13C/12C ratio double cyclicity in a Miocene browncoal: isotopic signals and orbital forcing

A detailed stable carbon isotopic profile of a late Miocene browncoal seam from the Lower Rhine Embayment, Germany, reveals two clear separate cycles of different frequency: this is the first instance of this type of isotopic signature being recognized within coals. The ratio of the two frequencies suggests this isotopic signal possibly resulted from climatic or vegetational responses to orbital forcing. The cyclicity has been enhanced by the application of conventional filtering methods on the data set. An analysis of the seam's palynology indicates a correlation between heavier isotopic compositions and the presence of Sequoiapollenites polyformosus , whose parent plant is believed to have favoured moist climates and higher groundwater tables.     

An alternative model for positive shifts in shallow-marine carbonate δ13C and δ18O

Abstract Positive shifts in global seawater δ¹³C_DIC are related to changes in the ratio of organic relative to inorganic carbon burial in oceanic basins, whereas factors such as climatic cooling and the accumulation of polar ice are known to cause positive shifts in δ¹⁸O. Here, an alternative model is proposed for the formation of local positive isotope shifts in shallow-marine settings. The model involves geochemically altered platform-top water masses and the effects of early meteoric diagenesis on carbonate isotopic composition. Both mechanisms are active on modern (sub)tropical carbonate platforms and result in low carbonate δ¹³C and δ¹⁸O relative to typical oceanic values. During high-amplitude transgressive events, the impact of isotopically light meteoric fluids on the carbonate geochemistry is much reduced, and ¹³C-depleted platform-top water mixes with open oceanic water masses having higher isotope values. Both factors are recorded as a transient increase in carbonate ¹³C and ¹⁸O relative to low background values. These processes must be taken into consideration when interpreting the geochemical record of ancient epeiric seas.     

The origin of magnesite deposits from the Polish Foresudetic Block ophiolites: preliminary δ13C and δ18O investigations

Twenty-three magnesite samples from vein deposits, found in ultramafic rocks related to ophiolites in the north-east Bohemian Massif, have been examined for carbon and oxygen isotope ratios. In these rocks two stages of antigorite serpentinization took place prior to magnesite precipitation. δ¹⁸O_SMOW in magnesites ranges from 24.5 to 27.9%o (corrected for acid fractionation factor) which leads us to conclude a meteoric origin of the ore-forming solution. This inference is further supported by δ¹³C values (?18.7 to ?4.4%o) which point to a biogenic origin of carbon in the magnesites.     

Effect of sample pretreatment and size fraction on the δ18O and δ13C values of foraminifera in Arabian Sea sediments

Stable oxygen and carbon isotope ratios (δ¹⁸O and δ¹³C, respectively) of a planktonic foraminiferal species (Globigerinoides sacculifer) and marble carbonate were measured with and without a variety of pretreatments like ultrasonication, soaking in H₂O₂, methanol and roasting under vacuum. Additionally, organic matter - carbonate mixtures were also analysed with and without the above pretreatments. No significant difference was found in the isotope ratios of treated and untreated samples. It appears that most of the pretreatments may not be necessary when dealing with planktonic foraminifera, especially G. sacculifer. Analysis of two different size fractions (> 400 μm and 250–400 μm) of this species reveals that the smaller size fraction is enriched in ¹⁸O and depleted in ¹³C relative to the bigger size fraction. It is therefore necessary to choose a proper size fraction for isotopic analyses.     

Long-term (105) or short-term (103) δ13C excursion near the Palaeocene-Eocene transition: evidence from the Tethys

Expanded sedimentary records from the Tethys reveal unique faunal and isotopic changes across the Palaeocene-Eocene (P-E) transition. Unlike in the open oceans, the Tethys exhibits a gradual decrease of 1.5% in δ¹³C values prior to the rapid δ¹³C excursion. Associated with the 6¹³C excursion is a decrease in calcite burial, increase in detrital content and appearance of a unique opportunistic planktic foraminifera1 assemblage (e.g. compressed acarininids). The existence of a prelude decrease in δ¹³C values in the Tethys suggests that the P-E δ¹³C excursion may have occurred in two steps and over a few hundred thousand years, rather than as one step over a few thousand years as previously suggested. This slower excursion rate is readily explained by changing organic carbon weathering or burial rates and avoids the need of invoking ad hoc scenarios.     

