Preservation of overmature,ancient, sedimentary organic matter in carbonate concretions during outcrop weathering

Concretions are preferentially cemented zones within sediments and sedimentary rocks. Cementation can result from relatively early diagenetic processes that include degradation of sedimentary organic compounds or methane as indicated by significantly ¹³C‐depleted or enriched carbon isotope compositions. As minerals fill pore space, reduced permeability may promote preservation of sediment components from degradation during subsequent diagenesis, burial heating and outcrop weathering. Discrete and macroscopic organic remains, macro and microfossils, magnetic grains, and sedimentary structures can be preferentially preserved within concretions. Here, Cretaceous carbonate concretions of the Holz Shale are shown to contain relatively high carbonate‐free total organic carbon (TOC) contents (up to ~18.5 wt%) compared to the surrounding host rock (with <2.1 wt%). TOC increases with total inorganic carbon (TIC) content, a metric of the degree of cementation. Pyrite contents within concretions generally correlate with organic carbon contents. Concretion carbonate carbon isotope compositions (δ¹³C_carb) range from ?22.5 to ?3.4‰ (VPDB) and do not correlate strongly with TOC. Organic carbon isotope compositions (δ¹³C_org) of concretions and host rock are similar. Thermal maturity data indicate that both host and concretion organic matter are overmature and have evolved beyond the oil window maturity stage. Although the organic matter in general has experienced significant oxidative weathering, concretion interiors exhibit lower oxygen indices relative to the host. These results suggest that carbonate concretions can preferentially preserve overmature, ancient, sedimentary organic matter during outcrop weathering, despite evidence for organic matter degradation genetic mechanisms. As a result, concretions may provide an optimal proxy target for characterization of more primary organic carbon concentrations and chemical compositions. In addition, these findings indicate that concretions can promote delayed oxidative weathering of organic carbon in outcrop and therefore impact local chemical cycling.     

A new model of the formation of Pennsylvanian iron carbonate concretions hosting exceptional soft‐bodied fossils in Mazon Creek,Illinois

Preservation of Pennsylvanian‐aged (307 Ma) soft‐bodied fossils from Mazon Creek, Illinois, USA, is attributed to the formation of siderite concretions, which encapsulate the remains of terrestrial, freshwater, and marine flora and fauna. The narrow range of positive δ³⁴S values from pyrite in individual concretions suggests microenvironmentally limited ambient sulfate, which may have been rapidly exhausted by sulfate‐reducing bacteria. Tissue of the decaying carcass was rapidly encased by early diagenetic pyrite and siderite produced within the sulfate reduction and methanogenic zones of the sediment, with continuation of the latter resulting in concretion cementation. Cross‐sectional isotopic analyses (δ¹³C and δ¹⁸O) and mineralogical characterization of the concretions point to initiation of preservation in high porosity proto‐concretions during the early phases of microbially induced decay. The proto‐concretion was cemented prior to compaction of the sediments by siderite as a result of methanogenic production of ¹³C‐rich bicarbonate—which varies both between Essex and Braidwood concretions and between fossiliferous and unfossiliferous concretions. This work provides the first detailed geochemical study of the Mazon Creek siderite concretions and identifies the range of conditions allowing for exceptional soft‐tissue fossil formation as seen at Mazon Creek.     

Formation of Siderite in Microbial Microcosms Derived from a Marine Sediment

Abstract

Exceptionally well-preserved fossils are frequently encased by carbonate concretions. The initial steps of their formation in marine and freshwater sediments are induced by microbial activity. The role of the involved microbial communities, however, is not well understood. In this study, siderite (FeCO₃) formation in microbial microcosms is observed, with various fatty acyl compounds (lipids, surfactants) as substrates and Wadden Sea sediment samples as inocula. In actively growing microcosms, sulfate-reducing bacteria (the genus Desulfofrigus in particular) dominate the microbial community and submicroscopic siderite precipitates on bacterial cell surfaces were identified. We suggest that these biologically induced mineralization processes may, in the natural environment, initiate the formation of large concretions under suboxic conditions in coastal sediments.     

