Sequence stratigraphy of Eocene incised valley clastics and associated sediments,Island of Rab,northern Adriatic Sea,Croatia

Clastic sediments of Middle–Late Eocene age were studied on the Island of Rab (northern Adriatic Sea, Croatia) in order to reconstruct their depositional history, depositional environments, and geometry of sandstone bodies. Detailed outcrop logging and mapping revealed the response of depositional systems to frequent relative sea-level changes, which initiated significant basinward and landward shifts of facies, respectively. Tidal sandstones are commonly underlain by shoreface sandstones, and overlain by offshore sandy marls, whereas the latter are again overlain by shoreface sandstones. Major relative sea-level falls initiated basinward shift of depositional systems and the incision of incised valleys or estuaries, and consequently truncated the underlying shelf sediments. In some cases, the accelerated sea-level fall caused rapid shoreface progradation which is interpreted as a forced regression. Relative sea-level rise caused flooding of the incised relief, and deposition of tidal sandstone bodies which overlie type-I sequence boundaries. The coarse lag sediment of these sequence boundaries locally disappears laterally, and the boundary is granulometrically less prominent. All of the major bounding surfaces have been recognized in the sections studied, although the maximum flooding surface is recognized as a thin “zone” instead of a single surface. Altogether, 28 complete sequences, and 15 parasequences are recognized in the informal unit of the Lopar sandstones, documenting the depositional response to high-frequency relative sea-level oscillations. They have so far not been recognized in the Eocene of the eastern Adriatic region.     

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.     

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.     

Origin and paleoecology of Middle Jurassic hiatus concretions from Poland

Bored and encrusted carbonate concretions, termed hiatus concretions, coming from the Middle Jurassic (Upper Bajocian and Bathonian) siliciclastics of the Polish Jura, south-central Poland, have been subjected to detailed paleoecological investigation for the first time. The concretions possess variable morphology and bear distinct traces of bioerosion and encrustation as a result of exhumation on the sea floor during intervals of low sedimentation and/or erosion. The borings are dominated by Gastrochaenolites and Entobia. Epilithozoans, represented by at least 26 taxa, are dominated by sabellid/serpulid worm tubes and bryozoans, while sponges and corals are minor. No relationship between the concretion size and the number of encrusters has been found, suggesting that concretion size was not the primary factor controlling diversity. Stable isotope analyses and the presence of crustacean scratch marks and Rhizocorallium traces on many of the hiatus concretions indicate that they formed just below the sediment–water interface, within the sulfate reduction zone. Moreover, crustacean activities may have been a prelude to their origin, as shapes of many concretions closely resemble thalassinoidean burrow systems. It is also possible that crustacean activity around the concretions promoted their exhumation by loosening the surrounding soft sediment. The presence of borings and encrusters on different concretion surfaces, as well as truncated borings and a number of abraded epilithozoans, indicate that after the concretions were exhumed they were repeatedly overturned and moved on the sea floor, probably due to episodic storm-related bottom currents in shallow subtidal environment.     

Stratigraphic application of Thalassinoides ichnofabric in delineating sequence stratigraphic surfaces (Mid-Cretaceous), Kopet-Dagh Basin,northeastern Iran

This study integrates ichnological and sedimentological data to refine depositional sequences and interpretations of sea-level dynamics for the shallow marine, Albian–Cenomanian Aitamir Formation in northeastern Iran. Three ichnofabrics are present in a succession of glauconitic mudstone and sandstone. This is a sequence that grades upward from a lower glauconitic sandstone unit with trough cross-stratification, hummocky and ripple cross-lamination into a fining-up unit of mudstone with intercalated sandstone beds. The lower unit contains an ichoassemblage of the Ophiomorpha–Palaeophycus ichnofabric (upper shoreface), whereas the upper unit bears ichnoassemblages of the Thalassinoides ichnofabric (in a distinctive level at the top cycle which demarcates the base of the next cycle) (middle shoreface) and the Chondrites–Planolites ichnofabric (lower shoreface). An upper shoreface–lower shoreface trend from the Ophiomorpha–Palaeophycus ichnofabric to the Chondrites–Planolites ichnofabric represents a deepening-upward sequence. An integrated sedimentological and ichnological approach has allowed the recognition of the internal organization of the sequence and the characterization of significant discontinuity surfaces at sequence scales. Thalassinoides ichnofabric reveals colonization of firmgrounds during prolonged times between erosion and deposition related to transgressive surfaces. Transgressive surfaces (sequence boundaries) are generally well-cemented and marked by increased glauconite content, and densely crowded, predominantly vertical or oblique, relatively large, very distinct, unlined, and uncompacted burrows (omission suite) and are associated with rare highly abraded and fragmented shell remains.     