Paleoceanography and climate of the Badenian (Middle Miocene, 16.4–13.0 Ma) in the Central Paratethys based on foraminifera and stable isotope (δ18O and δ13C) evidence

Benthic foraminifera and stable isotopes analyses revealed changes emerging in the paleoceanographic scenery in the Paratethys. The percentage of inbenthic, oxyphylic taxa and diversity in the benthic foraminiferal assemblage showed increasing food supply (organic matter), decreasing oxygen level and growing stress on the sea floor. Oxygen isotopes measured in planktonic and benthic foraminifera pointed to strengthening stratification during the Badenian period. The carbon isotopes indicated intensified accumulation of light marine organic matter. This increasing stratification trend is especially pronounced by Late Badenian (13.5–13 Ma) when surface water oxygen isotope values are rather negative. A simple two-layer circulation model was worked out for the Badenian Paratethys explaining these characteristic environmental changes. An antiestuarine (lagoonal) circulation is assumed for the Central Paratethys during the Early (16.4–15 Ma) and mid Badenian (15–13.5 Ma). The mid Badenian period of time comprises the short episode of evaporite formation in the Carpathian Foredeep and the Transylvanian Basin. Evidence presented here supported a reversal of circulation to estuarine type after the deposition of salts by Late Badenian (13.5–13 Ma). The Early Badenian antiestuarine circulation is suggested to associate with the high temperatures of the Mid-Miocene Climatic Optimum, and the Late Badenian estuarine circulation with the cooler period following it.     

Low δ18O eclogites from the Kokchetav massif, northern Kazakhstan

Oxygen isotopic compositions of silicates in eclogites and whiteschists from the Kokchetav massif were analyzed by whole‐grain CO₂‐laser fluorination methods. Systematic analyses yield extremely low δ¹⁸O for eclogites, as low as ?3.9‰ for garnet; these values are comparable with those reported for the Dabie‐Sulu UHP eclogites. Oxygen isotopic compositions are heterogeneous in samples of eclogite, even on an outcrop scale. Schists have rather uniform oxygen isotope values compared to eclogites, and low δ¹⁸O is not observed. Isotope thermometry indicates that both eclogites and schists achieved high‐temperature isotopic equilibration at 500–800 °C. This implies that retrograde metamorphic recrystallization barely modified the peak‐metamorphic oxygen isotopic signatures. A possible geological environment to account for the low‐δ¹⁸O basaltic protolith is a continental rift, most likely subjected to the conditions of a cold climate. After the basalt interacted with low δ¹⁸O meteoric water, it was tectonically inserted into the surrounding sedimentary units prior to, or during subduction and UHP metamorphism.     

Earthquake-induced resedimentation in the Badenian (middle Miocene) gypsum of southern Poland

In the Badenian (middle Miocene) basin of the Carpathian foreland of southern Poland, gypsum breccias occur associated with laminated gypsum deposits. These breccias consist of large clasts of gypsum, carbonates, marls and clay chips of variable size embedded in a gypsarenitic matrix. Constituent gypsum grains and clasts commonly appear to be mechanically abraded and chemically corroded crystals or fragments of selenitic, laminated and alabastrine gypsum. Gypsorudites are commonly accompanied by laminated gypsarenites and gypsolutites which show graded bedding; a vertical sequence of graded gypsum beds showing Bouma sequences may be recognized in borehole sections. Microfolding is common within the folded laminated gypsum, and is closely associated with expressions of extensional strain. Both are accompanied by pervasive microfaulting, suggesting a semi-coherent downslope mass movement. The stratiform geometry of the breccias, together with the intensity of slumping relatively independent of the palaeoslope, suggest earthquake shocks as the initial, main cause. Gypsum deposits form a constant, laterally extensive sequence of different lithofacies. The occurrence of the same lithologies and shallowing-up cycles over a wide area reflects thrusting of the Carpathians over the Carpathian foredeep. Local tectonism has also played a significant role. The tectonic framework favoured activation of dip-slip faults promoting shallow-focus earthquakes. These in turn resulted in the resedimentation of gypsum by slumps, debris flows and turbidites. A similar basinward resedimentation of clastic material by gravity flows initiated by fault-induced earthquakes could be of great importance in the foreland geological setting, and may explain some phenomena observed in other evaporite formations from different geological settings, especially of rift type.     