The microbially driven formation of siderite in salt marsh sediments

We employ complementary field and laboratory‐based incubation techniques to explore the geochemical environment where siderite concretions are actively forming and growing, including solid‐phase analysis of the sediment, concretion, and associated pore fluid chemistry. These recently formed siderite concretions allow us to explore the geochemical processes that lead to the formation of this less common carbonate mineral. We conclude that there are two phases of siderite concretion growth within the sediment, as there are distinct changes in the carbon isotopic composition and mineralogy across the concretions. Incubated sediment samples allow us to explore the stability of siderite over a range of geochemical conditions. Our incubation results suggest that the formation of siderite can be very rapid (about two weeks or within 400 hr) when there is a substantial source of iron, either from microbial iron reduction or from steel material; however, a source of dissolved iron is not enough to induce siderite precipitation. We suggest that sufficient alkalinity is the limiting factor for siderite precipitation during microbial iron reduction while the lack of dissolved iron is the limiting factor for siderite formation if microbial sulfate reduction is the dominant microbial metabolism. We show that siderite can form via heated transformation (at temperature 100°C for 48 hr) of calcite and monohydrocalcite seeds in the presence of dissolved iron. Our transformation experiments suggest that the formation of siderite is promoted when carbonate seeds are present.     

The interplay between event and background sedimentation and the origin of fossil‐rich carbonate concretions: a case study in Permian rocks of the Paraná Basin,Brazil

The Permian Serra Alta Formation was generated under transgressive conditions within a large, calm epeiric sea. A monotonous succession of ‘barren’, massive mudstones deposited under oxygen‐deficient conditions (mainly below storm wave base) is the main lithofacies of this unit. Fossils are generally rare and diluted in the matrix, but certain intervals contain shell‐rich concentrations with well‐preserved, closed articulated bivalves, mixed with shells and comminuted debris with variable quality of preservation, all encased in carbonate concretions. Two main scenarios may account for the origin of these bivalve‐rich concretions (i.e. unique events in sea‐water chemistry or unique burial‐starvation couplets). Sedimentological and taphonomic information indicates that the final deposition of the original shell‐rich mudstone intervals was probably tied to episodic influx of fine‐grained sediments in distal settings. Moderate bioturbation is also recorded suggesting low rates of sedimentation prior to early diagenesis. Hence, the fossil concentrations in concretions were formed due to the interplay of event and background sedimentation. These are internally simple concentrations with complex depositional histories. The concretion‐bearing beds are not randomly distributed in the Serra Alta Formation. Rather, they are found in the sparsely fossiliferous offshore deposits of the basal to intermediate portions of the unit. Thus, the concretionary mudstone beds and associated deposits are preserved in particular intervals and can be tracked for kilometres. This indicates that the conditions essential for concretion development existed only at particular stratigraphical intervals. Finally, our study strongly corroborates the idea that concretions are critical sources of sedimentological, taphonomic and stratigraphical information.     

Linking sedimentary sulfur and iron biogeochemistry to growth patterns of a cold‐water coral mound in the Porcupine Basin,S.W. Ireland (IODP Expedition 307)

Challenger Mound, a 150‐m‐high cold‐water coral mound on the eastern flank of the Porcupine Seabight off SW Ireland, was drilled during Expedition 307 of the Integrated Ocean Drilling Program (IODP). Retrieved cores offer unique insight into an archive of Quaternary paleo‐environmental change, long‐term coral mound development, and the diagenetic alteration of these carbonate fabrics over time. To characterize biogeochemical carbon–iron–sulfur transformations in the mound sediments, the contents of dithionite‐ and HCl‐extractable iron phases, iron monosulfide and pyrite, and acid‐extractable calcium, magnesium, manganese, and strontium were determined. Additionally, the stable isotopic compositions of pore‐water sulfate and solid‐phase reduced sulfur compounds were analyzed. Sulfate penetrated through the mound sequence and into the underlying Miocene sediments, where a sulfate–methane transition zone was identified. Small sulfate concentration decreases (<7 mm ) within the top 40 m of the mound suggested slow net rates of present‐day organoclastic sulfate reduction. Increasing δ³⁴S‐sulfate values due to microbial sulfate reduction mirrored the decrease in sulfate concentrations. This process was accompanied by oxygen isotope exchange with water that was indicated by increasing δ¹⁸O‐sulfate values, reaching equilibrium with pore‐water at depth. Below 50 mbsf, sediment intervals with strong ³⁴S‐enriched imprints on chromium‐reducible sulfur (pyrite S), high degree‐of‐pyritization values, and semi‐lithified diagenetic carbonate‐rich layers characterized by poor coral preservation, were observed. These layers provided evidence for the occurrence of enhanced microbial sulfate‐reducing activity in the mound in the past during periods of rapid mound aggradation and subsequent intervals of non‐deposition or erosion when geochemical fronts remained stationary. During these periods, especially during the Early Pleistocene, elevated sulfate reduction rates facilitated the consumption of reducible iron oxide phases, coral dissolution, and the subsequent formation of carbonate cements.     

