Carbon isotopes and lipid biomarkers from organic‐rich facies of the Shuram Formation,Sultanate of Oman

The largest recorded carbon isotopic excursion in Earth history is observed globally in carbonate rocks of middle Ediacaran age. Known from the Sultanate of Oman as the ‘Shuram excursion’, this event records a dramatic, systematic shift in δ¹³C_carbonate values to ca. ?12‰. Attempts to explain the nature, magnitude and origin of this excursion include (i) a primary signal resulting from the protracted oxidation of a large dissolved organic carbon reservoir in seawater, release of methane from sediment‐hosted clathrates, or water column stratification; and (ii) a secondary signal from diagenetic processes. The compositions and isotope ratios of organic carbon phases during the excursion are critical to evaluating these ideas; however, previous work has focused on localities that are low in organic carbon, hindering straightforward interpretation of the observed time‐series trends. We report carbon isotope data from bulk organic carbon, extracted bitumen and kerogen, in addition to lipid biomarker data, from a subsurface well drilled on the eastern flank of the South Oman Salt Basin, Sultanate of Oman. This section captures Nafun Group strata through the Ediacaran–Cambrian boundary in the Ara Group and includes an organic‐rich, deeper‐water facies of the Shuram Formation. Despite the high organic matter contents, the carbon isotopic compositions of carbonates – which record a negative δ¹³C isotope excursion similar in shape and magnitude to sections elsewhere in Oman – do not covary with those of organic phases (bulk TOC, bitumen and kerogen). Paired inorganic and organic δ¹³C data only display coupled behaviour during the latter part of the excursion's recovery. Furthermore, lipid biomarker data reveal that organic matter composition and source inputs varied stratigraphically, reflecting biological community shifts in non‐migrated, syngenetic organic matter deposited during this interval.     

Origin and cycling of riverine inorganic carbon in the Sava River watershed (Slovenia) inferred from major solutes and stable carbon isotopes

The Sava River and its tributaries in Slovenia represent waters strongly influenced by chemical weathering of limestone and dolomite. The carbon isotopic compositions of dissolved inorganic carbon (DIC) and suspended organic carbon (POC) fractions as well as major solute concentrations yielded insights into the origin and fluxes of carbon in the upper Sava River system. The major solute composition was dominated by carbonic acid dissolution of calcite and dolomite. Waters were generally supersaturated with respect to calcite, and dissolved CO₂ was about fivefold supersaturated relative to the atmosphere. The δ¹³C of DIC ranged from −13.5 to −3.3‰. Mass balances for riverine inorganic carbon suggest that carbonate dissolution contributes up to 26%, degradation of organic matter ∼17% and exchange with atmospheric CO₂ up to 5%. The concentration and stable isotope diffusion models indicated that atmospheric exchange of CO₂ predominates in streams draining impermeable shales and clays while in the carbonate-dominated watersheds dissolution of the Mesozoic carbonates predominates.     

Carbonate facies‐specific stable isotope data record climate,hydrology, and microbial communities in Great Salt Lake,UT

Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ¹⁸O_water, δ¹³C_DIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ¹⁸O_carb, δ¹³C_carb, ?₄₇), as well as carbon isotopic compositions of bulk organic matter (δ¹³C_org) and dissolved inorganic carbon (DIC; δ¹³C_DIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ?₄₇ isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(?₄₇)), δ¹⁸O_carb, and calculated δ¹⁸O_water in isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.     

Controls on the origin and cycling of riverine dissolved inorganic carbon in the Brazos River, Texas

Rivers draining watersheds that include carbonate bedrock or organic matter (OM)-rich sedimentary rocks frequently have ¹⁴C-depleted dissolved inorganic carbon (DIC) relative to rivers draining carbonate- and OM-free watersheds, due to dissolution of carbonate and/or decomposition of ancient OM. However, our results from a subtropical river, the Brazos River in Texas, USA, show that in this watershed human activities appear to dominate basin lithology in controlling the origin and metabolism of DIC. The middle Brazos flows through limestone and coal-bearing bedrock, but DIC isotope data suggest no limestone dissolution or respiration of ancient OM, and instead reflect efficient air?Cwater CO₂ exchange, degradation of relatively young OM and photosynthesis in the river as a result of river damming and urban treated wastewater input. The lower Brazos drains only small areas of carbonate and coal-bearing bedrock, but DIC isotope data suggest the strong influence of carbonate dissolution, with a potentially minor contribution from decomposition of old soil organic matter (SOM). Oyster shells and crushed carbonate minerals used in road construction are likely sources of carbonate in the lower Brazos, in addition to natural marl and pedogenic carbonate. Additionally, the generally low pCO₂ and high DIC concentration in the Brazos River lead to a low CO₂ outgassing:DIC export ratio, distinguishing the Brazos River from other rivers.     

