi2O6] and are enriched in Na2O (0.05–0.35 wt %), but depleted in K2O (19.9–20.9 wt %) compared to leucites from lamproites of other provinces. The BaO content reaches 0.3 wt %, SrO –0.04 wt %. The iron content in most leucite phenocrysts varies within 0.7–1.2 wt % Fe2O3, but some grains have the low Fe2O3 contents (<0.5 wt %). In leucite microlites of the groundmass and rims of phenocrysts, the Fe2O3 content can reach 2.4 wt %, which may indicate more oxidized conditions at lava eruption. Based on the study of natural samples, existing experimental data and numerical models, the order and conditions of crystallization of the Gaussberg lamproites were obtained. Crystallization proceeded in the following order: chromian spinel → chromian spinel + olivine → olivine + leucite (± chromian spinel) → olivine + leucite + clinopyroxene (± chromian spinel). The near-liquidus assemblage represented by high-Mg olivine phenocrysts with inclusions of Cr-spinel was formed in the temperature range from 1180 to 1250°C. Further crystallization of the melt with the formation of an association of olivine+leucite+clinopyroxene phenocrysts could occur at pressures below 2 GPa and temperatures of 1070–1180°C, corresponding to the presence of water in the magmatic system. Estimates of the redox conditions of crystallization of lamproites obtained using different oxybarometers vary in a wide range from QFM-0.5 to QFM+2.3. The elevated Ni contents in liquidus olivines of Gaussberg indicate the high nickel contents in the source. It is shown that the formation of ultra-alkaline magmas in the Gaussberg volcano area is likely related to melting of the continental lithosphere, which was heterogeneous and included both the peridotite mantle and hydrous pyroxenite fragments. [ABSTRACT FROM AUTHOR]

Previous studies have revealed dynamic and complex redox conditions of the late Ediacaran ocean. Integrated analyses of Ediacaran successions on different continents can help to better understand global ocean redox conditions. In this study, we used iron and redox-sensitive trace elements (RSTEs) geochemical analyses to present the detailed redox conditions of the late Ediacaran Dongpo Formation on the southern margin of the North China Craton (NCC). Paleoredox reconstruction reveals a dominantly anoxic late Ediacaran ocean punctuated by multiple transient oxygenation events across the southern margin of the NCC. These transient oxidation events in the NCC may have contributed to the appearance of the Ediacaran tubular fossil Shaanxilithes. Based on the assumption that local iron speciation data in a global framework can track the mean and variance of paleoredox conditions through time, we additionally analyzed about 3300 new and published iron speciation data from fine-grained clastic rocks to infer the global redox change in Ediacaran–Cambrian oceans. Our statistical analyses indicated dynamic Ediacaran marine redox conditions and stepwise early–middle Cambrian ocean oxygenation. The appearance and rise of the Ediacaran biota and the diversification of metazoans corresponded temporally with the middle Ediacaran global ocean oxygenation and the early–middle Cambrian stepwise oceanic oxygenation, respectively. Our results highlight the coevolutionary relationship between ocean redox conditions and early animals. [ABSTRACT FROM AUTHOR]

