Anoxic Bottom Water Conditions Research Articles

Widespread coastal upwelling along the marginal Yangtze Platform (South China) during the early Cambrian: Implications for hyper-enrichment of organic matter

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.

Latest Pliensbachian to Early Toarcian depositional environment and organo-facies evolution in the North-German Basin (Hondelage Section)

The Pliensbachian/Toarcian boundary interval represents a transition from a coldhouse into a hothouse climate state, involving the demise of a land-based cryosphere, initiating a third-order global sea-level rise. Within the intensely studied Northwest Tethyan shelf region, the South-German Basin has been investigated in more detail than the North-German Basin (NGB). We here provide a palaeoenvironmental reconstruction of the Pliensbachian/Toarcian transition from the Hondelage fossil excavation site located in the NGB employing organic, isotope, and major/trace element proxies. Here, the late Pliensbachian was characterized by cold climate, low sea level, and a slow hydrological cycle, causing minor terrigenous sediment and nutrient fluxes to the basin, instigating low marine productivity. Shallow, well-mixed shelf waters of normal salinity favored aerobic degradation of planktonic biomass, preventing sedimentary accumulation of organic matter. These conditions changed in the earliest Toarcian, where increased temperatures led to sea-level rise via meltdown of land-based ice and accelerated the hydrological cycle, causing salinity stratification. Enhanced riverine sediment and nutrient supply from nearby landmasses promoted marine primary productivity, which caused anoxic conditions in bottom and pore waters favoring enhanced preservation and accumulation of organic matter. A short-lived sea-level fall at the Lower Elegans Bed coincided with lowered productivity and enhanced carbonate precipitation, due to reduced runoff and recovery of the carbonate factory. Increased redox-sensitive trace element concentrations above the Lower Elegans Bed suggest a renewed inflow of low-salinity arctic water masses via the Viking Corridor and potentially increased freshwater input, promoting water column stratification, enhanced planktonic productivity, and re-establishment of bottom water anoxia/euxinia.Graphical abstract

Weathering Intensity, Paleoclimatic, and Progressive Expansion of Bottom-Water Anoxia in the Middle Jurassic Khatatba Formation, Southern Tethys: Geochemical Perspectives

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.

Lower Jurassic (Pliensbachian–Toarcian) marine paleoenvironment in Western Europe: sedimentology, geochemistry and organic petrology of the wells Mainzholzen and Wickensen, Hils Syncline, Lower Saxony Basin

Over the past few decades, Toarcian (Early Jurassic) black shale deposits of NW Europe have been extensively studied, and the possible global and regional mechanisms for their regional variation have been discussed. In this context, the black shales of the Northwest German Basin are still sparsely studied with regard to their palaeo-depositional history. This study aims to understand the connection between regional and global influences on the widespread Early Toarcian oceanic anoxic event by examining two wells covering the Upper Pliensbachian to Upper Toarcian sediments in the Northwestern German Basin. The core intervals were analysed using a multidisciplinary approach, including geochemistry, biostratigraphy and organic petrography. Marine palaeoenvironmental changes were reconstructed, and sediment sequences were stratigraphically classified to allow a supra-regional stratigraphic correlation. The results reveal complex interactions between sea level changes, climate warming, basin confinement, and Tethys–Arctic connectivity resulting in the Toarcian black shale deposition. Upper Pliensbachian sediments were deposited under terrigenous influence, shallow water depths, and predominantly oxic bottom water conditions. The deposition of black shale is characterized by algal organic material input and anoxic bottom water conditions. Strong correlations between water stratification, anoxia, and bioproductivity suggest that global warming and intensification of monsoonal rainfall, continental weathering, and increasing freshwater and nutrient inputs were the main factors controlling the formation of black shales. Prolonged deposition of OM-rich sediments in the NWGB may be related to intensified monsoonal precipitation in northern Europe and enhanced Tethys–Arctic connectivity at the serpentinum–bifrons transition.Graphical

Upwelling-driven biogenic silica accumulation in the Yangtze Sea, South China during Late Ordovician to Early Silurian time: A possible link with the global climatic transitions

