An important source of palaeoecological and palaeoenvironmental information is intra-specimen variability of isotopic composition of mammal tooth enamel. It reflects seasonal or behavioral changes in diet and climate occurring during a life of the animal. While well-known in ungulates, in carnivorans this variability is poorly recognized. However, carnivoran remains are amongst the most numerous in the Pleistocene fossil record of terrestrial mammals, so their isotopic signature should be of particular interest. The aim of the study was to verify if enamel of a fossil cave hyena (Crocuta crocuta spelaea) and a cave bear (Ursus ingressus) records any regular inter- or intra-tooth isotopic variability. We examined intra-individual variability of δ13C and δ18O values in permanent cheek teeth enamel of fossil cave hyena and cave bear from the site of the Perspektywiczna Cave (southern Poland). We conclude that the isotopic variability of the cave hyena is low, possibly because enamel mineralization took place when the animals still relied on a uniform milk diet. Only the lowermost parts of P3 and P4 enamel record a shift toward an adult diet. In the case of the cave bear, the sequence of enamel formation records periodic isotopic changes, possibly correlating with the first seasons of the animal life.
Samples for the study were collected from, known from the literature, outcrop profiles in Zarzecze, Radymno, Dybawka, Tarnawce and Pikulice-Nehrybka, situated at the Carpathian border, in the vicinity of the Przemyśl town, close to the San River valley (SE Poland). They represent the Vistulian loess-palaeosol sequences. Carbonates occur mainly in the loesses representing OIS 2 and 3. Pollen analysis, carried out for two profiles (Tarnawce, Radymno), throws light on palaeoecological conditions of loess cover formation and transformation.Isotopic analysis of authigenic carbonates was carried out on carbonate cemented bodies dispersed throughout the loess in forms of nodule, rhizolith and rhizocretion and on bioclasts, mainly snail shells, ostracod valves, and sparse globules (probably the internal shells of the naked snails).In the successions studied, the upper Vistulian loess deposited in environment with poor vegetation, contains rhizo- liths and rhizocretions mainly, while in the middle and lower Vistulian loess with well developed soils, gley horizons, and intercalations of subaqueous sediments, remains of snail shells and ostracod valves prevail. The two main forms of carbonates differ markedly in isotopic composition from one another. These differences seem to be more important than those between samples of one form of carbonates along particular sections. That is the result of numerous factors affecting the fractionation of carbon and, in particular, oxygen stable isotopes in the environment of precipitation of authigenic calcite. The isotopic composition of carbonates cementing sediments is controlled mainly by biominerali- zation of organic matter and local climatic parameters which were rather slightly differentiated during the formation of the studied sediments. The d13C values for bioclasts vary in a broader range than for calcitic cements. Usually the snail shell carbonate is more enriched with heavier carbon isotope than that from ostracod valves, resulting from the isotopic equilibrium with precipitation and with surface waters, respectively. Basing on our study we can conclude that fluctuations of isotope composition of authigenic carbonates make it hard to apply as a paleoclimatic indicator. However, the general trend of d18O variation in analysed carbonate fractions from leoss-palaeosol sequences displays some connections with climatic fluctuations.
A sediment core (LS-1) collected from Long Lake in King George Island, South Shetland Islands (West Antarctica) was analyzed for a variety of textural, geochemical, isotopic and paleontological properties together with 14C age dates. These data combined with published records of other studies provide a detailed history of local/regional postglacial paleoproductivity variation with respect to terrestrial paleoclimate change. The lithologic contrast of a lower diamicton and an upper fine-grained sediment demonstrates glacial recession and subsequent lake formation. The upper fine-grained deposit, intercalated by mid-Holocene tephra-fallout followed by a tephra gravity flow, was formed in a lacustrine environment. Low total organic carbon (TOC) and biogenic silica (Sibio) contents with high C/N ratios characterize the diamicton, whereas an increase of TOC and Sibio contents characterize the postglacial lacustrine fine-grained sediments, which are dated at c. 4000 yrBP. More notable are the distinct TOC maxima, which may imply enhanced primary productivity during warm periods. Changes in Sibio content and δ13C values, which support the increasing paleoproductivity, are in sympathy with these organic matter variations. The uniform and low TOC contents that are decoupled by Sibio contents are attributed to the tephra gravity flows during the evolution of the lake rather than a reduced paleoproductivity. A very recent TOC maximum is also characterized by high Sibio content and δ13C values, clearly indicating increased paleoproductivity consequent upon gradual warming across King George Island . Comparable with changes in sediment geochemistry, the occurrence and abundance of several diatom species corroborate the paleoproductivity variations together with the lithologic development. However, the paleoclimatic signature in local terrestrial lake environment during the postglacial period (for example the Long Lake) seems to be less distinct, as compared to the marine environment.