Nitrogen storage capacity and partitioning between main N hosts have been investigated in N-bearing Al-rich natural pelite at 3.0–7.8 GPa, 825–1070 °C and oxygen fugacity (f O 2) from NNO (Ni-NiO buffer)+0.3 to NNO-4.1 log units. Under the conditions of hot subduction, pelite converts into a phase assemblage typical of ultrahigh-pressure (UHP) eclogites. Phengitic muscovite in this assemblage is in equilibrium with a volatile-rich granite-like melt at 3.0 GPa and with supercritical fluid at 5.5–7.8 GPa, and contains, respectively, 115–135 and 759–962 wt ppm N H 4 + at f O 2 values close to NNO. Both melt and supercritical fluid have H 2 O and CO 2 as predominant volatiles and the NH 3 /(NH 3 + N 2) ratio from 0.04 to 0.12. The pattern of nitrogen partitioning between its main hosts in pelite (D NH 4 Ms - M e l t = 0.41–0.58 and D NH 4 Ms - F l u i d = 0.63–2.4) proves that the ammonium exhibits moderately incompatible to compatible behavior within a hot oxidized slab in the pressure range from 3.0 GPa to 7.8 GPa. Therefore, even relatively oxidized sediments containing phengitic muscovite can efficiently transport nitrogen to the mantle at sub-arc depths under the hot subduction conditions. At the same time, the changeover of the N host from biotite to muscovite at the arc depths in combination with subsequent pelite melting and an abrupt decrease in phengitic muscovite abundance in pelite may lead to an avalanche-like N outgassing of the slab. The incorporation of an additional nitrogen source of (NH 3 + N 2) into pelite reduces f O 2 to NNO-3.1 – NNO-4.1 log units and increases both the NH 3 /(NH 3 + N 2) ratio in the fluid (up to 0.44–0.86) and the N H 4 + concentration in phengitic muscovite (up to 3750–3820 wt ppm). K-cymrite was produced in pelite at P ≥ 6.3 GPa and the bulk nitrogen content 3.2–5.9 wt%. K-cymrite possesses exceptional nitrogen storage capacity: it hosts 1.4–1.6 wt% N H 4 + , up to 0.5 wt% NH 3 , and 4–6 wt% N 2. The D N - NH 4 Cym - M s coefficient is as high as 20. Being stable in sediments subducted to mantle depths, K-cymrite, with its extremely high storage capacity, can act as a huge hidden redox-insensitive nitrogen reservoir in the mantle and thus can be involved in the deep nitrogen cycle. [ABSTRACT FROM AUTHOR]

The Cambrian is a critical period in the evolution of life and environment. Reconstructing the marine sedimentary environment, notably redox conditions during this period is key to explore the spatial and temporal evolutionary characteristics of seawater chemistry and the relationship between biological evolution and environmental changes. In this study, the major elements, trace elements and organic carbon content (TOC) of the Lower Cambrian Xishanbulake-Xidashan formations in well Tadong 2 in the Tarim Basin were analyzed, and the sedimentary environment of the formations was reconstructed. The results show that the water body was in weak restriction condition when the formation was deposited. The redox state of bottom waters was dominated by anoxia, but the degree of anoxia varied obviously. Specifically, the middle part of the Xishanbulake Formation showed elevated anoxia (euxinia) in bottom waters compared to the lower and the upper parts, while the Xidashan Formation showed a decrease in anoxia from the middle and the lower parts to the upper part and an expansion of bottom water oxidability. The results are consistent with the observation in previous studies that the Early Cambrian seawaters was characterized by dynamic changes in the redox state. The analysis of organic matter enrichment mechanism of Xishanbulake-Xidashan formations in well Tadong 2 shows that organic matter enrichments in the formations is not controlled by a single factor. The anoxic/euxinic environment in the middle and the lower parts of the Xishanbulake Formation is more conducive to the preservation of organic matter, while the higher level of primary productivity played a key role in the sedimentation of the upper part of the Xishanbulake Formation and the Xidashan Formation.