A laboratory study on biochemical degradation and microbial utilization of organic matter comprising a marine diatom,land grass,and salt marsh plant in estuarine ecosystems

We studied the biochemical degradation of organic matter comprising marine diatom, land grass, and salt marsh plant in estuarine ecosystems in two laboratory microcosms consisting of estuarine sediments and coastal seawater. The materials were incubated separately and together under controlled oxic and anoxic conditions to test effects of co-metabolism and redox on overall degradation of organic matter. We followed variations of bulk parameters [total organic carbon (TOC), total nitrogen (TN), C/N ratio, δ¹³C_TOC, and δ¹⁵N_TN], fatty acid concentrations, and compound-specific δ¹³C values over 3 months. Coexistence of marine diatom (relatively labile) with land grass/salt marsh plant (relatively refractory) in the microcosms yielded a negative co-metabolism effect (retardation rather than acceleration) on the overall degradation of organic matter. The ratios of oxic to anoxic degradation rate constants (k _ox/k _an) of TOC and most fatty acids were in a range of 1.1–1.7, implying that redox conditions per se had a limited influence on degradation of fresh organic materials in estuarine ecosystems. Variations of two bacteria-specific fatty acids (iso- and anteiso-15:0) and their δ¹³C values indicated that bacterial metabolism could use organic carbon (OC) from any available material when only one single-source material was dominant in the ecosystems. However, bacteria probably utilized OC preferentially from labile marine diatom when multiple-source materials were almost equally present in the ecosystems.     

Formation of large carbonate concretions in black cherts in the Gufeng Formation (Guadalupian) at Enshi,South China

The formation of carbonate concretions is a cementation process which passively infills the pore spaces within sediments. They record the original environments of deposition and diagenetic conditions of the host rocks. Little is known about the precise mechanisms responsible for the precipitation of carbonate concretions. The most common host rocks are mudstones/shales, sandstones, and limestones. This study presents an example of large carbonate concretions from an unusual host rock, the black bedded cherts of the Gufeng Formation (Guadalupian) at Enshi on the northern Yangtze Platform, South China. Petrographic observations (X‐ray diffraction, optical microscopy, scanning electron microscopy) and multiple geochemical analyses (pyrite‐ and carbonate‐associated‐sulfate (CAS)‐sulfur isotopes, carbon isotopes) indicate that (a) the studied carbonate concretion are mainly composed of micritic calcite with subordinate dolomite; (b) the concretions may have been mainly formed in the bacterial sulfate reduction (BSR) zone during very early diagenesis near the sediment–water surface; (c) the paleo‐bottom water overlying the sediments during formation of the concretions was mainly euxinic; and (d) the growth of the studied concretions proceeded via a pervasive model, where later cementation phase initiated in the lower part of the concretions and progressed upward.     

Ammonite fauna from uppermost Bajocian (Middle Jurassic) calcitic concretions from the Polish Jura—biogeographical and taphonomical implications