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.     

Methane-flux-dependent lateral faunal changes in a Late Cretaceous chemosymbiotic assemblage from the Nakagawa area of Hokkaido, Japan

A Late Cretaceous carbonate body (2 m in maximum diameter) surrounded by clastic rocks, recently discovered in the Nakagawa area (Hokkaido, Japan), is interpreted as a methane‐seep deposit, on the basis of negative carbon isotopic composition (as low as ?43.5‰), variable sulphide sulphur isotopic composition, high carbonate content, and in situ fractures. It most likely formed owing to methane‐bearing pore‐water diffusion. We estimate that the concentration of methane decreased toward the margin of the carbonate body, and that only small carbonate concretions were precipitated at a certain distance from the methane‐seep centre. These spatial characteristics coincide well with the observed pattern of faunal distribution. The gastropod‐dominated association (indeterminate abyssochrysids and ataphrids and the acmaeid limpet Serradonta sp. are most common) co‐occurs with lucinid and thyasirid bivalves (Thyasira sp., Myrtea sp., and Miltha sp.), and was found within and just above the methane‐derived carbonate body. Acharax and Nucinella (solemyoid bivalves) are more typical of the peripheral part of the methane‐influenced sediments. We suggest that this pattern of faunal distribution reflects the decreasing concentration of methane and apparently also hydrogen sulphide when moving from the centre of discharge toward the periphery of the methane seep.     

Nutrients in pore waters from Dead Sea sediments

Pore waters were separated from 50 cm-long cores of Dead Sea sediments raised from waters depths of 25, 30 and 318 m. The salinity of the pore water is close to that of the overlying water at 225–230 g l^–1 chloride. The titration alkalinity of the pore water is about 60 % of the overlying water, and sulfate is also depleted. Ammonia and phosphate concentrations are higher than those of the water column with up to 50 mg l^–1 N-NH₃ (ten times increase) and 350 µg l^–1 P-PO _inf4 ^sup3– (four to eight times increase). Early diagenetic reactions are a result of decomposition of organic matter and of water-sediment interactions, resulting in aragonite precipitation, phosphate removal to the sediments, probably by absorption on iron-oxyhydroxides followed by remobilization, reduction of sulfate and formation of iron sulfides and accumulation of ammonia. Mass balance calculations show that pore water contribute about 80% of the ammonia and 30% of the phosphate input into the Dead Sea water column. On the other hand, the sediments act as a sink for carbonate and sulfate.     

Microscale Characterization and Trace Element Distribution in Bacteriogenic Ferromanganese Coatings on Sand Grains from an Intertidal Zone of the East China Sea

An ancient wood layer dated at about 5600 yr BP by accelerator mass spectrometry (AMS) ¹⁴C was discovered in an intertidal zone of the East China Sea. Extensive and horizontally stratified sediments with black color on the top and yellowish-red at the bottom, and some nodule-cemented concretions with brown surface and black inclusions occurred in this intertidal zone. Microscale analysis methods were employed to study the microscale characterization and trace element distribution in the stratified sediments and concretions. Light microscopy, scanning electron microscopy (SEM) and backscattered electron imaging (BSE) revealed the presence of different coatings on the sand grains. The main mineral compositions of the coatings were ferrihydrite and goethite in the yellowish-red parts, and birnessite in the black parts using X-ray powder diffraction (XRD). SEM observations showed that bacteriogenic products and bacterial remnants extensively occurred in the coatings, indicating that bacteria likely played an important role in the formation of ferromanganese coatings. Post-Archean Australian Shale (PAAS)-normalized middle rare earth element (MREE) enrichment patterns of the coatings indicated that they were caused by two sub-sequential processes: (1) preferentially release of Fe-Mn from the beach rocks by fermentation of ancient woods and colloidal flocculation in the mixing water zone and (2) preferential adsorption of MREE by Fe-Mn oxyhydroxides from the seawater. The chemical results indicated that the coatings were enriched with Sc, V, Cr, Co, Ni, Cu, Zn, Ba, especially with respect to Co, Ni. The findings of the present study provide an insight in the microscale features of ferromanganese coatings and the Fe-Mn biogeochemical cycling during the degradation of buried organic matter in intertidal zones or shallow coasts.     