Origin of jurassic ammonite concretions assemblages at Alfeld,Germany: a biogenic alternative

The ecology of macrofossils in ammonite-rich concretions and in coeval host sediments from Lower Bajocian mudstones in N.W. Germany indicates a predominantly epifaunal suspensionfeeding community living at maximally 50–90 m on a firm mud bottom during a hiatus or reduced sedimentation. Concretions are lined below with shell debris and contain numerous dimorphicStephanoceras [Ammonitina]. The dimorphs, however, are not a corresponding pair, showing instead extreme and uniquely inverse dimorphic ratios. Distribution of fossils and other debris within the concretions and the host sediments suggests the ammonite shells were swept by currents into subcircular depressions, lined with shell debris. We propose a biogenic alternative to the current/wave scour hypothesis for the origin of the depressions, which are essential to the accumulation of concretion assemblages: the pits were produced by rays feeding on the benthic fauna. Extant rays (Elasmobranchia) excavate such subcircular pits by jetting water through the gills (or mouth) for winnowing of the fauna from the sediment. The ammonite shells were transported post-mortem into the pits by moderate bottom currents. Rapid burial occurred by either a mudflow or renewal of strong sedimentation. Concretion growth was initiated by decomposition of organic matter within the mud.     

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.     

Toarcian–Kimmeridgian depositional cycles of the south-western Morondava Basin along the rifted continental margin of Madagascar

After rifting and final breakup of Gondwana along the former East-African-Antarctic Orogen during the Toarcian–Aalenian, passive margins formed around the Proto-Indian Ocean. Sedimentological and stratigraphic studies in the southern Morondava Basin contribute to an improved reconstruction of palaeoenvironmental changes during the syn-rift and post-rift margin formation. Depositional models based on outcrop and literature data in combination with subsurface data sets provide a stratigraphic framework of four transgressive-regressive (T-R) cycles. The incorporation of stratal architecture models derived from seismic images is essential. After a syn-breakup T-R cycle (T-R1), the post-breakup succession commenced with a Bajocian – Early Bathonian carbonate platform (T2). Middle–Late Bathonian sandstones (R2) formed when a global sea-level fall forced the shoreline to move basinward. Incised valleys and palaeokarst known from seismic lines are typical for forced regression cycles. In the Early Callovian again a widespread transgression occurs (T3). During a short regressive phase from the Late Callovian(?) to Early Oxfordian (R3), the siliciclastic shoreface deposits prograded onto the shelf. From the Early Oxfordian onwards a transgressive trend continued (T4). T1–T3 can be explained as the response to the structural development of the breakup rifting but they follow sea-level changes observed in other parts of the world. R3 and T4, in contrast, reflect eustacy.     

Morphological and chemical characterization of mineral concretions in the freshwater bivalve Anodonta cygnea (Unionidae)

The freshwater mussel Anodonta cygnea is commonly used as a model organism for biomineralization studies, its peculiar morphofunctional properties also make it an excellent environmental biomonitor. The first detailed on the calcareous concretions from gill and mantle tissue, as well as fluids of the freshwater bivalve A. cygnea, supported by histological, scanning, spectrometry, and spectroscopy analyses. Through these analyses, the morphology, structure, and chemical characterization of these biomineral concretions were accomplished. The concretions represent a high percentage of the dry weight of these organisms. In gill tissue, it can reach up to 50% of dry weight prior to reproductive maturity. Analysis of elemental composition of the tissue concretions showed the presence of calcium and phosphate, as main components, associated with other residual elements like iron, manganese, magnesium, and zinc. Concretions are arranged in concentric alternated layers of organic and inorganic matrix. The shape and size of the concretions vary substantially, from very small, less than 1 μm diameter with very regular round structure, found mainly in the mantle tissue, to more than 50 μm length with irregular globular clusters, found predominantly in the gills. The microstructural organization is of a hydroxyapatite polymorphism in the mantle, in contrast to the gills, which exhibit irregular structure and carbonated hydroxyapatite polymorphism. These differences are supported by higher contents of dinitrogen pentoxide, magnesium, and iron in the mantle concretions, but higher contents of manganese and zinc in the gills. Furthermore, the results indicate that the mineral concretion formation in A. cygnea is a hemocytes reaction to particle or toxic invasions. A second relevant role, concerns the close involvement of these microspherules on the adult and larval shell calcification. J. Morphol. 276:65–76, 2015. © 2014 Wiley Periodicals, Inc.     