The end-Devonian Hangenberg Crisis was one of the biggest Phanerozoic mass extinctions. However, the mechanism(s) that triggered this event is still debated. In this study, multiple geochemical paleoredox proxies (redox-sensitive trace metals [e.g., Mo, U, Re, V] and isotope systems [Mo, U, S, C]) were applied to the Exshaw Formation black shales to infer ocean redox conditions during the Hangenberg Crisis. The measured δ13C org values generally decrease upsection in the Exshaw Formation. The Exshaw black shales have increasing maturity levels from east to west in the Western Canada Sedimentary Basin. Large sulfur isotope fractionations (–15‰ to 65‰) between original seawater sulfate and pyrite is best explained by microbial sulfate reduction during deposition and early diagenesis rather than thermochemical sulfate reduction. Precise Re-Os ages previously reported for the Exshaw Formation suggest that metal geochemical signatures in these shales, including overmature shales, were minimally affected by hydrocarbon maturation and reflected depositional conditions. Both Sr/Ba and TS/TOC ratios (the latter only from immature shales affected minimally by hydrocarbon generation) suggest predominantly brackish and marine settings with significant water exchange between the basin and open ocean. The TOC contents, redox-sensitive trace metal concentrations (Mo, U, Re), and Fe speciation indicate local bottom waters ranged from suboxic (with sulfidic pore waters) to euxinic. The authigenic δ98Mo and δ238U values for the Exshaw shales range from 0.3‰ to 1.1‰, and from –0.23‰ to 0.39‰, respectively. The δ98Mo of the Exshaw Formation may have been offset to lower values than coeval seawater because of a local particulate Fe-Mn shuttle and/or local weakly euxinic bottom waters. Two different correlation patterns (positive correlation and no correlation) of δ238U and U enrichment factors (EF) were observed for Exshaw black shales deposited from locally euxinic bottom waters. The positive correlation group samples (−0.13‰ to 0.23‰) suggest U isotope fractionations (0.4‰ to 0.8‰) between sediments and seawater like those observed in modern euxinic basins. Higher δ238U values (>0.2‰) in the no correlation group suggest even larger U isotope offsets (0.8–1.2‰) from seawater, possibly associated with removal of U into organic floccule layers during deposition. Applying the above Mo and U isotope fractionations to the Exshaw shales, global seawater δ98Mo and δ238U at the Devonian-Carboniferous boundary (DCB) may have been in the range of 1.4‰ to 1.9‰ and −0.9‰ to −0.5‰, respectively. A Mo and U isotope mass balance model suggests a large areal extent of euxinic seafloor (6–10%) at the DCB, which could be pervasive along continental margins and in epicontinental seas during transgression. Therefore, our data support expanded ocean euxinia at the DCB as an important contributor to the Hangenberg Crisis. [ABSTRACT FROM AUTHOR]

Diagenesis of archaeological bones proceeds via a complex combination of chemical, physical and/or microbial processes often over several millennia. These processes are influenced by the depositional environment, including fluctuations in pH, mineral availability and water table. This study investigates diagenetic alterations to the mineral and organic (collagen) phases of bones from a Neolithic site, Etton Causewayed Enclosure (Cambridgeshire, UK). Archaeological bones from some layers of the gravel site at Etton exhibit unusual staining patterns, including iron and manganese rich layers underneath the exterior bone surface and manganese speckling throughout the bone. A range of analytical techniques (micro-CT, FTIR, XRF and SEM-EDS) were employed to investigate the mineralisation within three bones from this site. Diagenesis appears to have occurred through a combination of bacterial degradation and mineral formation due to the changing redox conditions at the site caused by fluctuating groundwater. The reason for the positioning of the manganese layers beneath the iron layers at the surfaces of the bone remains unclear. [ABSTRACT FROM AUTHOR]

In many alkaline complexes, large amounts of ultramafic rocks occur together with carbonatites, melilitolites and other alkaline silicate rocks. There is an ongoing debate if and how these contrasting lithologies were formed by differentiation of a common, mantle-derived silicate magma or rather by metasomatic processes between carbonatite and country rocks. In order to find petrological evidence for one or the other, two key examples, the Gardiner (E Greenland) and Kovdor (Russia) complexes are compared in this study. Despite their similar tectonic setting and succession of rock types, they show significant differences in the texture and mineral composition of ultramafic rocks. Ultramafic rocks from Kovdor include calcite- and biotite-rich dunites and pyroxenites without typical cumulate textures. They consist of Ni-poor forsterite, Cr-poor diopside and Ni-Cr-poor spinel and are possibly metasomatic reaction products between mantle-derived carbonatite melts and silicic host rocks. Similar ultramafic rocks are associated with carbonatites e. g. at Palabora (South Africa), Afrikanda (Russia), and Salitre (Brazil). In contrast, the ultramafic rocks from Gardiner show well-preserved cumulate textures and consist of Ni-rich forsterite, Cr-rich diopside as well as Cr-Ni-Ti-rich spinel and also contain F-Cl-rich apatite. They record an increase in aSiO2 from dunite to pyroxenite at similar f O2 (ΔFMQ ~ +1.2, with FMQ = fayalite-magnetite-quartz buffer), indicating that these rocks represent cumulates of an evolving, moderately oxidized mafic melt derived from a Ti-rich mantle source, similar to other rocks of the North Atlantic igneous province. In contrast to systems like Kovdor where carbonatite metasomatism is likely dominant, Ti-rich parental silicate magmas can abundantly crystallize Ti phases, as recorded by massive perovskite cumulates in Gardiner melilitolites. This can effectively scavenge HFSE from the magmatic system early in its evolution and likely explains HFSE-barren carbonatites at Gardiner, while those from Kovdor are highly HFSE-enriched. In summary, the results of our study provide strong textural and mineral chemical evidence that ultramafic rocks in alkaline complexes can be of both cumulate and metasomatic origin; the specific type has an important bearing on their HFSE enrichment and on the types of ores present in such complexes. [ABSTRACT FROM AUTHOR]