Uppermost Bajocian (Parkinsoni Zone, Bomfordi Subzone) calcitic concretions from the epicratonic basin in South-Central Poland (Polish Jura) contain numerous, well-preserved ammonites unique for this area. Characteristic of the assemblages is the presence of small, juvenile specimens. Associated with dominant parkinsoniids (Parkinsonia (Parkinsonia) aff. dorni Arkell) are lytoceratids [Nannolytoceras tripartitum (Raspail)], lissoceratids [(Lissoceras (Lissoceras) oolithicum (d'Orbigny) and Lissoceras (Microlissoceras) solitarium Zatoń and Marynowski nov. sp.)], leptosphinctids (Vermisphinctes sp.) and strigoceratids [(Strigoceras (Strigoceras) sp. juv. gr. strigifer/pseudostrigifer)], as well as fragments of phylloceratids (Phylloceras sp.). Parkinsoniids (the most numerous) are considered here as host fauna. Other ammonites, especially phylloceratids and nannolytoceratids, are supposed migrants from the Mediterranean area into the shallow epicratonic Polish Basin during the Late Bajocian sea-level rise. N. tripartitum, which has a broad geographical range probably drifted as a plankton-feeder in the upper water column and, together with phylloceratids, are considered to be unsuccessful immigrants which did not adapt to the new environment. It seems that the whole fauna, inclusive of plant remains, was accumulated by bottom currents in randomly situated depressions on the sea-floor, where carcasses became ideal nucleation sites for concretion genesis. Early diagenesis, which played an important role, resulted in well-preserved ammonite assemblages close to the original biological assemblage. Most of described ammonites (nannolytoceratids, lissoceratids, strigoceratids and leptosphinctids) are reported from the Upper Bajocian epicratonic deposits of Poland for the first time. This makes the concretions a true “taphonomic window” into latest Bajocian census biocenosis. The organic geochemistry results suggest predominance of terrestrial organic matter in both concretions and surrounding clays, with well oxygenated conditions in the sedimentary basin. The large concentrations of Δ¹³⁽¹⁷⁾diasterenes in the analysed carbonate concretions indicates that these compounds must have been formed by contact with clay minerals before formation of the carbonate concretions. The processes described may have followed early stage of diagenesis, but certainly under tens of cm to even a few meters of burial. The high negative δC¹³ values in the inner zone of the concretions suggest that concretion growth began in the sulphate reduction zone and may have continued in the methanogenesis zone.     

The carbon cycle and carbon dioxide over Phanerozoic time: the role of land plants

A model (GEOCARB) of the long-term, or multimillion year, carbon cycle has been constructed which includes quantitative treatment of (1) uptake of atmospheric CO₂ by the weathering of silicate and carbonate rocks on the continents, and the deposition of carbonate minerals and organic matter in oceanic sediments; and (2) the release of CO₂ to the atmosphere via the weathering of kerogen in sedimentary rocks and degassing resulting from the volcanic-metamorphic-diagenetic breakdown of carbonates and organic matter at depth. Sensitivity analysis indicates that an important factor affecting CO₂ was the rise of vascular plants in the Palaeozoic. A large Devonian drop in CO₂ was brought about primarily by the acceleration of weathering of silicate rock by the development of deeply rooted plants in well-drained upland soils. The quantitative effect of this accelerated weathering has been crudely estimated by present-day field studies where all factors affecting weathering, other than the presence or absence of vascular plants, have been held relatively constant. An important additional factor, bringing about a further CO₂ drop into the Carboniferous and Permian, was enhanced burial of organic matter in sediments, due probably to the production of microbially resistant plant remains (e.g. lignin). Phanerozoic palaeolevels of atmospheric CO₂ calculated from the GEOCARB model generally agree with independent estimates based on measurements of the carbon isotopic composition of palaeosols and the stomatal index for fossil plants. Correlation of CO₂ levels with estimates of palaeoclimate suggests that the atmospheric greenhouse effect has been a major factor in controlling global climate over the past 600 million years.     

Impact of eutrophication on the carbon stable‐isotopic baseline of benthic invertebrates in two deep soft‐water lakes

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Isotope alteration caused by changes in biochemical composition of sedimentary organic matter

Stable carbon (C) and nitrogen (N) isotope ratios of sedimentary organic matter (OM) can reflect the biogeochemical history of aquatic ecosystems. However, diagenetic processes in sediments may alter isotope records of OM via microbial activity and preferential degradation of isotopically distinct organic components. This study investigated the isotope alteration caused by preferential degradation in surface sediments sampled from a eutrophic reservoir in Germany. Sediments were treated sequentially with hot water extraction, hydrochloric acid hydrolysis, hydrogen peroxide oxidation and di-sodium peroxodisulfate oxidation to chemically simulate preferential degradation pathways of sedimentary OM. Residue and extracts from each extraction step were analyzed using elemental analyzer-isotope ratio mass spectrometry and solid-state ¹³C nuclear magnetic resonance spectroscopy. Our results show that stable C and N isotope ratios reacted differently to changes in the biochemical composition of sedimentary OM. Preferential degradation of proteins and carbohydrates resulted in a 1.2‰ depletion of ¹³C, while the isotope composition of ¹⁵N remained nearly the same. Sedimentary δ¹⁵N values were notably altered when lignins and lipids were oxidized from residual sediments. Throughout the sequential fractionation procedure, δ¹³C was linearly correlated with the C:N of residual sediments. This finding demonstrates that changes in biochemical composition caused by preferential degradation altered δ¹³C values of sedimentary OM, while this trend was not observed for δ¹⁵N values. Our study identifies the influence of preferential degradation on stable C isotope ratios and provide additional insight into the isotope alteration caused by post-depositional processes.

