Relations of petrographical and geochemical parameters in the middle Miocene Lavanttal lignite (Austria)

Samples from two lignite seams (Lower Seam, Upper Seam) of the Lavanttal basin (Austria) and additional xylite were investigated for variations in maceral composition, petrography-based facies indicators, bulk geochemical parameters, and molecular composition of hydrocarbons. Both seams originated in a topogenous mire and evolved within a transgressive setting. The final drowning of the mire is indicated by sapropelic shales. Whereas the sapropelic shale overlying the Lower Seam was deposited in a freshwater lake, the sapropelic shale above the Upper Seam represents a brackish lake.Numerous relationships are found between petrography-based facies indicators and the geochemical composition of organic matter. The contents of macerals of the liptinite group are positively correlated with soluble organic matter (SOM) yields and hydrogen index (HI). Consistent with maceral composition and high HI values, enhanced proportions of short-chain n-alkanes, which are predominantly found in algae and microorganisms, are obtained from samples of the sapropelic shales. The final drowning of the mire is reflected by decreasing pristane/phytane ratios, due to the rise in (ground)water table and the establishment of anaerobic conditions, as well as by decreasing ratios of diasterenes/sterenes, indicating increasing pH values in the mire. The degree of gelification of plant tissue (gelification index) is governed by the microbial activity in the mire, as indicated by the hopanes concentration. The differences in floral assemblage during the formation of the Lavanttal lignite seams are reflected by major differences in tissue preservation. Preservation of plant tissue (TPI) in the Lavanttal lignite is obviously controlled by the presence/absence of decay-resistant gymnosperms in the peat-forming vegetation, and additionally influenced by the relative contribution of wood to coal formation. The results provide evidence that valuable information for coal facies characterization could be obtained by petrography-based and geochemical facies indicators. An influence of the floral assemblage (gymnosperms/angiosperms ratio) and of the contribution of algal biomass on carbon isotopic composition of the organic matter (δ¹³C = − 24.2 to − 28.6‰) is proposed. Carbon cycling during biogeochemical decomposition of plant tissue by bacteria is suggested to affect the δ¹³C values of the coal. The chemotaxonomical classification of the xylites as gymnosperm remnants, based on the molecular composition of terpenoid biomarkers, is corroborated by the carbon isotopic composition of the xylites (mean δ¹³C = − 24.1‰) and the extracted cellulose (mean δ¹³C = − 20.2‰). The higher isotopic difference of about 3.9‰ between cellulose and total organic carbon of the xylites, compared to the difference between cellulose and wood found in modern trees, is explained by the smaller effect of decomposition on δ¹³C of cellulose.     

Sr isotope excursion across the Precambrian–Cambrian boundary in the Three Gorges area, South China

The Precambrian/Cambrian (PC/C) boundary is one of the most important intervals for the evolution of life. However, the scarcity of well-preserved outcrops across the boundary leaves an obstacle in decoding surface environmental changes and patterns of biological evolution.In south China, strata through the PC/C boundary are almost continuously exposed and contain many fossils, suitable for study of environmental and biological change across the PC/C boundary. We undertook deep drilling at four sites in the Three Gorges area to obtain continuous and fresh samples without surface alteration and oxidation. ⁸⁷Sr/⁸⁶Sr ratios of the fresh carbonate rocks, selected based on microscopic observation and geochemical signatures of Mn/Sr and Rb/Sr ratios, aluminum and silica contents, and δ¹³C and δ¹⁸O values, were measured with multiple collector-inductively coupled plasma–mass spectrometric techniques.The chemostratigraphy of ⁸⁷Sr/⁸⁶Sr ratios of the drilled samples displays a smooth curve and a large positive anomaly just below the PC/C boundary between the upper part of Baimatuo Member of the Dengying Formation and the lower part of the Yanjiahe Formation. The combination of chemostratigraphies of δ¹³C and ⁸⁷Sr/⁸⁶Sr indicates that the ⁸⁷Sr/⁸⁶Sr excursions preceded the δ¹³C negative excursion, and suggests that global regression or formation of the Gondwana supercontinent, possibly together with a high atmospheric pCO₂, caused biological depression.     