Role of Fungal Mycelium in the Formation of Carbonate Concretions in Growing Media—An Investigation by SEM and Synchrotron-Based X-Ray Tomographic Microscopy

Soil fungi can facilitate calcification. Mushroom Morchella sp . mycelium induced the formation of carbonate concretions on the surface of an organic-based growing media amended with sand and ground limestone. According to SEM observation and X-ray-tomographic microscopy a dense mycelial network induced calcification. The CaCO₃ content of concretions (?: 0.3–1.5 cm) was found to be at 30%. Microsparitic calcite cemented the pores between the sand grains forming a dense clogging microstructure. Besides water uptake by the mycelium, a high evaporation rate and a decrease in pCO₂ contributed to the formation of the concretions. Fungal mycelium in the concretions is surrounded by voids indicating that at the surface of the mycelium, calcification is counteracted most probably by the release of organic acids.     

Lacustrine Nostoc (Nostocales) and associated microbiome generate a new type of modern clotted microbialite

Microbialites are mineral formations formed by microbial communities that are often dominated by cyanobacteria. Carbonate microbialites, known from Proterozoic times through the present, are recognized for sequestering globally significant amounts of inorganic carbon. Recent ecological work has focused on microbial communities dominated by cyanobacteria that produce microbial mats and laminate microbialites (stromatolites). However, the taxonomic composition and functions of microbial communities that generate distinctive clotted microbialites (thrombolites) are less well understood. Here, microscopy and deep shotgun sequencing were used to characterize the microbiome (microbial taxa and their genomes) associated with a single cyanobacterial host linked by 16S sequences to Nostoc commune Vaucher ex Bornet & Flahault, which dominates abundant littoral clotted microbialites in shallow, subpolar, freshwater Laguna Larga in southern Chile. Microscopy and energy‐dispersive X‐ray spectroscopy suggested the hypothesis that adherent hollow carbonate spheres typical of the clotted microbialite begin development on the rigid curved outer surfaces of the Nostoc balls. A surface biofilm included >50 nonoxygenic bacterial genera (taxa other than Nostoc) that indicate diverse ecological functions. The Laguna Larga Nostoc microbiome included the sulfate reducers Desulfomicrobium and Sulfospirillum and genes encoding all known proteins specific to sulfate reduction, a process known to facilitate carbonate deposition by increasing pH. Sequences indicating presence of nostocalean and other types of nifH, nostocalean sulfide:ferredoxin oxidoreductase (indicating anoxygenic photosynthesis), and biosynthetic pathways for the secondary products scytonemin, mycosporine, and microviridin toxin were identified. These results allow comparisons with microbiota and microbiomes of other algae and illuminate biogeochemical roles of ancient microbialites.     

Arsenic precipitation by an anaerobic arsenic‐respiring bacterial strain isolated from the polluted sediments of Orbetello Lagoon,Italy

Aims: To isolate and characterize an anaerobic bacterial strain from the deeper polluted lagoon sediment able to use as electron acceptors [As(V)] and sulfate (), using lactate as an electron donor. Methods and Results: Methods for isolation from polluted lagoon sediments included anaerobic enrichment cultures in the presence of As(V) and . Reduction of As(V) to As(III) was observed during the growth of the bacterial strain, and the final concentration of As(III) was lower than the initial As(V) one, suggesting the immobilization of As(III) in the yellow precipitate. The precipitate was identified by energy dispersive spectroscopy X‐ray as arsenic sulfide. Scanning electron microscopy (SEM) revealed rod‐shaped bacterial cells embedded in the precipitate, where net‐like formations strictly related to the bacterial cells were visible. The surface of the precipitate showed the adhesion of bacterial cells, forming clusters. Transmission electron microscopy (TEM) also highlighted precipitates inside the bacterial cells and on their surface. Following 16S rRNA sequencing, the bacterial strain 063 was assigned to the genus Desulfosporosinus. Conclusions: This study reports, for the first time, the isolation from the polluted lagoon sediments of a strain capable of respiring and using As(V) and as electron acceptors with lactate as the sole carbon and energy source with the formation of an arsenic sulfide precipitate. Significance and Impact of the Study: The identification of these properties provides novel insight into the possible use of the anaerobic strain in bioremediation processes and also adds to the knowledge on the biogeochemical cycling of arsenic.     