Foraminiferal record of marine transgression during deposition of the Middle Miocene Badenian evaporites in Central Paratethys (Borków section,Polish Carpathian Foredeep)

Benthic and planktonic foraminifera from a marly clay intercalation sandwiched between mid‐Badenian (Middle Miocene) gypsum deposited in an environment of an evaporitic shoal (<1 m deep) at Borków (southern Poland) indicate a major marine flooding event in the previously isolated Carpathian Foredeep Basin (Central Paratethys). After this very short‐term environmental change, benthic foraminifers started to colonize a new niche which was previously defaunated, and the pattern of benthic foraminiferal colonization is similar to that related to the reflooding which terminated the Badenian evaporite deposition. The benthic foraminifer assemblages are composed of pioneer, opportunistic, r‐selected species dominated by elphidiids. The connection of the Carpathian Foredeep Basin with the marine reservoir was short‐lived. The marly clay intercalations in evaporite sequences originating in bared basins can thus register major environmental changes.     

Bryozoan event from Middle Miocene (Early Badenian) lower neritic sediments from the locality Kralice nad Oslavou (Central Paratethys,Moravian part of the Carpathian Foredeep)

Fossil Bryozoa occurs usually in shallow-water environments. One of the rare deep-water associations of Bryozoa has been studied in a profile at Kralice nad Oslavou. According to studies of foraminifera, the paleodepth was more than 150 m and less than 500 m. The bryozoan assemblages are poor, consisting of four species only, dominated by Tervia irregularis (Cyclostomatida) and Reteporella kralicensis sp.n. (Cheilostomatida), a new species being described in detail.     

The 14C age of the Toten' mammoth, eastern Norway

A mammoth tusk find from Toten in Oppland, eastern Norway, has been re-dated by the EDTA method. On examining the tusk for heavy metals, the porous parts were found to have the highest concentration. This fact, together with earlier experience from selecting bone samples for ¹⁴C dating, favour the choice of the hard non-porous parts. The influence of possible minor contaminants remaining after pretreatment is discussed. Because of high cosmic-ray intensity the background deviated from the normal stable value. The variations were studied carefully. The final result is that the net activity of the bone is so close to zero that it is questionable whether the age is 'finite'. It is concluded that the tusk is older than 28,000 years.     

87Sr/86Sr composition of evaporitic carbonates and sulphates from Miocene sediment cores in the Mediterranean Sea (D.S.D.P., Leg 13)

The ⁸⁷Sr/⁸⁶Sr ratios of evaporitic carbonates and sulphates from Miocene sediment cored in the Mediterranean Sea show a depletion of ⁸⁷Sr when compared to the isotopic composition of the Miocene contemporaneous marine strontium: 0.70803 versus 0.70936. The arrival into the evaporitic environment of strontium brought by continental waters can explain this difference. The variation of the ⁸⁷Sr/⁸⁶Sr ratios is, nevertheless, noticeable only when the influence of the continental waters is already well marked. This is proved when one compares the results obtained with strontium, to the results of isotopic analysis made on oxygen, carbon, sulphur and hydrogen taken from the same samples.     

Sedimentology of Badenian (middle Miocene) gypsum in eastern Galicia, Podolia and Bukovina (West Ukraine)

Primary gypsum is the main evaporite mineral in the middle Miocene (Badenian) of the West Ukraine. The lower part of the gypsum sequence is built of autochthonous gypsum while the upper part is composed of allochthonous gypsum that formed following a major, tectonically induced, change in basin morphology. This change resulted in the destruction of the gypsum deposited on the margins of the basin and formation of redeposition features. Autochthonous gypsum facies were deposited in two main environments: (1) giant gypsum intergrowths precipitated from highly concentrated brines; (2) very shallow subaqueous gypsum deposited in a vast brine pan. The brine pan was characterized by a facies mosaic that reflects an interplay of concentrated brines from the central part of the evaporite basin and diluted brines due to the influx of continental meteoric waters. The facies continuum, microbial gypsum - bedded selenite - massive selenite - sabre gypsum, indicates increasing salinity of the brine with time. This type of facies pattern has been established in recent salinas that are analogous to Badenian gypsum in their lateral facies changes. However, the pattern of facies distribution with respect to the open sea in the Badenian basin is opposite to that found in recent salinas. The pattern of the Badenian gypsum facies in the Ukraine indicates that facies repetition may have been related to climatically controlled salinity changes and not to depth changes, as is commonly used to explain the repetition of sulphate facies in a vertical succession.     