The relationship between the Late Ordovician–Early Silurian sedimentary system, weathering, paleoclimate, and primary productivity in the Yangzi region is not well understood. In this study, by analyzing the sedimentation cycle and major trace elements of the Youc well 2 in the southeast Sichuan Basin, the coupling relationships of weathering indicators, terrigenous debris input indicators, paleoclimate, redox condition indicators, U-Mo covariance model, Mo/TOC relationship, and paleoproductivity indicators are investigated. The results show that single-well logs delineate four third-order sedimentary sequences (SS1, SS2, SS3, and SS4), two sedimentary subfacies, and four sedimentary microfacies in the Wufeng Formation–Longmaxi Formation. The weathering degree is stronger at the bottom where the climate shifts from warm–wet to cold–dry, and the seawater is in an oxidic–anoxic–oxidic–anoxic environment. While the primary productivity and material source input decreases gradually in the middle and upper part, the climate becomes dry and cold, and the seawater is in an anoxic–oxidic environment. Thus, a rock enrichment model for the organic matter shale of the Wufeng Formation–Longmaxi Formation in southeast Sichuan has been established. This provides more information on the control factors concerning organic matter enrichment and their interactions. [ABSTRACT FROM AUTHOR]

Hydrogeochemical processes that govern selected inorganic substances distribution in a semi-confined aquifer were characterized using traditional hydrogeochemical approaches and natural background levels (NBLs). Saturation indices and bivariate plots were used to investigate the effects of water–rock interactions on natural evolution of the groundwater chemistry, whereas Q-mode hierarchical cluster analysis and one-way analysis of variance classified the groundwater samples into three distinct groups. To highlight the groundwater status, NBLs and threshold values (TVs) of the substances were calculated using pre-selection method. Piper's diagram showed that the Ca–Mg–HCO3 water type was the only hydrochemical facies of the groundwaters. Although all samples, except a borewell with a high NO3− concentration, had major ion and transition metal concentrations within the World Health Organization's recommended guideline values for drinking water, Cl−, NO3− and PO43− exhibited scattered distribution patterns, reflecting their nonpoint anthropogenic sources in the groundwater system. The bivariate and saturation indices revealed that silicate weathering and possible gypsum and anhydrite dissolution contributed to the groundwater chemistry. In contrast, NH4+, FeT and Mn abundance appeared to be influenced by redox conditions. Strong positive spatial correlations between pH, FeT, Mn and Zn suggested that mobility of these metals was controlled by pH. The relative high F− concentrations in lowland areas may imply the impact of evaporation on this ion's abundance. Contrary to TVs of HCO3−, those of Cl−, NO3−, SO42−, F− and NH4+ were below the guideline values, confirming the influence of chemical weathering on the groundwater chemistry. Based on the present findings, further studies that take into account more inorganic substances are required for NBLs and TVs determination in the area, thereby setting up a robust sustainable management plan for the regional groundwater resources. [ABSTRACT FROM AUTHOR]

