Stable carbon and oxygen isotope composition of Recent, Tertiary and Cretaceous foraminifera (Table III)

Oxygen isotope analyses of Tertiary and Cretaceous planktic foraminifera indicate that species have been stratified with respect to depth in the water column at least since Albian time. There is a relationship between morphology and depth habitat. Species with globigerine morphology have consistently occupied shallower depths than have species with globorotalid morphology. Biserially arranged species occupied both shallow and deep levels in the water column. On the average, it appears that ancient species with shallow habitats have been more susceptible to dissolution and have been preserved less well than species dwelling in deeper habitats. This relationship is similar to that observed for Recent planktic foraminifera. Comparison of carbon isotope ratios of adult and juvenile forms indicates that either the source of the carbon found in the shell or the carbon isotopic fractionations which occur during calcite secretion change during the development of individual foraminifera. The carbon isotopic ratios do not provide a reliable means for reconstructing the depth habitats of ancient species. Temperature-depth profiles for tropical Tertiary oceans have been reconstructed from the isotopic temperatures of planktic and benthic foraminifera. The vertical thermal structure of Oligocene oceans resembled that of modern oceans most closely. Those of Paleocene and Maastrichtian times differed most from that of modern oceans.

Data on the biogeochemical cycle of methane in the ocean

Geological, mineralogical and microbiological aspects of the methane cycle in water and sediments of different areas in the oceans are under consideration in the monograph. Original and published estimations of formation- and oxidation rates of methane with use of radioisotope and isotopic methods are given. The role of aerobic and anaerobic microbial oxidation of methane in production of organic matter and in formation of authigenic carbonates is considered. Particular attention is paid to processes of methane transformation in areas of its intensive input to the water column from deep-sea hydrothermal sources, mud volcanoes, and cold methane seeps.

Chemical and isotopic compositions of water, particulates, plankton, gases, sediments, and minerals from the Kara Sea and lower Ob and Yenisei Rivers

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea, into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions onboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO2 were examined throughout the whole sea area at more than 200 sites. The d13C varies from -22 and -24 per mil where Atlantic waters enter the Kara Sea and in the north-eastern part of the water area to -27 per mil in the Yenisei and Ob estuaries. The value of d13C of the plankton is only weakly correlated with the d13C of the organic matter from the sediments and is lower by as much as 3-4 per mil. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the river waters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the offshore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from -29 to -35 per mil in the riverine part, from -28 to -27 per mil in the estuaries, and from -27.0 to -25 per mil in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO2 concentrations, and long-distance CO2 supply to the sea with river waters. The data obtained on the isotopic composition of CO2 in the surface waters of the Kara Sea were used to map the distribution of d13C. The complex of hydrocarbon gases extracted from the waters included methane, C2-C5, and unsaturated C2=-C4= hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3-5 µl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with d13C from -105 to -90 per mil first occurs in the sediments at depths of 40-200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the d13C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (d13C from -25 to -60 per mil) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea.

Magnetic suceptibility, carbon and oxygen stable isotope ratios and reflectance from the Bottaccione Gorge and Furlo section, Italy