Carbon isotope chemostratigraphy of a Precambrian/Cambrian boundary section in the Three Gorge area, South China: Prominent global-scale isotope excursions just before the Cambrian Explosion

Carbon isotope chemostratigraphy has been used for worldwide correlation of Precambrian/Cambrian (Pc/C) boundary sections, and has elucidated significant change of the carbon cycle during the rapid diversification of skeletal metazoa (i.e. the Cambrian Explosion). Nevertheless, the standard δ¹³C curve of the Early Cambrian has been poorly established mainly due to the lack of a continuous stratigraphic record. Here we report high-resolution δ¹³C chemostratigraphy of a drill core sample across the Pc/C boundary in the Three Gorge area, South China. This section extends from an uppermost Ediacaran dolostone (Dengying Fm.), through a lowermost Early Cambrian muddy limestone (Yanjiahe Fm.) to a middle Early Cambrian calcareous black shale (Shuijingtuo Fm.). As a result, we have identified two positive and two negative isotope excursions within this interval. Near the Pc/C boundary, the δ¹³C_carb increases moderately from 0 to + 2‰ (positive excursion 1: P1), and then drops dramatically down to − 7‰ (negative excursion 1: N1). Subsequently, the δ¹³C_carb increases continuously up to about + 5‰ at the upper part of the Nemakit–Daldynian stage. After this positive excursion, δ¹³C_carb sharply decreases down to about − 9‰ (N2) just below the basal Tommotian unconformity. These continuous patterns of the δ¹³C shift are irrespective of lithotype, suggesting a primary origin of the record. Moreover, the obtained δ¹³C profile, except for the sharp excursion N2, is comparable to records of other sections within and outside of the Yangtze Platform. Hence, we conclude that the general feature of our δ¹³C profile best represents the global change in seawater chemistry. The minimum δ¹³C of the N1 (− 7‰) is slightly lower than carbon input from the mantle, thus implying an enhanced flux of ¹³C-depleted carbon just across the Pc/C boundary. Hence, the ocean at that time probably became anoxic, which may have affected the survival of sessile or benthic Ediacaran biota. The subsequent δ¹³C rise up to + 5‰ (P2) indicates an increase of primary productivity or an enhanced rate of organic carbon burial, which should have resulted in lowering pCO₂ and following global cooling. This scenario accounts for the cause of the global-scale sea-level fall at the base of the Tommotian stage. The subsequent, very short-term, and exceptionally low δ¹³C (− 9‰) in N2 could have been associated with the release of methane from gas hydrates due to the sea-level fall. The inferred dramatic environmental changes (i.e., ocean anoxia, increasing productivity, global cooling and subsequent sea-level fall with methane release) appear to coincide with or occur just before the Cambrian Explosion. This may indicate synchronism between the environmental changes and rapid diversification of skeletal metazoa.     

Further sulfur and carbon isotope studies of late Archean iron-formations of the Canadian shield and the rise of sulfate reducing bacteria

Sulfur and carbon contents and isotope ratios are reported for five Archean iron-formations, Helen, Nakina and Finlayson, Lumby and Bending Lake areas, distributed across 850 km of the Canadian shield all 2.7 Ga-old.A δ³⁴S profile through a complete stratigraphic column (oxide facies excluded) of the Helen iron-formation shows a δ³⁴S range of 30.2‰, mean δ³⁴S value of 2.5‰ and a standard deviation (δ_i) of 7.3‰ In sharp contrast to the sulfide and siderite facies, the oxide facies in the column shows a uniform δ³⁴S value close to zero. The δ³⁴S values obtained for the other four iron-formations are again wide ranging, highly variable in the sulfide and pyrite—siderite facies, but uniform and close to zero for the oxide facies.The carbon in the oxide, siderite, chert facies has δ¹³C values of +2.3 to −1.1‰ in the range of Phanerozoic marine carbonates. However, the carbonates in the graphite rich sulfide facies have δ¹³C values as low as −7.6‰. The mixing of reduced carbon with marine carbonate is suggested to explain the light carbonate values. The reduced carbon associated with the light carbonate is also relatively light at up to δ¹³C_org = 33.5‰, but is in the range of other Precambrian values. Distal, high temperature, abiogenic sulfate reduction as a source of highly fractionated sulfides in the Archean iron-formations is ruled out on the basis of both isotopic and geologic evidence. It is concluded that only the bacterial reduction of sulfate at low temperatures could produce the wide ranging, highly variable δ³⁴S values exhibited by these sulfides over large areas.     