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Early Cambrian Earth history witnessed significant changes in marine environments and biological evolution contemporaneous with extensive accumulation of organic-rich shale. However, major factors controlling hyper-enrichment of organic matter (OM) of lower Cambrian shale deposits remain controversial. Black shale of the lower Cambrian Niutitang Formation (NTT) of the marginal Yangtze Platform (South China) deposited during the Cambrian middle Age 2 are especially organic-rich, with total organic carbon (TOC) concentrations of as much as 13.0 wt%. Geochemical evidence suggests that cool, dry paleo-climatic conditions that prevailed on the Yangtze Platform during the Cambrian Fortunian-late Age 2, induced vigorous coastal upwelling. Paleo-productivity level assessments indicate that the magnitude of primary productivity contemporaneous with deposition of the NTT shale deposits exceeded that of modern upwelling systems (e.g., Peruvian Margin). The widespread occurrence of phosphate nodules within these deposits and decreased Co-EF × Mn-EF values of associated lower Cambrian black shale successions deposited along the margin of the Yangtze carbonate platform suggest extensive coastal upwelling. Widespread and strong coastal upwelling in tandem with elevated surface water primary productivity and anoxic (even euxinic) bottom water conditions are manifested by deposition of OM hyper-enriched black shale during Cambrian Fortunian to middle Age 2 time. However, weakened seasonal upwelling that appears to have prevailed during the late Cambrian Age 2 was accompanied by accumulation of NTT shale deposits of diminished TOC content. In summary, this study provides robust evidence of extensive coastal upwelling along the marginal Yangtze Platform during early Cambrian time that favored accumulation of OM hyper-enriched shale. These results help to elucidate the distribution of high-quality lower Cambrian natural gas source rocks in South China. • Early Cambrian upwelling history along the Marginal Yangtze Platform is reconstructed. • OM hyper-enrichment of lower Cambrian shale deposits was closely associated with strong coastal upwelling. • A conceptual model depicting OM enrichment along the marginal Yangtze Platform during Cambrian Fortunian-Late Age 2 time is presented. [ABSTRACT FROM AUTHOR]

Redox-sensitive trace metals have not only been widely used as the proxy for palaeoredox potential due to the strong enrichments under reducing conditions but also provide critical information into water-mass properties, such as the degree of basin restriction. In order to reveal the Early Silurian post-glacial transgression hydrographic restriction conditions throughout the Middle and Upper Yangtze region, trace metal concentrations and organic geochemical data of the lower Longmaxi Formation were analyzed by the Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Leco combustion techniques. We analyzed the hydrographic restriction conditions and redox conditions of different depocenters, including the Southern, Eastern, and Northern Sichuan Basin depocenters and the Western Hubei Region depocenter. The sedimentary Mo-TOC relationship, Mo EF -U EF covariation, and upwelling intensity suggest that the Southern, Eastern Sichuan Basin depocenters and the Western Hubei Region depocenter were deep water areas with moderate hydrographic restriction, whereas the restriction conditions of Northern Sichuan Basin depocenter was relatively weak. In addition, due to the combined effect of geographical location, connectivity with the open Qinling Ocean, and estuarine circulation, restriction degrees varied in the same depocenter. The redox proxy (C org /P) indicated that the lower Longmaxi Formation was deposited in an anoxic water column. There are significant spatial differences in redox conditions in different depocenters and different locations within the same depocenter, which may be controlled by relative sea level rise, hydrographic restriction, and upwelling intensity. Anoxic conditions were more likely to occur in areas where water column was relatively deep and restricted. In addition, the anoxic conditions in the Northern Sichuan Basin depocenter may also associated with the strong upwelling intensity and the behavior of P cycling back to water column, which can promote the primary productivity and further maintain persistent anoxic conditions. The correlation between C org /P and Mo/TOC indicates that, in relatively weak restriction basin, the trace elements enrichment in sediments was controlled by trace elemental concentrations in seawater. In moderate restriction basin, the trace elements enrichment was mainly controlled by redox conditions. Whereas under more reducing conditions, hydrographic restriction may tend to become the dominant factor. The application of sediment Mo-TOC relationship, Mo EF -U EF covariation, and upwelling can provide insights into hydrographic restriction conditions, but the Mo/TOC relationship is limited to anoxic facies, as little trace metal accumulation could also be the consequence of oxic conditions. • The Lower Longmaxi Formation was mainly deposited in anoxic conditions due to sea level rise, moderate hydrographic restriction, and upwelling. • The Yangtze Sea experienced weak and moderate hydrological restriction during the Early Silurian post-glacial transgression. • The Middle and Upper Yangtze Sea was dominated by intermittent seasonal upwelling. • Mo accumulation is a combined effect of basin restriction, redox conditions and Mo concentrations in seawater. [ABSTRACT FROM AUTHOR]