Silica accumulation in the Yangtze Sea during the Ordovician–Silurian (O–S) transition appears to have coincided with global climatic fluctuations, widespread upwelling, and volcanism. There is a need to further evaluate their respective contributions to silica deposition and potential relationships among these factors. The current study selected siliceous deposits in the Wufeng and Longmaxi Formations from four sections spanning the inner to outer Yangtze Sea, South China, to gain a deeper understanding of the climatic and oceanographic evolution associated with silica enrichment. Al/(Al + Fe + Mn) values, the presence of radiolarians, and Si isotope values of samples recovered from the investigated shale successions offer compelling evidence that the silica is largely of biogenic origin with some terrigenous contributions. Further, various productivity and redox proxies suggest that biogenic silica (BSi) accumulated under conditions of enhanced marine productivity and anoxic bottom water conditions. Hg/TOC and Zr/Al2O3 profiles suggest intermittent volcanism during the BSi deposition in the Yangtze Sea. However, the lack of correlation between BSi and Hg/TOC values indicates that volcanic iron fertilization was not responsible for BSi accumulation. Instead, most BSi-rich samples are dominated by low MnEF × CoEF values (<0.5), consistent with BSi deposited in modern upwelling settings. Hydrographic reconstruction based on Mo–U covariation indicates a more open water setting in the outer Yangtze Sea, while the coeval inner Yangtze Sea was relatively restricted. Therefore, upwelling events appear to have been more vigorous in the outer Yangtze Sea. Published and new Chemical Index of Alteration (CIA), BSi, and MnEF × CoEF data for the Wufeng and Longmaxi Formations across the inner to outer Yangtze Sea demonstrate that temporal and spatial variations of BSi were controlled by climate-driven upwelling. In particular, cool-water upwelling contemporaneous with Hirnantian glaciation may have been responsible for the establishment of the cool-water fauna of the shallow-water Guanyinqiao Bed and enhanced silica deposition in deeper water. Moreover, a moderate negative relationship between compiled CIA and BSi contents suggests that enhanced upwelling driving BSi accumulation appears to have been favored during cooling events. Integrated analysis of BSi deposits of the Laurentia and Baltica continental margins further suggests that BSi accumulation on continental margins during the O–S transition was primarily influenced by global cooling. Therefore, we suggest that wind patterns or/and thermohaline circulation, influenced by climate fluctuations, induced widespread cold water upwelling events during the O–S transition. Moreover, elevated BSi production diluted accumulating OM resulting in the observed parabolic relationship of BSi and TOC.

Pore-water nutrient concentrations variability under different oxygen regimes: A case study in Elefsis Bay, Greece

Anthropogenic pressures considerably affect coastal areas, increasing nitrogen and phosphorous loads that lead to eutrophication. Eutrophication sometimes results in hypoxic and/or anoxic conditions near the bottom water. Dissolved oxygen (DO) concentrations influence redox-sensitive nutrients, which can alter the benthic flux of nutrients. We retrieved sediment cores from two sites in the eastern and western parts of Elefsis Bay, a semi-enclosed area of the Eastern Mediterranean, Greece, during winter and summer. In the western part, seasonally hypoxic or anoxic conditions occurred. We analysed pore-water samples under normoxic, hypoxic and anoxic bottom water conditions to study the pore-water nutrient concentrations variability under different oxygen regimes. Ex situ incubation experiments were conducted at the site experiencing oxygen deficiency by manipulating the DO concentrations. The pore-water nutrient concentrations showed higher variability at the site experiencing oxygen deficiency. Notably, elevated ammonium concentrations were observed in the pore water during anoxic conditions, in the 2–20-cm sediment layer. However, the benthic fluxes of ammonium and phosphate at the 0–2-cm sediment layer were comparable under hypoxic and anoxic conditions. The results of the incubation experiments demonstrate a direct decrease in nitrate concentrations as the DO concentrations diminished in the overlying water. The incubations after re-oxygenating the overlying water show that phosphate was more efficiently scavenged when anoxic conditions prevailed in the bottom water. The incubation experiments indicate the rapid response of the seafloor to oxygen availability, particularly concerning processes that influence nitrate and phosphate concentrations. These observations highlight the dynamic nature of nutrient cycling in shallow, seasonally anoxic environments, such as Elefsis Bay, and emphasise the sensitivity of the seafloor ecosystem to changes in bottom water oxygen availability.