Palaeoenvironmental and diagenetic reconstruction of a closed‐lacustrine carbonate system – the challenging marginal setting of the Miocene Ries Crater Lake (Germany)

Chemostratigraphic studies on lacustrine sedimentary sequences provide essential insights on past cyclic climatic events, on their repetition and prediction through time. Diagenetic overprint of primary features often hinders the use of such studies for palaeoenvironmental reconstruction. Here the potential of integrated geochemical and petrographic methods is evaluated to record freshwater to saline oscillations within the ancient marginal lacustrine carbonates of the Miocene Ries Crater Lake (Germany). This area is critical because it represents the transition from shoreline to proximal domains of a hydrologically closed system, affected by recurrent emergent events, representing the boundaries of successive sedimentary cycles. Chemostratigraphy targets shifts related to subaerial exposure and/or climatic fluctuations. Methods combine facies changes with δ ¹³C–δ ¹⁸O chemostratigraphy from matrix carbonates across five closely spaced, temporally equivalent stratigraphic sections. Isotope composition of ostracod shells, gastropods and cements is provided for comparison. Cathodoluminescence and back‐scatter electron microscopy were performed to discriminate primary (syn‐)depositional, from secondary diagenetic features. Meteoric diagenesis is expressed by substantial early dissolution and dark blue luminescent sparry cements carrying negative δ ¹³C and δ ¹⁸O. Sedimentary cycles are not correlated by isotope chemostratigraphy. Both matrix δ ¹³C and δ ¹⁸O range from ca −7·5 to +4·0‰ and show clear positive covariance (R  = 0·97) whose nature differs from that of previous basin‐oriented studies on the lake: negative values are here unconnected to original freshwater lacustrine conditions but reflect extensive meteoric diagenesis, while positive values probably represent primary saline lake water chemistry. Noisy geochemical curves relate to heterogeneities in (primary) porosity, resulting in selective carbonate diagenesis. This study exemplifies that ancient lacustrine carbonates, despite extensive meteoric weathering, are able to retain key information for both palaeoenvironmental reconstruction and the understanding of diagenetic processes in relation to those primary conditions. Also, it emphasizes the limitation of chemostratigraphy in fossil carbonates, and specifically in settings that are sensitive for the preservation of primary environmental signals, such as lake margins prone to meteoric diagenesis.     

Influence de la diagenèse d''enfouissement sur l''homogénéisation isotopique K-Ar des illites: exemple du Jurassique-Crétacé du bassin d''Agadir, Maroc

The clay assemblages of the Late Jurassic-Early Cretaceous sediments of the Agadir Basin are affected by burial diagenesis. Apparent ages of these formations, from the K-Ar dating of fine grain size fractions (< 2 μm), decrease downward. This indicates an opening of the K-Ar isotopic system of detrital Hercynian minerals during burial. The extent of the isotopic rehomogenisation is more important in sandstones than in clayey marl facies. During burial diagenesis, a temperature of 165°C in clayey marl and 110°C in sandstone can be enough for isotopic rehomogenisation of fine-grained Hercynian illite. The migration of pore water seems to favour the diffusion of radiogenic ⁴⁰Ar in sandstones.     