The oceans at the time of the Cenomanian-Turonian transition were abruptly perturbed by a period of bottom-water anoxia. This led to the brief but widespread deposition of black organic-rich shales, such as the Livello Bonarelli in the Umbria-Marche Basin (Italy). Despite intensive studies, the origin and exact timing of this event are still debated. In this study, we assess leading hypotheses about the inception of oceanic anoxia in the Late Cretaceous greenhouse world, by providing a 6-Myr-long astronomically-tuned timescale across the Cenomanian-Turonian boundary. We procure insights in the relationship between orbital forcing and the Late Cretaceous carbon cycle by deciphering the imprint of astronomical cycles on lithologic, geophysical, and stable isotope records, obtained from the Bottaccione, Contessa and Furlo sections in the Umbria-Marche Basin. The deposition of black shales and cherts, as well as the onset of oceanic anoxia, is related to maxima in the 405-kyr cycle of eccentricity-modulated precession. Correlation to radioisotopic ages from the Western Interior (USA) provides unprecedented age control for the studied Italian successions. The most likely tuned age for the Livello Bonarelli base is 94.17 ± 0.15 Ma (tuning #1); however, a 405-kyr older age cannot be excluded (tuning #2) due to uncertainties in stratigraphic correlation, radioisotopic dating, and orbital configuration. Our cyclostratigraphic framework suggests that the exact timing of major carbon cycle perturbations during the Cretaceous may be linked to increased variability in seasonality (i.e. a 405-kyr eccentricity maximum) after the prolonged avoidance of seasonal extremes (i.e. a 2.4-Myr eccentricity minimum). Volcanism is probably the ultimate driver of oceanic anoxia, but orbital periodicities determine the exact timing of carbon cycle perturbations in the Late Cretaceous. This unites two leading hypotheses about the inception of oceanic anoxia in the Late Cretaceous greenhouse world.

Sedimentology, geochemistry and ostracodes from Lake Ohrid

Ancient Lake Ohrid, located in the southern Balkan Peninsula in Macedonia and Albania is characterized by a high degree of endemism and it is considered to be the oldest lake in Europe. But its exact age (between one and ten million years) and also its origin are so far not known. To unravel these uncertainties an ICDP (International Continental Scientific Drilling Program) drilling project (Scientific Collaboration On Past Speciation Conditions in Ohrid (SCOPSCO)), started in April 2013. In addition to the investigations about the age and origin, other paleolimnological studies, e.g., the reconstruction of past climate and of past lake level changes, should be performed with the drilled cores. Used proxies in such paleolimnological studies are, e.g., ostracodes because they respond sensitively to environmental changes but an accurate knowledge of their preferences and tolerances to specific environmental conditions is necessary for this purpose. So far, this knowledge about the, mostly endemic, Ohrid ostracodes was limited. Thus, within the framework of this thesis, ostracodes and a multiplicity of environmental data were collected in Lake Ohrid and its adjacent waters during four field campaigns. In a total of 47 ostracode species could be detected in the entire study area and 32 of them were found alive in Lake Ohrid. Multivariate statistic identified that water depth, salinity, conductivity, pH, and dissolved oxygen were the main determining factors for ostracode distribution in the entire study area. In Lake Ohrid, the distribution was mainly controlled by water depth, water temperature, and pH. Some ostracodes were identified as strong indicator species for important environmental variables, e.g., water temperature and water depth. A distinctive feature of Lake Ohrid was the finding of the ostracode genus Amnicythere whose species normally inhabit oligo-(meso-)haline waters and this could point to a marine origin of the lake. So far, the specialized endemic ostracodes show the highest abundances and the greatest spatial distribution in Lake Ohrid but during the sampling eight widespread species were found for the first time in the lake. They inhabited mainly the northern part of the lake, where two cities are located and industry and agriculture play a major role, and they were limited to water depths above 50 m and this could be an evidence for an increasing anthropogenic pressure because widespread ostracode species often replace endemic species. To unravel the human impact on Lake Ohrid during the last decades short sediment cores were taken and the multi-proxy study indicated that the lake productivity between the early 1920s and the late 1980s was relatively low. Diatom assemblages indicate a rising productivity in the southern part of Lake Ohrid since the mid 1970s and geochemical proxies and ostracodes point to an increasing productivity since the late 1980s in the southern and in the northern part. A slight increase in the productivity continued until 2009. Noticeable is the fact that since the early 1990s, the increasing productivity and the increasing concentrations of heavy metals correspond to a decreasing number of ostracodes in the northern part of Lake Ohrid. Perhaps, this indicates that living conditions in this lake part became less favorable for the mostly endemic ostracode species. Furthermore, the sediment samples from the cores show relatively high concentrations of arsenic, iron, and nickel. Fluctuations in ostracode assemblages from three longer sediment cores, the longest spans approximately 136 ka, taken in Lake Ohrid, correspond to fluctuations in the productivity, in the carbonate content, of the lake level, and of climate changes. Between the marine isotope stage (MIS) 6 and MIS 2 the number of ostracode valves is very low or the valves were completely absent. This corresponds to a low lake productivity, a low carbonate content, and a low lake level. At the onset of the Holocene, the number of valves increased markedly and this correlates with an increased productivity and carbonate content and a warmer climate. But during the Little Ice Age (LIA), the number of valves dropped again and species which prefer warmer waters disappeared completely. This drop corresponds also to a low productivity. After the LIA, the number of species increased again but since 1895 AD a strong and abrupt decrease is visible. A reason for this could be an increase in the heavy metal concentrations.