     

A diagenetic control on the Early Triassic Smithian–Spathian carbon isotopic excursions recorded in the marine settings of the Thaynes Group (Utah,USA)

In the aftermath of the end‐Permian mass extinction, Early Triassic sediments record some of the largest Phanerozoic carbon isotopic excursions. Among them, a global Smithian‐negative carbonate carbon isotope excursion has been identified, followed by an abrupt increase across the Smithian–Spathian boundary (SSB; ~250.8 Myr ago). This chemostratigraphic evolution is associated with palaeontological evidence that indicate a major collapse of terrestrial and marine ecosystems during the Late Smithian. It is commonly assumed that Smithian and Spathian isotopic variations are intimately linked to major perturbations in the exogenic carbon reservoir. We present paired carbon isotopes measurements from the Thaynes Group (Utah, USA) to evaluate the extent to which the Early Triassic isotopic perturbations reflect changes in the exogenic carbon cycle. The δ¹³C_carb variations obtained here reproduce the known Smithian δ¹³C_carb‐negative excursion. However, the δ¹³C signal of the bulk organic matter is invariant across the SSB and variations in the δ³⁴S signal of sedimentary sulphides are interpreted here to reflect the intensity of sediment remobilization. We argue that Middle to Late Smithian δ¹³C_carb signal in the shallow marine environments of the Thaynes Group does not reflect secular evolution of the exogenic carbon cycle but rather physicochemical conditions at the sediment–water interface leading to authigenic carbonate formation during early diagenetic processes.     

Sources of organic carbon and depositional environment in the Bengal delta plain sediments during the Holocene period

This study investigated the sources of organic matter and sediment depositional environment within fluviatile sediments of the Ganges–Meghna (GM) delta plains. The very low contents of trace metals e.g., chromium (Cr), cobalt (Co), scandium (Sc), and vanadium (V), organic carbon content, and cerium (Ce)-anomaly data of sediments indicate the redox conditions that fall within the boundary of oxic–anoxic condition, with dominantly oxic conditions in the sediment deposition environment. The higher atomic carbon nitrogen (C/N)a ratios and depleted stable carbon isotope ratio (δ¹³C) values for sediments from three study areas indicated the terrestrial sources of organic matter derived from C₃ plant materials, whereas the contribution of organic materials from C₄ vegetation and riverine productivity is low. Some silty sand samples exhibited lower (C/N)a ratios and enriched δ¹³C values in Sonargaon and Faridpur areas that are attributed to the adsorption of ammonium ions on clay minerals and the contribution of organic matter from C₄ plants. Total sulfur over total organic carbon (TS/TOC) ratios in sediments of the Ganges delta reflect the nonmarine environments of sediment deposition. The lower ratios of syringyl to vanillyl phenols (S/V), cinnamyl to vanillyl phenols (C/V), and acid to aldehyde in vanillyl phenols (Ad/Al)v observed in Daudkandi indicate that the lignin in sediments derived from dominant woody gymnosperm sources and is very highly degraded. By contrast, the S/V ratio, C/V ratios, and [Ad/Al]v ratios in Faridpur suggest that the lignin in sediments derived from a mixture of woody and nonwoody angiosperm plant tissue contribution that underwent high degradation as well.     