Phosphorus, as a long-term limiting nutrient, is essential for the rapid animal diversification in the early Cambrian ocean. However, the widespread occurrence of phosphorites during this period indicates anomalous phosphorus cycling mechanisms that remain inadequately explored. To investigate the interplay between marine redox conditions and phosphorus cycling, we used geochemical proxies and synchrotron-based P K -edge X-ray Absorption Near Edge Structure (XANES) spectroscopy to analyze the Cambrian Terreneuvian Yurtus Formation (Fortunian to Stage 2) from the Tarim Block. Redox-sensitive elements, iron speciation and nitrogen isotopes reveal an expansion of the surface oxygenated waters, despite persistent ferruginous bottom waters. Moreover, a shift of phosphorus speciation was observed in bedded cherts via P K -edge XANES, suggesting a transition of phosphorus cycling. Specifically, the samples exhibit low total phosphorus contents with a high rate of carbonate-fluorapatite authigenesis in the lower Yurtus Formation. This is followed by an increase in the proportion of terrestrial-derived fluorapatite and iron-bound phosphorus, corresponding to the expansion of surface oxygenated waters. Our findings reveal a significant shift in dominant phosphorus speciation in the early Cambrian marine sediments, which is intricately linked to the coupled phosphorus‑iron‑carbon‑oxygen cycles in the Cambrian ocean. • Defining phosphorus speciation in ancient marine bedded cherts, • A shift of phosphorus burial pathway in the early Cambrian ocean. • Alteration of phosphorus cycling in the early Cambrian ocean triggered oxygenation of surface waters. [ABSTRACT FROM AUTHOR]

Depositional events have a significant impact on the terrestrial redox conditions and provide evidence for studying the organic matter enrichment. The objective of this study was to evaluate the influence of volcanic and turbidity current events on benthic redox conditions during the Upper Triassic Chang 7 member (Ch7) of the Ordos Basin. To address these issues, the varying sedimentological settings, paleoredox conditions, and relationships between the redox environment and depositional events were investigated via sedimentary analysis of the profiles, microscopic analysis, organic geochemical analysis, and elemental geochemical data. The fine-grained sediments in the Chang 7 3 submember (Ch7 3) consist of abundant organic matter, collophanite, and framboidal pyrite. However, in the upper part of the Ch7 member, there was a decrease in organic matter, a decrease in the number of microorganisms, and an increase in pyrite size, indicating that the oxic environment is not favorable for organic matter enrichment. The element and geochemical proxies show similar vertical variations and redox changes. Volcanic activity can bring substantial amounts of material or elements to the basin. The enrichment of Hg and S exhibited considerable variation, ranging from 8.7 to 274.4 ppb and from 0.16 to 4.53 wt%, respectively, which influenced the organic matter accumulation through the flourishing and death of microorganisms and redox changes in the benthic environment of the terrestrial basin. As the lake basin shrinks, the Ti and Al contents increase with increasing frequency of turbidity current events, and the terrestrial debris transported to the lake basin gradually increases while carrying large amounts of oxygen and affecting sedimentation rates, contributing to the destruction of the reducing conditions of the benthic environment, subsequently, influencing organic matter accumulation. These results will be helpful in understanding the effect of multiple depositional events on organic matter enrichment in lacustrine basins. • Geochemical and sedimentary results suggest altered redox conditions. • Volcanic activity enhanced the redox conditions. • Turbidity current events influence dilution and biodegradation efficiency. [ABSTRACT FROM AUTHOR]