Sedimentary environment and benthic oxygenation history of the Upper Cretaceous Austin Chalk Group, south Texas: An integrated ichnological, sedimentological and geochemical approach

ABSTRACTOxygen concentration in the ocean is vital for sustaining marine ecosystems. While the potential impacts of deoxygenation on modern oceans are hard to predict, lessons can be learned from better characterizing past geological intervals formed under a greenhouse climate. The greenhouse Cretaceous containing several oceanic anoxic events characterized by widespread oxygen‐deficient water is ideal in this regard. The Austin Chalk Group in south Texas (USA) shows organic‐rich intervals that can be linked to oxygen depletion in the ocean, but the exact bottom water oxygenation conditions have not been estimated. This study aims to reconstruct both sediment interstitial and bottom water oxygenation history during Austin Chalk Group deposition by integrating detailed ichnological, sedimentological and geochemical (X‐ray fluorescence and X‐ray diffraction) analyses, thereby providing a consistent model that may be applicable across a range of marine shelf settings. The 141.12 m Gise #1 core contains a continuous record of the Austin Chalk Group, providing an opportunity for unravelling oxygenation and deoxygenation events. Whereas the anaerobic–exaerobic deposits are essentially nonbioturbated, four oxygen‐related ichnocoenoses are defined, further refining the transition of aerobic to dysaerobic conditions in the sediment interstitial water. Omission surfaces and glauconitic grains, products of current‐induced scouring and condensation, suggest sporadic high‐energy events in the Austin Chalk Group ramp that drove elevated terrestrial inputs. Geochemical data further help to identify anoxic bottom water conditions within the anaerobic facies. Additionally, the lowermost part of the Austin Chalk Group illustrates redox cycles, whereas dilution events characterized by elevated terrestrial input are identified throughout the rest of the Austin Chalk Group. The evolution of oxygenation levels in sediment interstitial water and bottom water disputes the existence of a long‐lasting oxygen‐deficient sea in south Texas. The refined depositional model may be applicable to coeval shelfal settings. Moreover, the results provide insights into variable, evolving palaeoclimatic and palaeoceanographic conditions of the greenhouse Late Cretaceous.

Controls on organic matter enrichment of the early-middle Miocene lacustrine oil shale, central Tibet (SW China): New insights from clay minerals and geochemistry

The Lunpola oil shale is the largest lacustrine oil shale deposit in Tibet (SW China), which deposited in a Cenozoic lacustrine rift basin and contains abundant organic matter (OM), whereas the crucial factors that controlled the OM enrichment remain elusive. Here, we present new datasets of total organic carbon (TOC) contents, clay minerals and whole-rock geochemistry of the early-middle Miocene Middle Dingqinghu Formation oil shale from the Lunpola basin, central Tibet, in order to elucidate the paleoclimate, paleo-environment condition and the controlling factors on the OM enrichment of the lacustrine oil shale.Oil shales from the Lunpola East section have high TOC contents (avg. 9.60%), while the contiguous mudstones contain low TOC contents (avg. 0.44%). During the oil shale deposition, high smectite and kaolinite contents, low illite contents and low Sr/Cu ratios suggest strong chemical weathering and hence warm and humid climate, which may probably have close relationship with the mid-Miocene climatic optimum (MMCO). However, during the mudstone deposition, the relatively high illite and low smectite contents and higher Sr/Cu ratios suggest weak chemical weathering, indicating relatively arid climatic condition. The paleo-environment indexes (Corg/P, MoEF and UEF) and MoEF-UEF covariation reflect an anoxic bottom water condition during the oil shale deposition, while the mudstone formed in oxic-dysoxic water environment. The weak and moderate positive relationship between bio-productivity proxies (P/Ti and Cu/Ti ratios) and TOC contents reveal that the bio-productivity condition is not the crucial factor for the OM enrichment. Moreover, the water column environment was brackish and stratified during the oil shale deposition, and the sedimentation rate was moderate, which were also conducive to the OM preservation. The positive correlations between the TOC and the paleoclimate and paleoenvironment proxies demonstrate that warm and humid climate during the MMCO and anoxic water conditions play predominant roles in OM enrichment of the Lunpola lacustrine oil shale. Besides, modest sedimentation rate can prevent the dilution of OM, which can also promote the OM enrichment. This study can not only deepen the understanding of OM enrichment mechanism in lacustrine rift basin but also provide important information for predicting the distribution of the oil shale in the Lunpola Basin.

Coastal upwelling and redox variations in the northwestern Tarim Basin (northwest China) during the Middle-Late Ordovician: implication for paleo-depositional conditions of the organic matter enrichment in the Saergan Formation

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.