Late Miocene nonmarine sedimentation and formation of magnesites in the Acıgöl Basin, southwestern Anatolia, Turkey

The Late Miocene lacustrine Acıgöl Basin, SW Turkey, formed as an orogen-top, extensional half-graben, with the subaqueous accommodation controlled by the lake level and the bulk accommodation provided by active subsidence along a WSW-trending normal fault at the basin's southern margin. The basin-fill sedimentary succession consists of terminal alluvial-fan facies overlain by ephemeral lake-margin facies and perennial lake facies, with widespread fluvial facies at the top. The distal alluvial-fan facies include massive to stratified sandstones and massive mudstones with intervening nodular dolostones and incipient pedogenic horizons. The lake-margin facies are micritic magnesites passing laterally into peloidal, irregularly laminated magnesites towards the palaeolake margin and overlain by marlstones and dolostones, all with abundant evidence of episodic subaerial exposure (desiccation cracks, pedogenic features, and tepee structures). The perennial lake facies are micritic magnesites passing upwards into clayey dolostones and dolomitic or clayey marlstones. The fluvial facies capping the succession include planar cross-stratified conglomerates (channel-fill deposits), planar parallel-stratified, planar cross-stratified and rippled cross-laminated sandstones (crevasse-fill and crevasse splay deposits), and assemblages of mudstones intercalated with thin sandstone beds (overbank floodplain deposits).The sedimentological, mineralogical and geochemical data reveal large variations in the basin's hydrological regime, including short-term oscillations and bulk rise of the lake level, periodical changes in the Mg/Ca ratio and terrigenous mud supply, and a negative covariance of δ¹⁸O and δ¹³C fluctuations. The composition of terrigenous sediment and the chemistry of water supplied to the lake were controlled by the weathering, chemical leaching and erosion of the ultramafic–dolomitic bedrock in the catchment area. The bedrock yielded Mg-rich carbonate solutions that caused the deposition of Mg-carbonates in the lake.Despite short-term lake-level fluctuations, the lake's net water budget remained positive. It is suggested that the region's present-day climate and Mg-rich alkaline lakes can serve as an analogue for the climatic and hydrological conditions in the Late Miocene Acıgöl Basin.     

Inter-annual variability in isotope and elemental ratios recorded in otoliths of an anadromous fish

Isotope ratios and elemental concentrations in otoliths are often used as natural tags to reconstruct migratory movements and connectivity patterns in marine and anadromous fishes. Although differences in otolith geochemistry have been documented among geographically separated populations, inter-annual variation within locations is less frequently examined. We compared otolith isotope (δ¹⁸O and ⁸⁷Sr:⁸⁶Sr) and elemental ratios (Sr:Ca and Ba:Ca) from several annual cohorts of juvenile American shad (Alosa sapidissima) in three rivers. These four geochemical signatures distinguished among river-specific populations of this species at both large and small geographic scales, with δ¹⁸O and ⁸⁷Sr:⁸⁶Sr generating the majority of multivariate variation. We found significant variation among years for all variables in two to three rivers. However, the magnitude of variability differed among ratios, with δ¹⁸O ratios showing substantial inter-annual shifts while ⁸⁷Sr:⁸⁶Sr ratios were relatively stable across years. Sr:Ca and Ba:Ca ratios also varied among years. These results imply that investigators using environmentally labile signatures must quantify geochemical signatures for each cohort of interest in order to confidently identify origins of migrants.     

Testing the preservation potential of early diagenetic dolomites as geochemical archives