Deglaciation history of the southwestern Fennoscandian Ice Sheet between 15 and 13 14C ka BP

Analysis of 2D and 3D seismic records from the continental shelf off western Norway, in combination with chronological constraints from ¹⁴C dates, has led to a model for the glacial development in these shelf areas between c. 15 and 13 ¹⁴C ka BP. On the shallow Måløy Plateau adjacent to the Norwegian Channel, iceberg scours are preserved below a prominent moraine ridge, which by correlation to the Norwegian Channel indicate ice retreat at c. 15 ¹⁴C ka BP. Subsequently, the ice advanced across the scoured surface and deposited a till sheet before stabilizing to deposit a prominent moraine, termed the Bremanger Moraine. Based on location on the shelf, seismic stratigraphy, morphology and C dates the Bremanger Moraine is correlated with a significant moraine on the continental shelf off Trøndelag. We suggest that these features are products of a regional glacial event, the Bremanger Event, dated to <15–13.3 ¹⁴C ka BP. The Bremanger Event is probably a result of the deteriorating climatic conditions in the NE Atlantic during Heinrich event 1.     

Determination of Total Organic Carbon Content and δ13C in Carbonate-Rich Detrital Sediments

The determination of total organic carbon content and composition in detrital sediments requires careful removal of their carbonate minerals. In detrital sediments containing large amounts of carbonates, including dolomite, this can only be achieved by liquid acid leaching that may solubilise a significant proportion of the organic carbon. For a set of detrital sediments from the Himalayan system and the Amazon River as well as five geological reference materials, we determined the proportion of organic carbon (C_org) solubilised during acid leaching. This proportion is significant for all analysed sediments and generally tends to increase with the organic carbon content. Compared to other types of sediments analysed, clay fractions extracted from river sediments and bed sediments with very low organic carbon content have high and low proportions of acid soluble C_org respectively. In Himalayan and Amazon river sediments, the proportion of C_org solubilised during acid leaching was relatively constant with average values of 14 and 19 % respectively. Thus, it is possible to correct the C_org content for the dissolved organic carbon content measured after decarbonation. Data presented here show that C_org dissolved during liquid acid leaching must be taken into account. After careful calibration, the method presented here should, therefore, be applied to any carbonate-rich detrital sediment.     

Palaeoproterozoic evaporites in Fennoscandia: implications for seawater sulphate, the rise of atmospheric oxygen and local amplification of the δ13C excursion

This paper addresses global oxygenation and establishment of a marine sulphate reservoir in the Palaeoproterozoic. We report syn-depositional, marine, anhydrite-containing pseudomorphs after Ca-sulphates as widespread throughout the Tulomozero Formation in the SE Fennoscandian Shield, implying that surface waters were oxidized and a large SO marine reservoir was developed as early as 2100 Ma. The Ca-sulphates and associated magnesite and halite precipitated syn-depositionally from oxidized, evolved and modified seawater in coastal playa, sabkha and intertidal flat settings. ⁸⁷Sr/⁸⁶Sr and δ¹³C of associated ¹³C-rich stromatolitic dolostones were environmentally controlled with the highest ratios occurring in playa and sabkha carbonates. The results imply that the Palaeoproterozoic δ¹³C_carb excursion was amplified by 8‰ by local environmental factors and calls into question many observations of putative δ¹³C global signals reported previously from similar Palaeoproterozoic, evaporitic, dolostones. The local environmental amplification can explain a large regional and intercontinental δ¹³C discrepancy observed in synchronous carbonates.     

Gypsum facies transitions in basin-marginal evaporites: middle Miocene (Badenian) of west Ukraine

In the middle Miocene Badenian gypsum basin of the Carpathian Foredeep, west Ukraine, three main zones of gypsum development occur in the peripheral parts of the basin. Zone I consists entirely of stromatolitic gypsum formed in a nearshore zone. Zone II is located more basinward and is characterized by stromatolitic gypsum in the lower part of the section, overlain by a sabre gypsum unit. Zone III occurs in still more basinward areas and is characterized by giant gypsum intergrowths (or secondary nodular gypsum pseudomorphs of these) in the lowermost part, overlain by stromatolitic gypsum, sabre gypsum and then by clastic gypsum units. Correlation between these facies and zones has been achieved using lithological marker beds and surfaces. Of particular importance for correlation is a characteristic marker bed (usually 20–40 cm thick) of cryptocrystalline massive gypsum occurring in zones II and III. The marker was not distinguished in zone I, possibly because this bed is older than the entire gypsum section of that zone. These new results strongly suggest that the deposition of giant gypsum intergrowth facies and stromatolitic gypsum facies was coeval. In some sections of zones I and II, limestone intercalations have been recorded within the upper part of the gypsum sections. Considerable scatter of the δ¹⁸O and δ¹³C values of these limestones indicates variable diagenetic overprints of marine carbonates, but a marine provenance of the limestones is confirmed by microfacies analysis. Some of the limestones are coeval with an intercalation of gypsarenitic, mostly laminated gypsum occurring in the sabre gypsum unit of zones II and III. Badenian gypsum formed in extremely shallow‐water to subaerial environments on broad, very low relief areas of negligible brine depth, which could be affected by rapid transgressions. Stable isotope (δ³⁴S, δ¹⁸O) studies of the gypsum demonstrate that the sulphate was of sea‐water origin or was derived from dissolution of Miocene marine evaporites. Investigations of individual inclusions in the gypsum indicate decreased water salinity when compared with modern marine‐derived, calcium sulphate‐saturated water. Groundwater influences are indicated by high calcium sulphate contents of the brines in the evaporite basin. The chemical composition of Badenian waters was thus a mixture of relic sea water (depleted in NaCl), groundwater (enriched in calcium sulphate) and surface run‐off.     