Table 2: Isotopic and elemental compositions of Mesoproterozoic carbonates from Yanshan, North China

In Yanshan, located in the northern part of North China, Mesoproterozoic carbonate sequences (1.6-1.4 Ga) form a 10, 000m thick succession in an aulacogen basin. Carbon and oxygen isotope (d13O and d18O, resp.) data were obtained from 110 carbonate samples across three sections of these Mesoproterozoic deposits. From the early to late Mesoproterozoic, low negative values of d13O appear, followed by low positive variation and then a stable increase. An abrupt decrease in d13O values, with subsequent rapid increase, is found at the end of the Mesoproterozoic. During the whole Mesoproterozoic, d18O shows a mainly negative trend and occasional highly negative isotopic shifts (from lower to upper deposits). Whole-rock carbon and oxygen isotopic compositions and profilesmust be studied to provide a paleogeochemical record that can be associated with paleocean sedimentary environments, temperature, biological productivity, and sea-level fluctuations. Results of the present study correlate well with other international carbon and oxygen isotope profiles, suggesting that a global marine geochemical system existed during the interval of 1.6-1.4 Ga under a globally united tectonic, sedimentary, and geochemical background.

Carbon and oxygen isotope ratios, and geochemistry of the Precambrian-Cambrian Sukharikha River section, northwestern Siberian platform

A high-resolution carbon isotope profile through the uppermost Neoproterozoic-Lower Cambrian part of the Sukharikha section at the northwestern margin of the Siberian platform shows prominent secular oscillations of d13C with peak-to-peak range of 6-10 ?. There are six minima, 1n-6n, and seven maxima 1p-7p, in the Sukharikha Formation and a rising trend of d13C from the minimum 1n of -8.6 ? to maximum 6p of +6.4 ?. The trough 1n probably coincides with the isotopic minimum at the Precambrian-Cambrian boundary worldwide. Highly positive d13C values of peaks 5p and 6p are typical of the upper portion of the Precambrian-Cambrian transitional beds just beneath the Tommotian Stage in Siberia. A second rising trend of d13C is observed through the Krasnoporog and lower Shumny formations. It consists of four excursions with four major maxima that can be cor related with Tommotian-Botomian peaks II, IV, V, and VII of the reference profile from the southeastern Siberian platform. According to the chemostratigraphic cor relation, the first appearances of the index forms of archaeocyaths are earlier in the Sukharikha section than in the Lena-Aldan region.

Geomicrobiology, bulk sediment characteristics and pore water chemistry of sediment cores from Laguna Potrok Aike, southern Patagonia

Authigenic minerals can form in the water column and sediments of lakes, either abiotically or mediated by biological activity. Such minerals have been used as paleosalinity and paleoproductivity indicators and reflect trophic state and early diagenetic conditions. They are also considered potential indicators of past and perhaps ongoing microbial activity within sediments. Authigenic concretions, including vivianite, were described in late glacial sediments of Laguna Potrok Aike, a maar lake in southernmost Argentina. Occurrence of iron phosphate implies specific phosphorus sorption behavior and a reducing environment, with methane present. Because organic matter content in these sediments was generally low during glacial times, there must have been alternative sources of phosphorus and biogenic methane. Identifying these sources can help define past trophic state of the lake and diagenetic processes in the sediments. We used scanning electron microscopy, phosphorus speciation in bulk sediment, pore water analyses, in situ ATP measurements, microbial cell counts, and measurements of methane content and its carbon isotope composition (d13C CH4) to identify components of and processes in the sediment. The multiple approaches indicated that volcanic materials in the catchment are important suppliers of iron, sulfur and phosphorus. These elements influence primary productivity and play a role in microbial metabolism during early diagenesis. Authigenic processes led to the formation of pyrite framboids and revealed sulfate reduction. Anaerobic oxidation of methane and shifts in pore water ion concentration indicated microbial influence with depth. This study documents the presence of active microbes within the sediments and their relationship to changing environmental conditions. It also illustrates the substantial role played by microbes in the formation of Laguna Potrok Aike concretions. Thus, authigenic minerals can be used as biosignatures in these late Pleistocene maar sediments.