Early marine diagenetic dolomite is a rather thermodynamically-stable carbonate phase and has potential to act as an archive of marine porewater properties. However, the variety of early to late diagenetic dolomite phases that can coexist within a single sample can result in extensive complexity. Here, the archive potential of early marine dolomites exposed to extreme post-depositional processes is tested using various types of analyses, including: petrography, fluid inclusion data, stable δ¹³C and δ¹⁸O isotopes, ⁸⁷Sr/⁸⁶Sr ratios, and U-Pb age dating of various dolomite phases. In this example, a Triassic carbonate platform was dissected and overprinted (diagenetic temperatures of 50 to 430°C) in a strike-slip zone in Southern Spain. Eight episodes of dolomitization, a dolostone cataclasite and late stage meteoric/vadose cementation were recognized. The following processes were found to be diagenetically relevant: (i) protolith deposition and fabric-preservation, and marine dolomitization of precursor aragonite and calcite during the Middle–Late Triassic; (ii) intermediate burial and formation of zebra saddle dolomite and precipitation of various dolomite cements in a Proto-Atlantic opening stress regime (T ca 250°C) during the Early–Middle Jurassic; (iii) dolomite cement precipitation during early Alpine tectonism, rapid burial to ca 15 km, and high-grade anchizone overprint during Alpine tectonic evolution in the Early Eocene to Early Miocene; (iv) brecciation of dolostones to cataclasite during the onset of the Carboneras Fault Zone activity during the Middle Miocene; and (v) late-stage regression and subsequent meteoric overprint. Data shown here document that, under favourable conditions, early diagenetic marine dolomites and their archive data may resist petrographic and geochemical resetting over time intervals of 10⁸ or more years. Evidence for this preservation includes preserved Late Triassic seawater δ¹³C_DIC values and primary fluid inclusion data. Data also indicate that oversimplified statements based on bulk data from other petrographically-complex dolomite archives must be considered with caution.     

The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.     

Loss of primary texture and geochemical signatures in speleothems due to diagenesis: Evidences from Castañar Cave, Spain

Geochemical signals from speleothems are commonly used in the investigation of palaeoenvironments. In most cases, however, little attention is paid to whether or not these signals are primary or altered by diagenesis. The speleothems of the Castañar Cave (Cáceres, Spain), which are initially formed of calcite or aragonite, have undergone a variety of meteoric diagenetic processes such as micritization and neomorphism (inversion), that collectively modify their primary features (textures, mineralogy, geochemical signals). The mean δ¹³C and δ¹⁸O values of the aragonites in the cave are −8.66 and −4.64 respectively, whereas the primary calcites have mean δ¹³C and δ¹⁸O values of −9.99 and −5.77, respectively. Following the diagenetic process of micritization, the aragonite isotopic signals averaged −7.63 δ¹³C and −4.74 δ¹⁸O and the calcite micrite signals −9.53 δ¹³C and −5.21 δ¹⁸O. Where inversion took place, some secondary calcites after the aragonite show preserved aragonite, whereas others do not. The secondary calcites without aragonite relics show isotopic values slightly higher than those of the primary calcite due to the inheritance of the aragonite signal. Where aragonite relics are preserved, the isotopic signatures are very similar to those of the aragonite micrite.In addition, the stable isotopic values and Sr and Mg contents of the speleothems became also modified by micritization and/or inversion. These diagenetic processes were driven by the changes in composition of the cave waters over time and space, but also, in the case of aragonite, by its initial unstable mineralogy.The present results highlight how important diagenesis is in caves and how the initial features of cave minerals may be lost. These changes alter the geochemical signals shown by speleothems, which may have an impact on the interpretation of the results obtained in palaeoenvironmental studies.     

Matrix micrite δC and δO reveals synsedimentary marine lithification in Upper Jurassic Ammonitico Rosso limestones (Betic Cordillera, SE Spain)

Matrix micrites are a commonly used carbonate archive for the reconstruction of past environmental parameters, but one that is submitted to known limitations. Main reasons for the often ambiguous value of many micrite-based isotope data sets are the unknown origin of the micrite components and their poorly resolved diagenetic history. Here we present carbon and oxygen-isotope data retrieved from Oxfordian to Tithonian Ammonitico Rosso nodular micrites sampled from three sections in the Betic Cordillera (Southern Spain). All three sections were correlated and sampled using a rigorous biostratigraphic framework. A noteworthy feature is that analyzed matrix micrites are more conservative in terms of their isotopic composition than other carbonate materials commonly considered to resist diagenetic alteration under favourable circumstances. Remarkably, this refers not only to δ¹³C ratios, which reflect the typical Late Jurassic global trend, but also to δ¹⁸O ratios that range around 0.3‰. The ¹⁸O-enriched oxygen-isotope ratios are considered to represent diagenetic stabilization of carbonate ooze under the influence of marine porewaters within the sediment–water interphase (i.e., the immature sedimentary section, usually submitted to biogenic activity). This interpretation agrees with the very early lithification of micrite nodules with cements precipitated from marine porewaters, enriched by the dissolution of aragonite skeletals (i.e., ammonite shells). According to the model proposed, low sedimentation rates as well as rapid early marine differential cementation, under the influence of currents and seawater pumping, affected the sediment–water interphase of epioceanic swells where deposition resulted in early lithified Ammonitico Rosso facies. The data obtained show that special care must be taken to prevent oversimplified interpretations of carbonate archives, particularly in the context of epioceanic settings.     