The Apectodinium acme and terrestrial discharge during the Paleocene-Eocene thermal maximum: new palynological, geochemical and calcareous nannoplankton observations at Tawanui, New Zealand

Manifestations of profound perturbations in biogeochemical systems during the Paleocene-Eocene thermal maximum (PETM) include a prominent global negative δ¹³C and a pronounced increase in the relative abundance of dinoflagellate cysts (dinocysts) assigned to the genus Apectodinium. While motile representatives of Apectodinium were most likely thermophilic and heterotrophic, the underlying causes of this dinoflagellate response are not well understood. Here we provide new insight by examining the palynology, chemistry and calcareous nannoplankton across the PETM in a continental slope section at Tawanui, New Zealand. Across the PETM, marked changes in the relative abundance of Apectodinium vary antithetically with significant changes in the δ¹³C of carbonate and organic matter. In general, the high relative abundance of Apectodinium relates to enhanced concentrations of dinocysts, signifying a ‘bloom’ of Apectodinium in surface waters during the PETM. Changes in Apectodinium and δ¹³C records correspond to variations in many other parameters, including a smaller negative shift in bulk carbonate δ¹³C than expected, increased terrestrial palynomorphs, elevated TOC and C/N ratios, lower carbonate contents, higher SiO₂ and Al₂O₃ contents, and lower Si/Al ratios. All of these variations can be explained by an increase in delivery of terrigenous material to the continental margin. A peak in the relative abundance of Glaphyrocysta dinocysts at the onset of the PETM may indicate greater down slope transport of neritic material. Changes in calcareous nannoplankton abundances suggest increased nutrient availability in surface waters during the PETM. The combined results show that Apectodinium-dominated assemblages, global perturbations in carbon isotopes and enhanced terrigenous delivery closely correspond in time at Tawanui. A sudden and massive carbon injection to the ocean-atmosphere system may have enhanced weathering and increased terrigenous inputs to continental margins during the PETM. We further suggest that these inputs caused the Apectodinium acme by elevating primary productivity in marginal seas.     

Controls of organic and inorganic carbon in randomly selected Boreal lakes in varied catchments

Organic and inorganic carbon concentrations in lakes and the links to catchment and water quality were studied in variable landscapes using the Finnish Lake Survey data base including 874 randomly selected lakes sampled during autumn overturn. The median total organic carbon (TOC) in these boreal lakes was 7.8 mg l^?1, the median total inorganic carbon (TIC) 1.6 mg l^?1 and the median partial pressure of CO₂ (pCO₂) 900 μatm. When the data was divided into subgroups according to land use in the catchment, the proportion of TIC of the total carbon (TC) in lakes was highest (31%) in agricultural areas and lowest (10%) in peatland areas. Elevated TIC concentrations were associated with agricultural land in the catchment, whereas elevated TOC concentrations were observed in lakes with high peatland proportion in the catchment. Two contrasting important sources of CO₂ in lakes were identified on the basis of statistical analysis of the data; weathering processes in the catchments and decomposition of organic matter. CO₂ was also strongly associated with total nutrients TN and TP, implying the importance of quality of organic matter and availability of nutrients for the decomposition processes.     

Mineralized microbialites as archives of environmental evolution,Laguna Negra,Catamarca Province,Argentina

Environmental fluctuations are recorded in a variety of sedimentary archives of lacustrine depositional systems. Geochemical signals recovered from bottom sediments in closed‐basin lakes are among the most sensitive paleoenvironmental indicators and are commonly used in reconstructing lake evolution. Microbialites (i.e., organosedimentary deposits accreted through microbial trapping and binding of detrital sediment or in situ mineral precipitation on organics [Palaios, 2, 1987, 241]), however, have been largely overlooked as paleoenvironmental repositories. Here, we investigate concentrically laminated mineralized microbialites from Laguna Negra, a high‐altitude (4,100 m above sea level) hypersaline, closed‐basin lake in northwestern Argentina, and explore the potential for recovery of environmental signals from these unique sedimentary archives. Spatial heterogeneity in hydrological regime helps define zones inside Laguna Negra, each with their own morphologically distinct microbialite type. Most notably, platey microbialites (in Zone 3A) are precipitated by evaporative concentration processes, while discoidal oncolites (in Zone 3C) are interpreted result from fluid mixing and biologically mediated nucleation. This spatial heterogeneity is reflected in petrographically distinct carbonate fabrics: micritic, botryoidal, and isopachous. Fabric type is interpreted to reflect a combination of physical and biological influences during mineralization, and paired C‐isotope measurement of carbonate and organic matter supports ecological differences as a dominant control on C‐isotopic evolution between zones. Laminae of Laguna Negra microbialites preserve a range of δ¹³C_carb from +5.75‰ to +18.25‰ and δ¹⁸O_carb from ?2.04‰ to +9.28‰. Temporal trends of lower carbon and oxygen isotopic compositions suggest that the influence of CO₂ degassing associated with evaporation has decreased over time. Combined, these results indicate that microbialite archives can provide data that aid in interpretation of both lake paleohydrology and paleoenvironmental change.     