Palaeoenvironmental significance of 'bone-beds' in organic-rich mudstone successions: an example from the Upper Triassic of south-west Britain

A combined field-based/petrographic study to investigate the formation of Rhaetian 'bone-beds' from the Westbury Formation, Upper Triassic of south-west Britain, has been undertaken. 'Bone-beds' in the Westbury Formation have been found at the top of coarsening upward successions, on flooding surfaces which underlie organic-rich mudstones. These 'bone-beds' are frequently found either overlying or amalgamated with 'shell-beds', and often contain large (up to cobble-sized) intraclasts. This work indicates that they formed during a period of relative sea-level rise, when the sediment was being reworked (forming a transgressive lag) and a condensed section had developed. Phosphate authigenesis is thought to have occurred at the oxic/Fe-reduction interface, where the pore waters were dysoxic, enriched with dissolved phosphate and relatively acidic. 'Bone-bed' formation was terminated when siliciclastic mud prograded over the condensed section and 'normal' anoxic/sulfidic pore water conditions were established in the sediment.     

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.     

Iron–Manganese Concretions Sustaining Microbial Life in the Baltic Sea: The Structure of the Bacterial Community and Enrichments in Metal-Oxidizing Conditions

The abundant deposits of spherical iron-manganese concretions in the Gulf of Finland are colonized by bacteria in vast numbers. Communities on the surface and in the porous interior have formed two separate clusters, in accordance with their genetic differences. The overall bacterial community in the concretions was highly diverse, representing 12 phyla. Half of the bacteria were affiliated with the most common classes of Proteobacteria, while a third of the bacteria were unclassified. Cloned 16S rRNA-gene sequences of the concretion bacteria showed high scores for similarity to the sequences obtained from sea sediments, metal-rich environments, and ocean crust. The clone library of native concretions was not dominated by known Fe- and Mn-oxidizing species. Known Mn-oxidizing bacteria Sphingomonas, Pseudomonas, and Bacillus were enriched in experiments with Mn²⁺-containing liquid media, whereas Prosthecobacter (Verrucomicrobia) and Rheinheimera were enriched in semisolid media possibly better simulating the natural conditions in the concretions. In a corresponding experiment, the Fe²⁺-oxygen gradient favored the enrichment of Shewanella baltica and Thalassolituus oleivorans, which are known to reduce Fe and to degrade petroleum hydrocarbons, respectively. An individual spherical concretion forms a microcosm for a diverse microbial community having potential to oxidize Fe and Mn as shown in cultivation experiments. Therefore, bacteria may significantly affect the formation of the concretions in the Gulf of Finland.     

Origin,structure, composition and age-dependence of mineralized dense bodies (concretions) in the midgut epithelium of the adult housefly, Musca domestica

The epithelial cells of the midgut in 1–40 day old adult female houseflies were examined by electron microscopic, X-ray microanalytic and histochemical techniques in order to study the mode of genesis, chemical nature and age-associated distribution of dense bodies. Dense bodies contain high concentrations of phosphorus, sulphur, chlorine, calcium, iron and copper; they are therefore termed concretions. Concretionary material is initially deposited within Golgi vesicles, lamellar bodies and residual bodies. The average size of the concretion granules and the concentration of the sequestered material increases with age, while new concretions are continually formed throughout life. With advancing age, concretions accumulate in the epithelial cells and occupy a considerable proportion of the cytoplasm in old flies. It is postulated that the concretions sequester superfluous minerals and may play an important role in the excretory system of the adult housefly.     

Late Cenomanian–Early Turonian facies development and sea-level changes in the Bodenwöhrer Senke (Danubian Cretaceous Group, Bavaria, Germany)

The Upper Cenomanian–Lower Turonian litho-stratigraphic units of the Danubian Cretaceous Group of the proximal Bodenwöhrer Senke (Regensburg, Eibrunn and Winzerberg formations, the latter consisting of a lower Reinhausen Member and an upper Knollensand Member), have been investigated with a focus on facies analysis and sequence stratigraphy. Analyses of litho-, bio-, and microfacies resulted in the recognition of 12 predominantly marine facies types for the Eibrunn and Winzerberg formations. Petrographic and paleontological properties as well as gradual transitions in the sections suggest that their depositional environment was a texturally graded, predominantly siliciclastic, storm-dominated shelf. The muddy–siliceous facies types FT 1–3 have been deposited below the storm wave-base in an outer shelf setting. Mid-shelf deposits are represented by fine- to medium-grained, bioturbated, partly glauconitic sandstones (FT 4–6). Coarse-grained, gravelly and/or shell-bearing sandstones (FT 7–10) developed in the inner shelf zone. Highly immature, arkosic coarse-grained sandstones and conglomerates (FT 11 and 12) characterize an incised, high-gradient braided river system. The Winzerberg Formation with its general coarsening- and thickening-upward trend reflects a regressive cycle culminating in a subaerial unconformity associated with a coarse-grained, gravelly unit of marine to fluvial origin known as the “Hornsand” which is demonstrably diachronous. The overlying Altenkreith Member of the Roding Formation signifies the onset of a new transgressive cycle in the early Middle Turonian. The sequence stratigraphic analysis suggests that the deposition of the Upper Cenomanian and Lower Turonian strata of the Bodenwöhrer Senke took place in a single cycle of third-order eustatic sea-level change between the major sequence boundaries SB Ce 5 (mid-Late Cenomanian) and SB Tu 1 (Early–Middle Turonian boundary interval). The southeastern part of the Bodenwöhrer Senke was flooded in the mid-Late Cenomanian (Praeactinocamax plenus transgression) and a second transgressive event occurred in the earliest Turonian. In the central and northwestern parts of the Bodenwöhrer Senke, however, the initial transgression occurred during the earliest Turonian, related to pre-transgression topography. Thus, the Regensburg and Eibrunn formations are increasingly condensed here and cannot be separated anymore. Following an earliest Turonian maximum flooding, the Lower Turonian Winzerberg Formation filled the available accommodation space, explaining its constant thickness of 35–40 m across the Bodenwöhrer Senke and excluding tectonic activity during this interval. Rapid sea-level fall at SB Tu 1 terminated this depositional sequence. This study shows that Late Cenomanian–Early Turonian deposition in the Bodenwöhrer Senke was governed by eustatic sea-level changes.     