Multiple origin and regional significance of bedding parallel veins in a fold and thrust belt: The example of a carbonate slice along the Appalachian structural front

The development and evolution of bedding parallel veins (BPV) are investigated in the Saint-Dominique carbonate slice (southern Québec Appalachian structural front), in order to emphasize the regional significance of BPV in a fold and thrust belt and their importance in establishing its structural and diagenetic evolution. Structural and microstructural analyses reveal that most BPV display a laminated structure locally crosscut by a massive one. Both structures show mutual crosscutting relationships with bedding parallel or bedding perpendicular stylolites and with bedding perpendicular veinlets, indicating that BPV cementation and deformation are continuous processes. Opening both sub-parallel and sub-perpendicular to the BPV walls are documented. Early BPV are planes of weakness that focus later reactivation, and evidence of successive and sometimes opposite senses of opening are locally preserved within a single BPV. The bedding parallel orientation of these veins proved particularly helpful in establishing the structural evolution of an area mostly characterized by front parallel structures with little crosscutting relationships otherwise. Petrographic and geochemical (δ¹⁸O _VPDB and δ¹³C) analyses of structural cements suggest a common, locally derived source for the fluids that percolated through BPV, non-bedding parallel veins and faults. The isotopic ratios also reveal a significant enrichment in ¹⁸O and ¹³C through time. This evolution is tentatively correlated with tectonic, syn-convergence exhumation of the Saint-Dominique slice during its imbrication along the Appalachian structural front, after its burial under Taconian thrust sheets.     

Deconstructing Terminations I and II: revisiting the glacioeustatic paradigm based on deep-water temperature estimates

Benthic and planktonic oxygen isotope (δ¹⁸O_cc) and Mg/Ca analyses in two cores from the Northeast Atlantic have permitted the reconstruction of surface- and deep-water temperature (T_dw) and δ¹⁸O (δ¹⁸O_w) variations across the last two deglaciations. These records allow the timing of de-glacial melt-water pulses reaching the Northeast Atlantic to be compared with the evolution of local deep-water T_dw–δ¹⁸O_w conditions. Although each glacial termination is unique in detail, a similar pattern of hydrographic change is reconstructed for both deglaciations, with the first major decrease in deep-water δ¹⁸O_w (due to sea-level and/or purely local deep-water change) occurring in parallel with the onset of intensely cold glacial surface-water temperatures, and prior to a ‘terminal’ ice-rafting and melt-water event. The evolution of deep-water across both de-glaciations involved two transient incursions of cold, low-δ¹⁸O water into the deep Northeast Atlantic, the second of which was particularly pronounced each time. These pulses of cold deep-water are interpreted to reflect the incursion of water directly analogous to modern Antarctic Bottom Water (AABW), and containing a significant component of brine rejected during sea-ice formation. The results presented here show that the same type of transient changes in deep-water circulation that occurred across Termination I also occurred across Termination II, and that as a result of these deep-ocean changes, the timing of each benthic δ¹⁸O ‘termination’ cannot precisely reflect the timing of de-glacial sea-level change, as many palaeoceanographic interpretations (and some controversies) are prone to assume. Such ‘imprecision’ (in timing especially) may well extend to marine isotope stage (MIS) boundaries in general, as a principle of hydrographic variability and its expression in the geological record.     