The organic carbon (OC)-rich, black shale succession of the Middle Triassic Bravaisberget Formation in Spitsbergen contains scattered dolomite-ankerite cement in coarser-grained beds and intervals. This cement shows growth-related compositional trend from non-ferroan dolomite (0–5 mol % FeCO3) through ferroan dolomite (5–10 mol % FeCO3) to ankerite (10–20 mol % FeCO3, up to 1.7 mol % MnCO3) that is manifested by zoned nature of composite carbonate crystals. The d13C (-7.3‰ to -1.8‰ VPDB) and d18O (-9.4‰ to -6.0‰ VPDB) values are typical for burial cements originated from mixed inorganic and organic carbonate sources. The dolomite-ankerite cement formed over a range of diagenetic and burial environments, from early post-sulphidic to early catagenic. It reflects evolution of intraformational, compaction-derived marine fluids that was affected by dissolution of biogenic carbonate, clay mineral and iron oxide transformations, and thermal decomposition of organic carbon (decarboxylation of organic acids, kerogen breakdown). These processes operated during Late Triassic and post-Triassic burial history over a temperature range from approx. 40°C to more than 100°C, and contributed to the final stage of cementation of the primary pore space of siltstone and sandstone beds and intervals in the OC-rich succession.
51 samples from the Middle Triassic black shales (organic carbon−rich silt− stones; up to 4.9% TOC – Total Organic Carbon) from the stratotype section of the Bravaisberget Formation (western Spitsbergen) were analyzed with respect to isotopic composition of pyritic sulphur (δ34S) and TOC. Isotopic composition of syngenetic py− rite−bound sulphur shows wide (δ34S from −26‰ to +8‰ VCDT) and narrow (δ34S from −4‰ to +17‰ VCDT) variation of the δ34S in upper and lower part of the section, respec− tively. Range of the variation is associated with abrupt changes in dominant lithology. Wide δ34S variation is found in lithological intervals characterized by alternation of black shales and phosphorite−bearing sandstones. The narrow δ34S variation is associated with the lithological interval dominated by black shales only. Wide and narrow variation of the δ34S values suggests interplay of various factors in sedimentary environment. These fac− tors include oxygen concentration, clastic sedimentation rate, bottom currents and bur− rowing activity. Biological productivity and rate of dissimilatory sulphate reduction had important impact on the δ34S variation as well. Wide variation of the δ34S values in the studied section resulted from high biological productivity and high rate of dissimilatory sulphate reduction. Variable degree of clastic sedimentation rate and burrowing activity as well as the activity of poorly oxygenated bottom currents could also cause a co−occurrence of isotopically light and heavy pyrite in differentiated diagenetic micro−environments. Occurrence of organic matter depleted in hydrogen could also result in a wide variation of the δ34S values. Narrow variation of the δ34S values was due to a decrease of biological productivity and low rate of dissimilatory sulphate reduction. Low organic matter supply, low oxygen concentration and bottom currents and burrowing activity were also responsible for narrow variation of the δ34S. The narrow range of the δ34S variation was also due to occurrence of hydrogen−rich organic matter. In the studied section the major change in range of the δ34S variation from wide to narrow appears to be abrupt and clearly associated with change in lithology. The change of lithology and isotopic valuesmay sug− gest evolution of the sedimentary environment from high− to low−energy and also facies succession from shallow to deeper shelf. The evolution should be linked with the Late Anisian regional transgressive pulse in the Boreal Ocean.
Stable isotopes 18O and 13C record of the Kapp Starostin Formation (Late Permian) is presented. The interdependence of δ18O nad δ13C isotope time series is applied for calculating paleotemperatures in the depositional basin of the Kapp Starostin Formation. The obtained results indicate overall cooling from c. 25°—10°C, and confirm some paleogeographical and paleoclimatical inferrences.