Palaeoclimatic influence on lake palaeoenvironment and organic matter accumulation in the Middle Jurassic Shimengou formation (Qaidam basin, NW China)

The formation and accumulation of lacustrine organic-rich shales are strongly related to palaeoclimate and palaeoenvironmental conditions. Middle Jurassic organic-rich lacustrine shales in the Qaidam Basin, NW China, are important source rocks for unconventional oil and gas exploration, but factors controlling their organic matter (OM) abundance and preservation are unclear. To understand how palaeoclimate and palaeoenvironmental conditions influenced depositional processes and elucidate the factors controlling OM accumulation of lacustrine organic-rich shales, we investigated total organic carbon (TOC), mineral compositions, and element geochemistry the Shale Member of the Middle Jurassic (J2s2) Shimengou Formation from the Yuqia Coalfield in the Qaidam Basin. From the bottom to the top, the Shale Member includes three significant stages based on their average TOC values of 5.45% (Stage I), 9.90% (Stage II), and 1.10% (Stage III). Paleoclimate proxies including C-values and Rb/Sr ratios indicate that in Stage I the lake developed under warm and humid conditions, while in Stage II climate changed to hot and arid/semiarid conditions before returning to warm and humid climates in Stage III. Correlation analysis among proxies for palaeoclimate, terrestrial influx (Al2O3 and TiO2 contents), sedimentation rate ((La/Yb) N ratios), palaeosalinity (Sr/Ba ratios and B/Ga ratios), palaeoproductivity (P/Ti ratios and Sibio contents), redox conditions (Corg/P ratios), and TOC values revealed that palaeoclimate had little direct impact on OM accumulation, with palaeoenvironmental conditions the main controlling factor for OM accumulation. OM accumulation in Stage I was primarily controlled by redox conditions, followed by palaeoproductivity, terrigenous influx, and sedimentation rate. In Stage II, high palaeoproductivity and anoxic bottom water conditions controlled OM accumulation, resulting in the deposition of oil shales with abundant hydrocarbon potential. In Stage III, poor OM preservation related to oxic redox condition was the primary controlling factor for OM accumulation. We suggest that variations in lake palaeoenvironments induced by palaeoclimate change controlled OM accumulation and petroleum potential.

Variable depositional environments and organic matter enrichment of Early Cambrian shales in the Middle Yangtze region, South China

Organic-rich shales of the Lower Cambrian Shuijingtuo Formation (SJT) in the Middle Yangtze region (South China) represent an important target for shale gas exploration and development in China. The lower section of the SJT mainly consisting of organic-rich black shale deposits has been regarded to be a favorable target for shale gas exploration and received substantial attentions, while the upper section of the SJT primarily consisting of limestone, silty shale and black shale deposits has been rarely studied. Most recently, a major breakthrough of shale gas exploration and development has been made in the upper section shale deposits. In order to better understand the redox evolution of sedimentary environment throughout the whole Early Cambrian time and organic matter (OM) enrichment mechanism of the SJT shale deposits, geochemical investigations, including analyses of total organic carbon (TOC), as well as major and trace element compositions, were conducted on the upper section of the SJT shales from Well EYY1. Our results showed that the upper section of the SJT shale deposits was accumulated during the Cambrian Stage 3. The TOC values of the studied SJT shale samples ranged from 0.34 to 3.65 wt%. The lower part of the upper section of the SJT shale, which exhibited relatively high TOC contents (∼2.0 wt%), was deposited under anoxic bottom-water conditions during the early Cambrian Stage 3, while the upper part, showing relatively low TOC content (1.0 wt%), was deposited under suboxic bottom-water conditions with intermittent episodes of anoxic bottom-water conditions during the middle–late Cambrian Stage 3. The palaeo-productivity of the SJT shale was estimated to be generally low, and displayed little variation. The OM enrichment mechanism of the SJT shale deposits underwent dynamic changes due to relative sea-level changes in the Yangtze Ocean. The OM enrichment of the early and late Cambrian Stage 3 shale deposits was primarily controlled by reducing conditions, while that of the middle Cambrian Stage 3 shale deposits may have been influenced by episodic upwelling activities.