Carbon dioxide consumption during soil development

Carbon is sequestered in soils by accumulation of recalcitrant organic matter and by bicarbonate weathering of silicate minerals. Carbon fixation by ecosystems helps drive weathering processes in soils and that in turn diverts carbon from annual photosynthesis-soil respiration cycling into the long-term geological carbon cycle. To quantify rates of carbon transfer during soil development in moist temperate grassland and desert scrubland ecosystems, we measured organic and inorganic residues derived from the interaction of soil biota and silicate mineral weathering for twenty-two soil profiles in arkosic sediments of differing ages. In moist temperate grasslands, net annual removal of carbon from the atmosphere by organic carbon accumulation and silicate weathering ranges from about 8.5 g m^–2 yr^–1 for young soils to 0.7 g M^–2 yr^–1 for old soils. In desert scrublands, net annual carbon removal is about 0.2 g m^–2 yr^–1 for young soils and 0.01 g m^–2 yr^–1 for old soils. In soils of both ecosystems, organic carbon accumulation exceeds CO₂ removal by weathering, however, as soils age, rates of CO₂ consumption by weathering accounts for greater amounts of carbon sequestration, increasing from 2% to 8% in the grassland soils and from 2% to 40% in the scrubland soils. In soils of desert scrublands, carbonate accumulation far outstrips organic carbon accumulation, but about 90% of this mass is derived from aerosolic sources that do not contribute to long-term sequestration of atmospheric carbon dioxide.     

An isotopic and geochemical study of carbonate-clay mineralization in basaltic caves: abiotic versus microbial processes

Stable isotope and geochemical data are used here to differentiate between contemporaneous abiotic and microbial processes leading to formation of modern carbonate‐ (calcite, aragonite and magnesite) and silicate‐rich (kerolite) mineralization in basaltic sea caves on the island of Kauai, Hawaii. Strontium isotope and Ca/Sr ratios in meteoric water and cave carbonates suggest that the majority of Sr and Ca are derived from rock–water interaction within the host basalts situated above the caves. Oxygen and hydrogen isotope ratios and chemical compositions of cave and surface waters indicate that evaporation does not control cave‐water composition. However, evaporation of drops and thin films of water in microenvironments can lead to precipitation of some phases. This behaviour is suggested by the covariance in δ¹⁸O and δ¹³C values of some carbonates, especially magnesite, which is considered to be a late‐stage evaporative precipitate. Modelling of water evolution suggests that evaporation can be a cause of supersaturation for magnesite, kerolite and some Ca carbonates. However, the highly elevated δ¹³C values (up to +8.2) of some Ca carbonates, compared to average dissolved inorganic carbon δ¹³C values (~?12), are best explained as the product of microbial photosynthesis, in particular by cyanobacteria, present in the upper layers of active microbial mats on cave surfaces. The preferential uptake of ¹²C by cyanobacteria is recorded in the low δ¹³C values (?29.1 to ?22.6) of organic matter in mats and mineralized microbialites. The resulting ¹³C‐enrichment of dissolved inorganic carbon is recorded in the elevated δ¹³C values of these Ca carbonates. A positive correlation exists between the δ¹³C values of the carbonates and coexisting organic matter. The large enrichment in ¹³C of carbonate minerals, relative to dissolved inorganic carbon, and its covariance with the δ¹³C values of coexisting organic matter are useful for identification of carbonate‐rich mineralization resulting from autotrophic microbial activity.     