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ18O of Early Palaeozoic sea water

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.     

40Ar/39Ar and oxygen isotope studies of polymetamorphism from Tinos Island, Cycladic blueschist belt, Greece

Abstract Petrological, oxygen isotope and ⁴⁰Ar/³⁹Ar studies were used to constrain the Tertiary metamorphic evolution of the lower tectonic unit of the Cyclades on Tinos. Polyphase high-pressure metamorphism reached pressures in excess of 15 kbar, based on measurements of the Si content in potassic white mica. Temperatures of 450–500° C at the thermal peak of high-pressure metamorphism were estimated from critical metamorphic assemblages, the validity of which is confirmed by a quartz–magnetite oxygen isotope temperature of 470° C. Some ⁴⁰Ar/³⁹Ar spectra of white mica give plateau ages of 44–40 Ma that are considered to represent dynamic recrystallization under peak or slightly post-peak high-pressure metamorphic conditions. Early stages in the prograde high-pressure evolution may be documented by older apparent ages in the high-temperature steps of some spectra. Eclogite to epidote blueschist facies mineralogies were partially or totally replaced by retrograde greenschist facies assemblages during exhumation. Oxygen isotope thermometry of four quartz–magnetite pairs from greenschist samples gives temperatures of 440–470° C which cannot be distinguished from those deduced for the high-pressure event. The exhumation and overprint is documented by decreasing ages of 32–28 Ma in some greenschists and late-stage blueschist rocks, and ages of 30–20 Ma in the lower temperature steps of the Ar release patterns of blueschist micas. Almost flat parts of Ar–Ar release spectra of some greenschist micas gave ages of 23–21 Ma which are assumed to represent incomplete resetting caused by a renewed prograde phase of greenschist metamorphism. Oxygen isotope compositions of blueschist and greenschist facies minerals show no evidence for the infiltration of a δ¹⁸O-enriched fluid. Rather, the compositions indicate that fluid to rock ratios were very low, the isotopic compositions being primarily controlled by those of the protolith rocks. We assume that the fundamental control catalysing the transformation of blueschists into greenschists and the associated resetting of their isotopic systems was the selective infiltration of metamorphic fluid. A quartz–magnetite sample from a contact metamorphic skarn, taken near the Miocene monzogranite of Tinos, gave an oxygen isotope temperature of 555° C and calculated water composition of 9.1%. The value of δ¹⁸O obtained from this water is consistent with a primary magmatic fluid, but is lower than that of fluids associated with the greenschist overprint, which indicates that the latter event cannot be directly related to the monozogranite intrusion.     

The role of inter-specific, micro-habitat and climatic factors on the carbon isotope (δ13C) variability of a modern leaf assemblage from northern Scandinavia: implications for climate reconstruction

To provide a basis for the interpretation of past climatic conditions from Quaternary leaf records, leaf carbon isotope (δ¹³C) results are presented for 12 northern European dwarf-shrub, shrub and tree species growing across a network of 18 sites in northern Scandinavia. The role of micro-habitat (hummock/hollow) on carbon isotope trends is explored in addition to a comparison of the carbon isotope composition of both cellulose and wholeleaf material. The data are also examined against local meteorological variables (temperature, precipitation and vapour pressure deficit) at both species and genus levels. Results exhibit only modest coherence between selected plant species and low-order correlations with external climate forcings consistent with accepted models for carbon isotope fractionation. Potential for the analysis and interpretation of stable isotopic time series may still be identified; however, factors such as inter-plant variability, senescence, diagenesis and homogeneity need to be thoroughly addressed before such an approach may be used for palaeoenvironmental reconstructions. These findings highlight the complexities and limitations of spatial calibration methods.