Productivity-induced redox transition within the Niobrara formation, western Interior seaway, Colorado

Deposition of organic rich shale/marl within the Niobrara Formation during the Coniacian to Santonian Ocean anoxic event (OAE 3) within the Western Interior Seaway presents a unique record of variable organic carbon burial under a greenhouse climate. In order to understand the mechanisms behind the changes from low to high organic carbon burial, and how this high burial rate was sustained for over 3 Ma, productivity within the surface waters and subsequent preservation of organic matter within the sediments were investigated in this study. Based on the multiproxy approach adopted herein, the sedimentary record of the Niobrara Formation in northern Colorado can be separated into two distinct intervals: Interval 1 and Interval 2. Interval 1 is bioturbated, organic lean and oxic, with low to moderate trace metal enrichment except for Mn. Interval 2 is laminated, organic-rich, more enriched in trace metals U, V and Mo, and less enriched in Mn, typical of anoxia during deposition. The transition from oxic to anoxic conditions coincides with greater enrichments in TOC, Cu and Ni, suggesting enhanced productivity is associated with redox transitions within the Niobrara Formation. These local changes in productivity and redox conditions are sudden and coincide with recurring iron (Fe) and phosphorus (P)-rich bentonites, evidence of ash deposition that could have enhanced nutrient supply, productivity and accumulation of organic carbon. Consequently, perturbations of the global carbon cycle associated with OAE 3 were inferred to have occurred in Interval 2.High total Fe, total sulfur, Fe/Al, and trace metal enrichments in Interval 2 are intrinsically linked to prevalence of anoxic bottom-water conditions which enhanced burial of pyrite and organic matter. Results from productivity proxies and Fe–S–C ternary plots show that Fe limitation on pyrite formation under anoxic porewater enhanced organic carbon burial and preservation. This implies Fe enrichment within the sediments favored pyrite formation instead of organic matter sulfidization, leading to a complex relationship between S and organic carbon in the marine sediments during Niobrara deposition.

Early–Middle Jurassic brachiopods from Ponor Mountain, Western Balkan Mountains, Bulgaria; taxonomy, biostratigraphy and occurrence in the context of the early Toarcian Oceanic Anoxic Event

ABSTRACT An upper Pliensbachian–Aalenian brachiopod succession is reported from Ponor Mountain, Western Balkan Mountains, Bulgaria. This includes nine species (6 rhynchonellides and 3 terebratulides) from eight genera. A new genus Bulgariarhynchia and two new species, Bulgariarhynchia ponorensis and Capillirhynchia brezenensis, are formally described. A single species Homoeorhynchia ? aff. prona was found in the upper Pliensbachian. Most of the brachiopods derived from the Toarcian–Aalenian interval, and comprise: Pseudogibbirhynchia jurensis, Rhynchonelloidea angulata, Globirhynchia subobsoleta, Sphaeroidothyris uretae, Lobothyris? hispanica, and Telothyris jauberti. The brachiopod assemblages were dated using coeval ammonite biostratigraphy. Both ammonites and brachiopods display clear northwest European affinities. The new brachiopod taxa are considered autochthonous for the Balkan Mountains. Three biofacies (BF2, BF3 and BF5) were recognised and implied alternating suboxic to anoxic bottom water conditions. A few geochemical proxies are indicative of the early Toarcian Oceanic Anoxic Event (T-OAE) in the stratigraphic column. The main T-OAE pulse was fixed at the coeval positive δ13C and negative δ18O excursions, as well as increases in Hg/TOC ratios and redox-sensitive elements. The late Pliensbachian–earliest Toarcian time span was found to be the most hostile for the brachiopods. Above it, brachiopods lived in less stagnant environments.urn:lsid:zoobank.org:pub:22EF76B7-6A4B-4E54-A5BC-38C87125253E

Weak and intermittent anoxia during the mid-Tournaisian (Mississippian) anoxic event in the Montagne Noire, France