Benthic iron cycling in a high‐oxygen environment: Implications for interpreting the Archean sedimentary iron isotope record

The most notable trend in the sedimentary iron isotope record is a shift at the end of the Archean from highly variable δ⁵⁶Fe values with large negative excursions to less variable δ⁵⁶Fe values with more limited negative values. The mechanistic explanation behind this trend has been extensively debated, with two main competing hypotheses: (i) a shift in marine redox conditions and the transition to quantitative iron oxidation; and (ii) a decrease in the signature of microbial iron reduction in the sedimentary record because of increased bacterial sulfate reduction (BSR). Here, we provide new insights into this debate and attempt to assess these two hypotheses by analyzing the iron isotope composition of siderite concretions from the Carboniferous Mazon Creek fossil site. These concretions precipitated in an environment with water column oxygenation, extensive sediment pile dissimilatory iron reduction (DIR) but limited bacterial sulfate reduction (BSR). Most of the concretions have slightly positive iron isotope values, with a mean of 0.15‰ and limited iron isotope variability compared to the Archean sedimentary record. This limited variability in an environment with high DIR and low BSR suggests that these conditions alone are insufficient to explain Archean iron isotope compositions. Therefore, these results support the idea that the unusually variable and negative iron isotope values in the Archean are due to dissimilatory iron reduction (DIR) coupled with extensive water column iron cycling.     

Fluvial transport of carbon along the river-to-ocean continuum and its potential impacts on a brackish water food web in the Iwaki River watershed, northern Japan

Riverine transport of dissolved inorganic carbon (DIC) from land to the ocean is an important carbon flux that influences the carbon budget at the watershed scale. However, the dynamics of DIC in an entire river network has remained unknown, especially in mountainous Japanese watersheds. We examined the effects of watershed land use and geology on the transports of inorganic carbon as well as weathered silica (Si) and calcium (Ca) in the Iwaki River system where agricultural and residential areas have developed in the middle and lower parts of the watershed. The concentration and stable carbon isotope ratios (δ¹³C) of DIC showed the longitudinal increase of ¹³C-depleted inorganic carbon along the river. As a result, most streams and rivers were supersaturated in dissolved CO₂ that will eventually be emitted to the atmosphere. The possible origin of ¹³C-depleted carbon is CO₂ derived from the decomposition of organic matter in agricultural and urban landscapes, as well as from in-stream respiration. In addition, agricultural and urban areas, respectively, exported the large amount of dissolved Si and Ca to the rivers, suggesting that CO₂ increased by respiration accelerates the chemical weathering of silicate and carbonate materials in soils, river sediments, and/or urban infrastructure. Furthermore, riverine bicarbonate flux is likely to enter shell carbonates of Corbicula japonica, an aragonitic bivalve, in the downstream brackish lake (Lake Jusan). These results revealed that the flux of DIC from the human-dominated watersheds is a key to understanding the carbon dynamics and food-web structure along the land-to-river-to-ocean continuum.     

Geochemical characteristics of the Chang 7 Member in the southwestern Ordos Basin,China: the influence of sedimentary environment on the organic matter enrichment

The enrichment of organic matter is of great significance to the formation of source rocks, while its mechanism in the Chang 7 Member (Chang 7₁, Chang 7₂, and Chang 7₃ periods) of the southwestern Ordos Basin has not been studied in depth. Forty-eight samples obtained from Chang 7 Member were subjected to rock pyrolysis, gas chromatography-mass spectrometry (GC-MS) analysis, and determination experiments of major and trace elements to evaluate the hydrocarbon potential of the source rock, to reconstruct the sedimentary environment, and to analyze the factors of the organic matter enrichment. The results showed that the average total organic carbon (TOC) contents were 0.70%, 5.48%, and 7.70% for Chang 7₁, Chang 7₂, and Chang 7₃, respectively. From Chang 7₃ to Chang 7₁ period, the contents of TiO₂, Al₂O₃, Fe₂O₃, and P₂O₅ represented a gradual increase of terrigenous input and a gradual decrease in volcanism; the Chemical Alteration Index and the Sr/Cu values reflected warm and humid paleoclimate conditions with a gradual decrease in temperature; the V/(V+Ni) and the Mo-U covariation revealed an anoxic environment with a weakened reduction; and the P/Ti-Cu/Ti model indicated a gradual decrease in paleoproductivity. The linear relationship between indicators of paleoenvironment and TOC indicated that a small amount of terrigenous input, volcanism, warm and humid climate and reducing conditions were more conducive to the enrichment of organic matter; thus we propose a Chang 7₃ organic matter enrichment production model and a Chang 7₁ organic matter enrichment preservation-dilution model.