Lower Eocene carbonate-cemented “chimney” structures (Varna, Bulgaria) — Control of seepage rates on their formation and stable isotopic signature

The genesis of Lower Eocene calcite-cemented columns, “pisoid”-covered structures and horizontal interbeds, clustered in dispersed outcrops in the Pobiti Kamani area (Varna, Bulgaria) is related to fossil processes of hydrocarbon migration. Field observations, petrography and stable isotope geochemistry of the cemented structures and associated early-diagenetic veins, revealed that varying seepage rates of a single, warm hydrocarbon-bearing fluid, probably ascending along active faults, controlled the type of structure formed and its geochemical signature. Slow seepage allowed methane to oxidize within the sediment under ambient seafloor conditions (δ¹⁸O = − 1 ± 0.5‰ V-PDB), explaining columns' depleted δ¹³C ratios of − 43‰. Increasing seepage rates caused methane to emanate into the water column (δ¹³C = − 8‰) and raised precipitation temperatures (δ¹⁸O = − 8‰). Calcite-cemented conduits formed and upward migrating fluids also affected interbed cementation. Even higher-energy fluid flow and temperatures likely controlled the formation of “pisoids”, whereby sediment was whirled up and cemented.     

Stable and clumped isotopes in desert carbonate spring and lake deposits reveal palaeohydrology: A case study of the Lower Jurassic Navajo Sandstone,south‐western USA

Carbon, oxygen and clumped isotope (Δ₄₇) values were measured from lacustrine and tufa (spring)‐mound carbonate deposits in the Lower Jurassic Navajo Sandstone of southern Utah and northern Arizona in order to understand the palaeohydrology. These carbonate deposits are enriched in both ¹⁸O and ¹³C across the basin from east to west; neither isotope is strongly sensitive to the carbonate facies. However, ¹⁸O is enriched in lake carbonate deposits compared to the associated spring mounds. This is consistent with evaporation of the spring waters as they exited the mounds and were retained in interdune lakes. Clumped isotopes (Δ₄₇) exhibit minor systematic differences between lake and tufa‐mound temperatures, suggesting that the rate of carbonate formation under ambient conditions was moderate. These clumped isotope values imply palaeotemperature elevated beyond reasonable surface temperatures (54 to 86°C), which indicates limited bond reordering at estimated burial depths of ca 4 to 5 km, consistent with independent estimates of sediment thickness and burial depth gradients across the basin. Although clumped isotopes do not provide surface temperature information in this case, they still provide useful burial information and support interpretations of the evolution of groundwater locally. The findings of this study significantly extend the utility of combining stable isotope and clumped isotope methods into aeolian environments.     

Variations in organic geochemistry and lithology of a carbonate sequence deposited in a backplatform basin (Triassic, Hungary)

The variations in the organic matter quantity and quality were studied with respect to the mineral composition of the carbonate sequences accumulated on a gentle slope (Zl-1 well) and at the toe of the slope (Rzt-1 well) located between a Late Triassic carbonate platform and a backplatform basin. Parallel variations observed in mineral composition and organic geochemical features of the successions appeared to be controlled by the change in climate and by sea-level fluctuations. The repetitive sea-level changes resulted in a variation in the carbonate-rich basin facies and in the mineralogically heterogenous slope and toe-of-slope ones. According to Rock Eval pyrolysis, organic petrography and carbon isotope ratios, the immature organic matter is of predominantly marine origin and composed of mainly liptinites in both of the studied boreholes. The results of the GC and GC/MS analyses of the saturated hydrocarbon fractions of bitumens together with the composition of kerogen pyrolysates reveal a predominant algal input with a minor variable bacterial and subordinate terrestrial contribution for the Rzt-1 borehole. In the Zl-1 borehole a significantly higher proportion of the bacterial biomass contributed to the organic precursors. The δ¹³C values and the composition of the kerogen pyrolysates together with the results of the maceral analysis and GC data suggest a relatively higher, but moderate, higher plant derived contribution in the slope facies and at the top of the toe-of-slope facies. The elementary composition of kerogens and Rock Eval data display type II-S kerogen in the basin and the slope facies, and type I-II-S one in the toe-of-slope facies. Variations in the hydrogen content of the organic matter mainly reflect variations in the preservation conditions and in primary productivity. The presence of the 2,6,10,15,19-pentamethyleicosane and the extremely low pristane/phytane ratios indicate a relatively high methanogenic bacterial activity and strongly anoxic depositional conditions in the Rzt-1 well, especially in two most organic-rich toe-of-slope facies.     