AbstractThe mid-Tournaisian black radiolarian cherts of the Lydiennes Formation are exposed in deep-shelf successions of the Puech de la Suque and Col des Tribes sections of the Mont Peyroux Nappe area in the Montagne Noire, southern France. This interval represents the mid-Tournaisian anoxic event that is also termed the Lower Alum Shale Event. This event is associated with a global marine transgression that was characterized by increased productivity and drastic facies changes from pelagic carbonate sedimentation to the widespread deposition of black organic-rich siliceous shales and radiolarites in many parts of the world. In the present study, high-resolution inorganic geochemistry and framboidal pyrite analyses were employed to decipher changes in depositional conditions during the mid-Tournaisian anoxic event in the Montagne Noire. The results show that the total organic carbon contents of sediments associated with the Lower Alum Shale Event vary from 0.09 to 1.9 wt %. These low to moderate total organic carbon contents, high U/Th, low Corg/P and intermediate V/Cr ratios, enrichment in redox-sensitive trace elements, such as U, Mo and V, as well as varying sizes of pyrite framboids, indicate periodic dysoxic to anoxic bottom-water conditions during deposition of the studied sediments. Anomalous Hg spikes (&gt;500 ppb) are also reported in the mid-Tournaisian deep-water marine succession of the Montagne Noire in the present study, which confirm a possible influence of increased regional volcanic activity during this environmental turnover.

Geochemical Characteristics and Organic Matter Accumulation of Wufeng-Longmaxi Shales in the Southeast of the Sichuan Basin of South China

The Upper Ordovician Wufeng Formation and Lower Silurian Longmaxi Formation black shales are the critical targets for shale gas exploration in the Sichuan Basin of South China. The enrichment of organic matter (OM) in shale is the basis for the generation of large-scale shale gas; however, its controlling factors in Wufeng-Longmaxi shales are still under debate, and few studies have focused on the edge of the Sichuan Basin. Based on the mineral composition, total organic carbon (TOC), and systematic inorganic geochemistry analysis of 72 core samples from Wufeng and Longmaxi formations in Well Xike 1, southeastern Sichuan Basin, the sedimentary conditions (palaeoclimate, palaeoredox, and palaeoproductivity) were reconstructed, and the controlling factors of OM enrichment were identified. The mineral compositions are dominated by quartz, clay minerals, calcite, and feldspar, associated with minor dolomite, pyrite, and anhydrite. The TOC contents (0.31%-6.84%, avg. 2.22%) show an upward decreasing trend from the Wufeng Formation to Longmaxi Formation. The chemical index of alteration (CIA) ranges from 65 to 71 (avg. 69), indicating warm and humid climate with moderate weathering. The diagrams of Al2O3-TiO2, TiO2-Zr, Zr/Sc-Th/Sc, La/Th-Hf, and La-Th-Sc jointly indicate the contribution from felsic and intermediate rock weathering. The P/Al, Cu/Al, and Ni/Al ratios suggest that marine paleoproductivity was relatively high in the Wufeng Formation and relatively low to moderate in the Longmaxi Formation. The V/Cr, V/Sc, U/Th, MoEF/UEF, and Corg/P ratios indicate that the bottom water was anoxic during the Wufeng Formation deposition and then fluctuating dysoxic and/or oxic in the overlying Longmaxi Formation. The TOC content was positively correlated with productivity proxies (P/Al, Cu/Al, and Ni/Al) as well as redox proxies (U/Th, V/Cr, MoEF/UEF, and Corg/P), indicating that the OM accumulation in Wufeng-Longmaxi shales is mainly controlled by high productivity and anoxic bottom water conditions.

Dynamics, distribution, and transformations of mercury species from pyrenean high-altitude lakes

While mercury (Hg) is a major concern in all aquatic environments because of its methylation and biomagnification pathways, very few studies consider Hg cycling in remote alpine lakes which are sensitive ecosystems. Nineteen high-altitude pristine lakes from Western/Central Pyrenees were investigated on both northern (France) and southern (Spain) slopes (1620–2600 m asl.). Subsurface water samples were collected in June 2017/2018/2019 and October 2017/2018 for Hg speciation analysis of inorganic mercury (iHg(II)), monomethylmercury (MMHg), and dissolved gaseous mercury (DGM) to investigate spatial and seasonal variations. In June 2018/2019 and October 2018, more comprehensive studies were performed in four lakes by taking water column depth profiles. Besides, in-situ incubation experiments using isotopically enriched Hg species (199iHg(II), 201MMHg) were conducted to investigate Hg transformation mechanisms in the water column. While iHg(II) (0.08–1.10 ng L−1 in filtered samples; 0.11–1.19 ng L−1 in unfiltered samples) did not show significant seasonal variations in the subsurface water samples, MMHg (<0.03–0.035 ng L−1 in filtered samples; <0.03–0.062 ng L−1 in unfiltered samples) was significantly higher in October 2018, mainly because of in-situ methylation. DGM (0.02–0.68 ng L−1) varies strongly and can exhibit higher levels in comparison with other pristine areas. Depth profiles and incubation experiments highlighted the importance of in-situ biotic methylation triggered by anoxic conditions in bottom waters. In-situ incubations confirm that significant methylation, demethylation and photoreduction extents are taking place in the water columns. Overall, drastic environmental changes occurring daily and seasonally in alpine lakes are providing conditions that can both promote Hg methylation (stratified anoxic waters) and MMHg photodemethylation (intense UV light). In addition, light induced photoreduction is a major pathway controlling significant gaseous Hg evasion. Global warming and potential eutrophication may thus have direct implications on Hg turnover and MMHg burden in those remote ecosystems.