Abstract We have determined rare-earth element (REE) abundances in oldhamites (CaS) from 13 unequilibrated and equilibrated enstatite chondrites (5 EH and 8 EL) and in a few enstatites by in situ, laser ablation ICP-MS. In EH chondrites, oldhamite REE patterns vary from the most primitive petrographic types (EH3) to the most metamorphosed types (EH5). In EH3, CI-normalized REE patterns are convex downward with strong positive Eu and Yb anomalies, whereas EH5 display flat patterns with enrichments reaching about 80 times CI abundances. The positive anomalies of Eu and Yb found in oldhamites of primitive EH chondrites indicate that they represent the condensation of a residual gas fraction, in a manner similar to fine-grained CAIs of carbonaceous chondrites. The early condensate may have been preserved in the matrix of unequilibrated EH. Equilibrated EH oldhamite patterns may result from metamorphic evolution and REE redistribution on the EH parent body. On the contrary, all the oldhamites from EL chondrites (EL3 to EL6) display a single kind of patterns, which is convex upward and is about 100 times enriched relative to CI, with a negative Eu anomaly. In addition, the EL pattern is similar to that of oldhamites from aubrites (enstatite achondrites). The latter observation suggests that oldhamites of all EL metamorphic types (including primitive ones) bear the signature of a magmatic event accompanied by FeS loss as vapor, prior to the assembly of the EL parent body. Given the difficulty of obtaining precise ages on enstatite chondrites, it is not possible to discuss the chronology of the events recorded by the oldhamite REE patterns.

A quantitative local analytical method with the application of inductively coupled plasma mass spectrometry with laser ablation (LA-ICP-MS) was tested at Vernadsky Institute for the determination of contents of trace elements (Cu, Zn, Co, Ni, Mn, Cr, Sc, V, Ca, Ti, Al, Y, and REE) in olivine. Olivine phenocrysts from volcanic rocks of various geological settings have been studied: island-arc basalts, mid-ocean ridge (MOR) basalts, and high-alkaline continental volcanic rocks. The contents of some elements (Ni, Co, Mn, Cr, Sc, and Zn) systematically vary during the evolution of the composition of olivine, and the concentration fields of these elements in olivine from different settings overlap one another. At the same time, the contents of some other elements (Ca, Al, Ti, V, and Cu) fundamentally differ in olivine from different geological settings. Copper content in olivine from oceanic tholeiites and highly alkaline continental volcanics is 1–3 ppm, which is systematically lower than copper content in olivine from island-arc basalts (3–9 ppm). The concentrations of vanadium in olivine in MOR basalts are higher than in island-arc and alkaline continental ones, which may be due to relatively more reduced crystallization conditions as more favorable for the incorporation of V3+ into the olivine structure. Variations in the distribution coefficients of trace elements between olivine and silicate melt () were determined for volcanic rocks from Kamchatka, the Bouvet Triple Junction, and Gaussberg volcano. It has been demonstrated that the unusually high values of = 50–150 previously identified for the lamproites of Gaussberg volcano indicate a mismatch between the composition of the quenched glass and the composition of the equilibrium melt for olivine phenocrysts. When using the bulk compositions of Gaussberg rocks, values of = 11–21 were obtained, which correspond to experimental estimates for high-potassium rocks. The redox crystallization conditions of the studied rocks were estimated using several oxybarometers based on the distribution of vanadium between coexisting olivine and melt. These values were: ΔQFM= +0.6 to +1.5 for oceanic tholeiites of the Bouvet Triple Junction area, South Atlantic, and ΔQFM = +1.5 to +2.4 for Mutnovsky volcano, Kamchatka. Estimates of the redox crystallization conditions of the highly alkaline rocks of Gaussberg volcano significantly vary depending on which model is chosen: ΔQFM= +0.2 to +4.8, which may be due to the strong effect of K2O content in the melt involved in one of the models. The newly acquired analytical data confirmed the possibility of using contents of trace elements in olivine to characterize igneous systems from different geological settings and highlighted the need for additional experimental studies on the distribution of these elements between olivine and melt, especially in highly alkaline systems. [ABSTRACT FROM AUTHOR]