Environmental control of carbon isotope variations in Pennsylvania black-shale sequences, Midcontinent, U.S.A.

A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ¹³C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ¹³C_kerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ¹³C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO₂-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO₂” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.     

Geochemistry and occurrence of inorganic gas accumulations in Chinese sedimentary basins

Inorganic gases are commonly seen in eastern China and occasionally in southern China from the shallow water columns above hot and cold springs. The gases contain 68% to nearly 100% CO₂, with δ¹³C_CO2 and δ¹³C₁ values in the range of −1.18‰ to −6.00‰ and −19.48‰ to −24.94‰, respectively. All of the 34 large inorganic CO₂ and one inorganic methane accumulations discovered in China are distributed in eastern parts of the country, from both onshore and continental shelf basins. No commercial inorganic gas accumulation has been found in central and western China. This is a review of the occurrence and geochemical characteristics of inorganic gas accumulations in Chinese sedimentary basins. A detailed study of gas samples collected from four representative inorganic CO₂ pools and one possible inorganic methane pool indicates that inorganic alkane gases typically show δ¹³C₁ values greater than −10‰ versus PDB (mostly −30‰), with a positive stable carbon isotope sequence of δ¹³C₁ < δ ¹³C₂ < δ¹³C₃ < δ ¹³C₄. In contrast, the δ¹³C₁ values of biogenic alkane gases are lighter than −30‰, with a negative isotope sequence (i.e. δ¹³C₁ > δ¹³C₂ > δ ¹³C₃ > δ¹³C₄). Inorganic gases also tend to show less negative δ¹³C_CO2 values (−10‰) than biogenic gases (<−10‰).     

S- and O-isotopic character of dissolved sulphate in the cover rock aquifers of a Zechstein salt dome

Sulfur and O isotope analyses of dissolved SO₄ were used to constrain a hydrogeological model for the area overlying the Gorleben–Rambow Salt Structure, Northern Germany. Samples were collected from 80 wells screened at different depth-intervals. The study area consists of a set of two vertically stacked aquifer systems. Generally, the isotope data show a good spatial correlation, outlining well-defined groundwater zones containing SO₄ of characteristic isotopic composition. Highly saline waters from deeper parts of the lower aquifer system are characterized by rather constant SO₄ isotopic compositions, which are typical of Permian Zechstein evaporites (δ³⁴S=9.6–11.9‰; δ¹⁸O=9.5–12.1‰). Above this is a transition zone containing ground waters of intermediate salinity and slightly higher isotopic values (average δ³⁴S=16.6‰; δ¹⁸O=15.3‰). The confined groundwater horizon on the top of the lower aquifer system below the low permeable Hamburg Clays is low in total dissolved solids and is characterized by an extreme ³⁴S enrichment (average δ³⁴S=39.1‰; δ¹⁸O=18.4‰), suggesting that bacterially mediated SO₄ reduction is a dominant geochemical process in this zone. Two areas of distinct isotopic composition can be identified in the shallow ground water horizons of the upper hydrogeological system. Sulfate in groundwaters adjacent to the river Elbe and Löcknitz has a typical meteoric isotopic signature (δ³⁴S=5.2‰; δ¹⁸O=8.2‰), whereas the central part of the area is characterized by more elevated isotopic ratios (δ³⁴S=12.7‰; δ¹⁸O=15.6‰). The two major SO₄ pools in the area are represented by Permian seawater SO₄ and a SO₄ of meteoric origin that has been mixed with SO₄ resulting from the oxidation of pyrite. It is suggested that the S-isotope compositions observed reflect the nature of the SO₄ source that have been modified to various extent by bacterial SO₄ reduction. Groundwaters with transitional salinity have resulted from mixing between brines and low-mineralized waters affected by bacterial SO₄ reduction.