Potential role of submerged macrophytes for oxic methane production in aquatic ecosystems

AbstractMethane (CH4) from aquatic ecosystems contributes to about half of total global CH4emissions to the atmosphere. Until recently, aquatic biogenic CH4production was exclusively attributed to methanogenic archaea living under anoxic or suboxic conditions in sediments, bottom waters, and wetlands. However, evidence for oxic CH4production (OMP) in freshwater, brackish, and marine habitats is increasing. Possible sources were found to be driven by various planktonic organisms supporting different OMP mechanisms. Surprisingly, submerged macrophytes have been fully ignored in studies on OMP, yet they are key components of littoral zones of ponds, lakes, and coastal systems. High CH4concentrations in these zones have been attributed to organic substrate production promoting classic methanogenesis in the absence of oxygen. Here, we review existing studies and argue that, similar to terrestrial plants and phytoplankton, macroalgae and submerged macrophytes may directly or indirectly contribute to CH4formation in oxic waters. We propose several potential direct and indirect mechanisms: (1) direct production of CH4; (2) production of CH4precursors and facilitation of their bacterial breakdown or chemical conversion; (3) facilitation of classic methanogenesis; and (4) facilitation of CH4ebullition. As submerged macrophytes occur in many freshwater and marine habitats, they are important in global carbon budgets and can strongly vary in their abundance due to seasonal and boom‐bust dynamics. Knowledge on their contribution to OMP is therefore essential to gain a better understanding of spatial and temporal dynamics of CH4emissions and thus to substantially reduce current uncertainties when estimating global CH4emissions from aquatic ecosystems.

Holocene Paleosecular Variations Recorded by Relict Magnetic Minerals in the Anoxic Black Sea Sediments

Continuous paleosecular variations reconstructed from sedimentary archives have remarkably deepened our insights into the dynamics of the Earth's magnetic field as well as the chronological purpose. Nevertheless, to construct reliable sedimentary paleomagnetic records in diagenetic reducing sediments is challenging generally due to the pervasive magnetic mineral diagenesis. The relict magnetic minerals are residuals after diagenesis and probably able to record a depositional remanent magnetization, thus it is worthy to explore their paleomagnetic potentials. For this study, two Black Sea sediment cores covering the past 8 ka were subjected to mineralogical and paleo- and rock magnetic analyses. Paramagnetic pyrite framboids are pervasive in the studied sediments deposited under anoxic bottom water conditions in the Black Sea. In addition, relict magnetic minerals of ferrous hemoilmenite, Fe-Mn and Fe-Cr spinels, and magnetite inclusions are also present in the studied cores. Compared to the previous published paleomagnetic results from the same cores over the last glacial period (20-30 ka) which are dominated by detrital (titano-)magnetite particles, the studied relict magnetic mineral samples exhibit a similar behavior in recording the depositional remanent magnetization. Furthermore, the obtained paleosecular variations spanning the past 8 ka reproduce the high intensity patterns observed in the regional archeomagnetic and volcanic datasets. Thus, the successful reconstruction of paleomagnetic secular variations from the anoxic Black Sea sediments greatly extend the application of paleomagnetism in sediments deposited in water with a reducing sub-surface environments from where paleomagnetic data are generally sparse.