Oxygen isotopic composition of sulfate in deep sea pore fluid: evidence for rapid sulfur cycling

We present new data of oxygen isotopes in marine sulfate (δ¹⁸O_SO4) in pore fluid profiles through organic‐rich deep‐sea sediments from 11 ODP sites around the world. In almost all sites studied sulfate is depleted with depth, through both organic matter oxidation and anaerobic methane oxidation. The δ¹⁸O_SO4 increases rapidly near the top of the sediments, from seawater values of 9 to maxima between 22 and 25, and remains isotopically heavy and constant at these values with depth. The δ¹⁸O_SO4 in these pore fluid profiles is decoupled from variations in sulfur isotopes measured on the same sulfate samples (δ³⁴S_SO4); the δ³⁴S_SO4 increases continuously with depth and exhibits a shallower isotopic increase. This isotopic decoupling between the δ³⁴S_SO4 and the δ¹⁸O_SO4 is hard to reconcile with the traditional understanding of bacterial sulfate reduction in sediments. Our data support the idea that sulfate or sulfite and water isotopically exchange during sulfate reduction and that some of the isotopically altered sulfur pool returns to the environment. We calculate that the rapid increase in the δ¹⁸O_SO4 in the upper part of these sediments requires rates of this oxygen isotope exchange that are several orders of magnitude higher than the rates of net sulfate reduction calculated from the sulfate concentration profiles and supported by the δ³⁴S_SO4. We suggest several mechanisms by which this may occur, including ‘net‐zero’ sulfur cycling, as well as further experiments through which we can test and resolve these processes.     

Development of a protocol for recognizing sulfidic sediments (potential acid sulfate soils) in freshwater wetlands

Summary   The presence of sulfidic sediments (potential acid sulfate soils) is an emerging problem in the management of inland wetlands. Using data from 81 wetlands in the Murray-Darling Basin, a simple protocol was developed to assess whether a wetland will contain sulfidic sediments at levels that could cause ecological damage. Risk factors include whether or not the wetland receives municipal waste or irrigation return water, elevated salinity in the overlying water (>1750 µS/cm) or sediment (400 µS/cm in a 1:5 soil : water extract) and high levels of sulfate in the water column (>10 mg/L). Neutral or basic sediment pH indicates that, even if the sediment does contain sulfidic sediments, there is a reduced likelihood of acidification if the sediments are oxidized.     

Palaeoecology of the Aptian Santana Formation (Northeastern Brazil)

In the interior of northeastern Brazil there occurs the Santana Formation of Aptian age, composed lithologically of three members: Crato — an alternation of thin limestones and shales; Ipubi — gypsum; and Romualdo — almost pure limestone. The formation is very fossiliferous; pollen, plant remains, ostracodes, conchostracans, mollusks, echinoids, fishes and a few reptiles. The fishes and reptiles occur in limestone concretions. All data on sediment character and on fossils have been considered together for the interpretation of the palaeoenvironment of the formation.It was concluded that at the time of the Crato Member the deposition occurred in shallow lakes and swamps. Later (Ipubi Member), a marine invasion took place during a time of dry climate, causing anhydrite precipitation. Gradually the connection with the sea became obstructed so that the environment at the end of the depositional period became once more one of fresh water (Romualdo Member). Faunal assemblages and sediments point to a fairly great supply of river water during the whole time of basin deposition, under warm and dry climatic conditions. The connection with the sea persisted for a rather short period.     

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate‐reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu‐2, mixed‐layer illite‐smectite RAr‐1 and ISCz‐1, and illite IMt‐1) were exposed to D. vulgaris in a non‐growth medium with and without anthraquinone‐2,6‐disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X‐ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals.     