Marine carbonate fabrics are intrinsically related to ocean chemistry, physical processes and biological activity. Molar tooth structure (MTS), a globally distributed structure in Proterozoic carbonate sediments, has been widely studied for more than a century; yet its connections with physical and biological processes remain unclear. Using multiple techniques, we studied ∼1.57 Ga MTS and identified a connection between its occurrence and increased marine oxygenation. In our samples, the matrix surrounding MTS is typically dominated by carbonate mud with early diagenetic dolomite crystals. High I/(Ca + Mg) ratios (up to 4.1 μmol/mol) and negative Ce anomalies (∼0.8) detected in the matrix are consistent with the oxidative removal of inhibitors such as Fe2+ and Mn2+ in the water‐column that permitted carbonate "whiting" mud precipitation stimulated by cyanobacterial photosynthesis. This cohesive but not rigid seafloor carbonate mud was a prerequisite for synsedimentary MTS crack formation. Systematically higher carbon isotope (δ13C) values in MTS microspars, relative to host sediment, support origination of the cracks by methane degassing in the organic‐rich carbonate mud. Low, but non‐zero, I/(Ca + Mg) values of the MTS microspar suggest that the precipitation of the microspar that filled the MTS cracks was triggered by oxidative removal of residual Fe2+ and Mn2+ in porewater through mixing with overlying oxygenated seawater. We therefore propose that MTS formed under moderately oxygenated conditions and that its sporadic occurrence prior to ∼1.2 Ga reflects episodes of pulsed marine oxygenation in an overall anoxic setting. Plain Language Summary: Molar tooth structure (MTS) has been identified in Precambrian carbonate sedimentary rocks for more than a century. However, its formation and significance are still not fully understood. Precambrian ocean chemistry and low oxygen levels have previously been linked to MTS formation. Here, we use carbonate iodine data as a proxy for oxygenation, and carbon isotope data to decipher microbial processes. The iodine data indicate an oxygenated environment, and the carbon isotope data support previous suggestions that degassing of microbial methane was responsible for MTS crack formation. For the first time, we show that MTS occurred in oxygenated conditions. We propose that the oxidative removal of ions such as Fe2+ and Mn2+ that can inhibit carbonate precipitation was a key factor in the formation of the cohesive carbonate mud matrix of MTS, and in the rapid precipitation of the microspar cement that filled and preserved the MTS cracks. The relatively rare occurrence of MTS prior to 1,200 Ma could therefore be a sedimentary indicator of sporadic marine oxygenation when marine conditions were mostly anoxic. Key Points: Petrographic and geochemical data constrain molar tooth structure (MTS) development in ∼1.57 Ga carbonates from North ChinaMicrobially induced water column carbonate mud and CH4 degassing from the sediment are critical for MTS formationThe connection between MTS formation and marine oxygenation suggests MTS as a sedimentary redox proxy [ABSTRACT FROM AUTHOR]

The assessment of nitrogen cycle processes in paleomarine and paleolake systems commonly relies solely on total nitrogen isotopes. If organic nitrogen and adsorbed nitrate can be effectively extracted from samples, the application of nitrogen isotopic systematics in different N forms would be beneficial for reconstructing the nitrogen cycle process in pore water and would mutually complement water chemistry information. According to the variations in δ13Corg, δ15NTN, δ15Norg and δ15Nnitrate data of the Cretaceous Nenjiang Formation in the Songliao Basin, NE China, the profile could be divided into three intervals (intervals A–C). We attribute the anomalously high δ15Nnitrate (∼+20‰) from intervals A and C to the effect of sedimentary denitrification that occurred in the benthic sediments during the early diagenetic stage. We also recognize the intimate relationship between δ15Nnitrate and δ15Norg values, which are interpreted to reflect the effect of water column denitrification in the bottom waters and/or surface pore water. Based on the comparison of nitrogen isotope variability and the evolving environmental context, we interpret the water column denitrification as primarily reflecting anoxic bottom water or surface pore waters, while the sedimentary denitrification indicated by abnormally high δ15Nnitrate can effectively represent oxic bottom water. This study not only reveals that the adsorbed nitrate can be well extracted from mudstones with low thermal decomposition degrees but also suggests that the organic nitrogen‐nitrate isotope proxies can be used as a potential parameter to track the redox structure in water masses. Key Points: Abnormally high nitrate nitrogen isotopes imply massive sedimentary denitrificationSimilar organic nitrogen isotope and nitrate nitrogen isotope distributions suggest water denitrificationOrganic nitrogen isotope and nitrate nitrogen isotope proxies provide independent evidence for redox structure [ABSTRACT FROM AUTHOR]

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