Climatic and environmental conditions during the Pleistocene in the Central Qaidam Basin, NE Tibetan Plateau: Evidence from GDGTs, stable isotopes and major and trace elements of the Qigequan Formation

Sediments in the Tibetan Plateau (TP) region of NW China provide sensitive records of climate change and its impact on past ecosystems. The Qaidam Basin, located in the north-eastern part of the TP contains an exceptionally thick Meso-Cenozoic sedimentary succession; it is also the largest sedimentary basin in the TP. Here, new data on Pleistocene sediments on the TP are reported. Evidence from GDGTs, stable isotopes as well as major and trace elements of the Pleistocene Qigequan Formation was used to decipher depositional conditions within the water column and the origin of kerogen. This information was further applied to interpret factors controlling organic matter (OM) accumulation and climate conditions. In accordance with a previous study, the results show that two completely different organic facies are present, representing vastly different lake environments. OM of organic facies A samples is mainly derived from a mixture of C3 higher plants and phytoplankton, deposited in a shallow freshwater lake environment under dysoxic to anoxic bottom water conditions. In contrast, OM of organic facies B is mainly derived from a hypersaline and more distal lake environments mainly under oxic conditions. OM accumulation in both organic facies was primarily controlled by the paleo-redox conditions rather than paleo-productivity. By contrast, there is no significant difference between organic facies A and B samples with respect to the paleo-climate proxies. Generally, the sediments were deposited under arid/cold conditions with weak chemical weathering during the Pleistocene. The soils on the Tibetan Plateau tended to be alkaline at this time. Combined with the published data, the Pleistocene indices based on GDGT biomarkers indicate a rather continuous cooling and aridification process from Miocene to present. The Pleistocene Mean Annual Air Temperature based on bGDGTs (0.54–4.91 °C, 2.23 °C on average) was slightly higher than the present temperature, and the reconstructed lake surface temperature ranges from 5.7 to 19.6 °C (in winter 2.4–13.7 °C).

Geochemical characteristics and depositional paleoenvironment of source rocks from the Lower Cretaceous Chijinbao Formation in Jiuxi Basin, China

The Lower Cretaceous Chijinbao Formation is one of the primary source rocks in the Jiuxi Basin in Northwest China. However, it is poorly studied due to the lack of a complete stratigraphic sequence exposed by drilling. In this research, an integrated analysis of palynofacies, organic geochemistry, and element geochemistry was systematically conducted on samples with longitudinal continuity collected from the Chijinbao Formation in the Hanxia Section of the Jiuxi Basin to determine the distribution of source rocks and the source and type of organic matter and to reconstruct the depositional paleoenvironment of the Chijinbao Formation. The lower part of the sequence, which is governed by poor source rocks with Type III organic matter, is characterized by palynofacies A (woody tissue–charcoal assemblage) grown in a proximal alluvial fan–shallow lacustrine environment. The excellent source rocks with mostly Type II 1 organic matter are considerable in the middle part of the sequence, which is marked by palynofacies B (amorphous organic matter assemblage), and occur in a distal semi-deep lacustrine–deep lacustrine environment. The upper part of the sequence is largely composed of poor and fair source rocks, represented by palynofacies C (amorphous organic matter–woody tissue assemblage), and a small amount of sporadically distributed good and excellent source rocks (approximately 1/3), which may be deposited in a proximal fan delta and a local semi-deep lacustrine–deep lacustrine environment. A semiarid–semi-humid climate and a freshwater–brackish water environment prevailed during the deposition of the Chijinbao Formation. The lower part of the sequence is characterized by the highest terrestrial detritus influx, strong weathering, humid paleoclimate, oxic water column conditions, and the lowest paleoproductivity. The middle part of the sequence has the lowest terrestrial detritus influx, relatively weak weathering, relatively arid paleoclimate, predominantly anoxic water environment, and the highest paleoproductivity. The climate became humid again during the deposition of the upper part, which is typified by an intermediate terrestrial detritus influx, strong weathering, fluctuations of oxic–anoxic bottom-water conditions, and moderate paleoproductivity. The correlation analysis of element proxies suggests that the increase in salinity during the deposition of the middle part is associated with an arid climate. Amorphous organic matter, which is derived mostly from aquatic organisms and degraded terrestrial higher plants, is the major hydrocarbon generation component in the source rocks of the Chijinbao Formation. It increases in abundance with an improvement in water reducibility and productivity, favoring the formation and preservation of excellent source rocks. • Excellent source rocks distribute in middle part of Chijinbao Formation. • AOM dominate organic components in excellent source rocks of Chijinbao Formation. • Excellent source rocks were deposited under anoxic and relative arid conditions. • High salinity correlates with arid climate during the deposition of middle part.