The formation of giant tubular concretions triggered by anaerobic oxidation of methane as revealed by archaeal molecular fossils (Lower Eocene, Varna, Bulgaria)

Impressive, several meters high tubular concretions in shallow marine calcareous sands and sandstones represent part of the well-exposed, subsurface plumbing network of an Early Eocene methane seep system in the Balkanides foreland (Pobiti Kamani area, Varna, NE Bulgaria). An integrated approach, including petrography, inorganic geochemistry and lipid biomarker analyses was used to reconstruct the evolution of pore fluids and cementation conditions during tube formation and particularly, the role of methane-related carbonate diagenesis. Host sediment lithification from marine pore waters was perturbed soon after deposition by oxidation of predominantly microbial methane causing pervasive cementation by a ¹³C-poor, homogeneous calcite cement (δ¹³C values as low as − 44.5‰ V-PDB). The importance of microbially mediated anaerobic oxidation of methane (AOM) is confirmed by extremely ¹³C-depleted archaeal biomarkers (δ¹³C values as low as − 123‰ V-PDB). A suite of macrocyclic dialkyl glycerol diethers (MDGD-0 to -2) and sn-3-hydroxyarchaeol comprises a characteristic trait of the Eocene tubular concretions and might represent molecular fossils of so far unknown methane-oxidizing archaea (ANME). Subsurface calcite cementation surrounding the ascending methane plume, resulted from the changing pore water chemistry in response to AOM and could have, on a local scale, been encouraged by the concurrent alteration of detrital feldspar. Fluctuating δ¹³C (up to − 8‰ V-PDB) and δ¹⁸O (− 0.5 to − 9‰ V-PDB) signatures within a single tubular sandstone concretion are at least partly the consequence of isotopic resetting during late meteoric water circulation.     

Controls on Devonian hemi-pelagic limestone deposition analyzed on cephalopod ridge to slope sections,Eastern Anti-Atlas,Morocco

The hemi-pelagic Tafilalt Ridge separating the Maider Basin from the Tafilalt Basin developed progressively from an Early Devonian homoclinal ramp, through a Middle Devonian ramp-slope stage of moderate topography, to a mature cephalopod ridge during the Late Devonian and formed a spur-like element extending from the southern shallow-water Maider Platform to the broader northern hemi-pelagic Tafilalt Platform. During the Middle Devonian, thick lowstand aprons were shed onto the ridge-slope from an active mid-ramp carbonate factory in the south (Maider Platform). The shallow-water derived sediments first by-passed the central paleohigh, but then onlapped the ridge during start of sea-level rise. The allodapic limestones (storm-induced turbidites, tempestites, and debrites) of the aprons consist of large parts or entirely of reworked lithic peloids. The lithic peloids are interpreted as the main foundation of all micritic lithofacies types in the distal ramp locations, including those on the hemi-pelagic cephalopod ridge. Lateral facies transition of allodapic limestones into nodular cephalopod limestones on the ridge suggests the latter originate from allodapic beds and were subsequently transformed into nodular limestones by bioturbation, early diagenesis, and the faunal input from a hemi-pelagic community. Iron-rich hardgrounds formed on the ridge during major regressive phases as a result of increased winnowing by the wave-base and correlate with siliciclastic turbidite deposition on the slope. The hardgrounds can be correlated with hiatuses on the Tafilalt Platform, which formed a broader hemi-pelagic swell to the north. During the Late Devonian, the southern Maider Basin carbonate factory became unproductive or disappeared, and a ridge facies of truly hemi-pelagic autochthonous limestones developed. Allodapic deposits on the slope were shed from the ridge itself at this time but did not form well-defined aprons.