The Silurian Pelplin Formation is a part of a thick, mud-prone distal fill of the Caledonian foredeep, which stretches along the western margin of the East European Craton. The Pelplin Formation consists of organic carbon- rich mudstones that have recently been the target of intensive investigations, as they represent a potential source of shale gas. The Pelplin mudstones host numerous calcite concretions containing authigenic pyrite and barite. Mineralogical and petrographic examination (XRD, optical microscopy, cathodoluminoscopy, SEM-EDS) and stable isotope analyses (δ13Corg, δ13C and δ18O of carbonates, δ34S and δ18O of barite) were carried out in order to understand the diagenetic conditions that led to precipitation of this carbonate-sulfide-sulfate paragenesis and to see if the concretions can enhance the understanding of sedimentary settings in the Baltic and Lublin basins during the Silurian. Barite formed during early diagenesis before and during the concretionary growth due to a deceleration of sedimentation during increased primary productivity. The main stages of concretionary growth took place in yet uncompacted sediments shortly after their deposition in the sulfate reduction zone. This precompactional cementation led to preferential preservation of original sedimentary structures, faunal assemblages and early- diagenetic barite, which have been mostly lost in the surrounding mudstones during burial. These components allowed for the reconstruction of important paleoenvironmental conditions in the Baltic and Lublin basins, such as depth, proximity to the detrital orogenic source and marine primary productivity. Investigation of the concretions also enabled estimation of the magnitude of mechanical compaction of the mudstones and calculation of original sedimentation rates. Moreover, it showed that biogenic methane was produced at an early-diagenetic stage, whereas thermogenic hydrocarbons migrated through the Pelplin Formation during deep burial.
Pyrite framboids occur in loose blocks of plant−bearing clastic rocks related to volcano−sedimentary succession of the Mount Wawel Formation (Eocene) in the Dragon and Wanda glaciers area at Admiralty Bay, King George Island, West Antarctica. They were investigated by means of optical and scanning electron microscopy, energy−dispersive spectroscopy, X−ray diffraction, and isotopic analysis of pyritic sulphur. The results suggest that the pyrite formed as a result of production of hydrogen sulphide by sulphate reducing bacteria in near surface sedimentary environments. Strongly negative δ34SVCDT values of pyrite (−30 – −25 ‰) support its bacterial origin. Perfect shapes of framboids resulted from their growth in the open pore space of clastic sediments. The abundance of framboids at cer− tain sedimentary levels and the lack or negligible content of euhedral pyrite suggest pulses of high supersaturation with respect to iron monosulphides. The dominance of framboids of small sizes (8–16 μm) and their homogeneous distribution at these levels point to recurrent development of a laterally continuous anoxic sulphidic zone below the sediment surface. Sedimentary environments of the Mount Wawel Formation developed on islands of the young magmatic arc in the northern Antarctic Peninsula region. They embraced stagnant and flowing water masses and swamps located in valleys, depressions, and coastal areas that were covered by dense vegetation. Extensive deposition and diagenesis of plant detritus in these environments promoted anoxic conditions in the sediments, and a supply of marine and/or volcanogenic sulphate enabled its bacterial reduction, precipitation of iron mono− sulphides, and their transformation to pyrite framboids.
Diagenetic carbonate deposits (concretions, cementation bodies and cementstone bands) commonly occur in organic carbon-rich sequence of the Agardhfjellet Formation (Upper Jurassic) in Spitsbergen . They are dominated by dolomite/ankerite and siderite. These deposits originated as a result of displacive cementation of host sediment in a range of post-depositional environments, from shallow subsurface to deep-burial ones. Preliminary results of the carbon and oxygen isotopic survey of these deposits in southern Spitsbergen (Lĺgkollane, Ingebrigtsenbukta, Reinodden, and Lidfjellet sections) show the δ13C values ranging between –13.0‰ and –1.8‰ VPDB, and the δ18O values between –16.0‰ and –7.7‰ VPDB. These results suggest that the major stage of formation of the carbonate deposits occurred during burial diagenesis under increased temperature, most probably in late diagenetic to early catagenic environments. Carbonate carbon for mineral precipitation was derived from dissolution of skeletal carbonate and from thermal decomposition of organic matter.