In situ S‐isotope compositions of sulfate and sulfide from the 3.2 Ga Moodies Group,South Africa: A record of oxidative sulfur cycling

Sulfate minerals are rare in the Archean rock record and largely restricted to the occurrence of barite (BaSO₄). The origin of this barite remains controversially debated. The mass‐independent fractionation of sulfur isotopes in these and other Archean sedimentary rocks suggests that photolysis of volcanic aerosols in an oxygen‐poor atmosphere played an important role in their formation. Here, we report on the multiple sulfur isotopic composition of sedimentary anhydrite in the ca. 3.22 Ga Moodies Group of the Barberton Greenstone Belt, southern Africa. Anhydrite occurs, together with barite and pyrite, in regionally traceable beds that formed in fluvial settings. Variable abundances of barite versus anhydrite reflect changes in sulfate enrichment by evaporitic concentration across orders of magnitude in an arid, nearshore terrestrial environment, periodically replenished by influxes of seawater. The multiple S‐isotope compositions of anhydrite and pyrite are consistent with microbial sulfate reduction. S‐isotope signatures in barite suggest an additional oxidative sulfate source probably derived from continental weathering of sulfide possibly enhanced by microbial sulfur oxidation. Although depositional environments of Moodies sulfate minerals differ strongly from marine barite deposits, their sulfur isotopic composition is similar and most likely reflects a primary isotopic signature. The data indicate that a constant input of small portions of oxidized sulfur from the continents into the ocean may have contributed to the observed long‐term increase in Δ³³S_sulfate values through the Paleoarchean.     

Microbialite concretions in a dolostone crust at the Permian–Triassic boundary of the Xishan section in Jiangsu Province,South China

Carbonate concretions with structures and fossil groups associated with microbialite developed in a dolostone crust at the Permian–Triassic boundary of the Xishan section in Jiangsu Province, South China. These structures include clotted fabrics and laminated carbonate needles, as well as abundant carbonate crystal fans. Fossil groups associated with microbialite include microconchids, small gastropods, and small foraminifers. These fabrics and fossils suggest that the concretions are carbonate microbialite blocks developed in the dolostone crust. On the basis of the analysis of the microfabrics and the fossil groups together with a comparison to modern analogues, we attribute the formation of the micritic patches in the microbialite concretions to the calcification of cyanobacterial mats via carbonate nanoparticles and we attribute the carbonate crystal fans to the direct recrystallization of micritic carbonates. The sparitic patches were interpreted as either the direct recrystallization of micritic carbonates or the precipitation of carbonate spars in the inter-/intra-spaces of metazoan shells together with the recrystallization of these shells. The similarities to modern stromatolites, both in morphology and in internal texture, suggest that the laminated carbonate needles are stromatolite laminae built by filamentous cyanobacteria. The preservation of these microbialite microfabrics indicates that early lithification by carbonate precipitation was widespread and intense following the end-Permian boundary events. The weak development of microbialites as small concretions may be attributed to the deeper water depth and the lower water energy in the Xishan area during the earliest Triassic.     

Lake Biwa and the ocean: geochemical similarity and difference

The average composition of water, bottom sediments, manganese (Mn) crusts, and Mn concretions from Lake Biwa (the largest freshwater lake in Japan) are re-examined, in conjunction with those of seawater, oceanic pelagic clay, and deep-sea Mn nodules. The purpose is to gain additional insights into the geochemical behaviors of elements in Lake Biwa and the ocean, which are quite different in ionic strength (or salinity), pH, water residence times, sediment accumulation rates, carbon fluxes to sediments, and the redox potential in sediments. Excluding a few millimeters of oxic surface sediment, there is no appreciable accumulation of Mn in the Lake Biwa bottom sediments due to reducing condition there. Consequently, other B-type cations [such as iron (Fe), gallium (Ga), copper (Cu), lead (Pb), cobalt (Co), tin (Sn), and bismuth (Bi), with subshell valence electron configuration of d ¹⁻¹⁰] are also less concentrated in the lake sediments than in the oceanic pelagic clay. In turn, B-type cations have much higher dissolved concentrations in the lake water than in the ocean. The rare earth elements (REE) mainly form organic complexes in the lake water and carbonate complexes in the ocean. REE are mostly associated with detritus aluminosilicate phases in Lake Biwa sediments but with phosphate phases in deep-sea sediments. Fe and Mn oxide phases are clearly separated in marine Mn nodules and crusts but not in Mn crusts and concretions from Lake Biwa. Useful parameters such as the enrichment factor (E _Al) and logarithms of the distribution coefficient (log K _d) of elements between solid and liquid phases were estimated in both systems for further discussions.