Geochemical and stable isotope composition of Middle Campanian marl-limestone rhythmites of the Lehrte West Syncline near Hannover (Lower Saxony, northern Germany)

A cyclic marl-limestone succession of Middle-Late Campanian age has been investigated with respect to a Milankovitch-controlled origin of geochemical data. In general, the major element geochemistry of the marl-limestone rhythmites can be explained by a simple two-component mixing model with the end-members calcium carbonate and 'average shale'-like material. Carbonate content varies from 55 to 90%. Non-carbonate components are clay minerals (illite, smectite) and biogenic silica from sponge spicules, as well as authigenically formed zeolites (strontian heulandite) and quartz. The redox potential suggests oxidizing conditions throughout the section. Trace element and stable isotopic data as well as SEM investigations show that the carbonate mud is mostly composed of low-magnesium calcitic tests of planktic coccolithophorids and calcareous dinoflagellate cysts (calcispheres). Diagenetic overprint results in a decrease of 2% d18O and an increase in Mn of up to 250 ppm. However, the sediment seems to preserve most of its high Sr content compared to the primary low-magnesium calcite of co-occurring belemnite rostra. The periodicity of geochemical cycles is dominated by 413 ka and weak signals between 51 and 22.5 ka, attributable to orbital forcing. Accumulation rates within these cycles vary between 40 and 50 m/Ma. The resulting cyclic sedimentary sequence is the product of (a) changes in primary production of low-magnesium calcitic biogenic material in surface waters within the long eccentricity and the precession, demonstrated by the CaCO3 content and the Mg/Al, Mn/Al and Sr/Al ratios, and (b) fluctuations in climate and continental weathering, which changed the quality of supplied clay minerals (the illite/smectite ratio), demonstrated by the K/Al ratio. High carbonate productivity correlates with smectite-favouring weathering (semi-arid conditions, conspicuously dry and moist seasonal changes in warmer climates). Ti as the proxy indicator for the detrital terrigenous influx, as well as Rb, Si, Zr and Na, shows only low frequency signals, indicating nearly constant rates of supply throughout the more or less pure pelagic carbonate deposition of the long-lasting third-order Middle-Upper Campanian sedimentary cycle.

Geochemical measurements of the Tasmanian Gateway from ODP Hole 189-1172A

Tectonic changes that produced a deep Tasmanian Gateway between Australia and Antarctica are widely invoked as the major mechanism for Antarctic cryosphere growth and Antarctic Circumpolar Current (ACC) development during the Eocene/Oligocene (E/O) transition (34-33 Ma). Ocean Drilling Program (ODP) Leg 189 recovered near-continuous marine sedimentary records across the E/O transition interval at four sites around Tasmania. These records are largely barren of calcareous microfossils but contain a rich record of siliceous- and organic-walled marine microfossils. In this study we integrate micropaleontological, sedimentological, geochemical, and paleomagnetic data from Site 1172 (East Tasman Plateau) to identify four distinct phases (A-D) in the E/O Tasmanian Gateway deepening that are correlative among ODP Leg 189 sites. Phase A, prior to 35.5 Ma: minor initial deepening characterized by a shallow marine prodeltaic setting with initial condensation episodes. Phase B, 35.5-33.5 Ma: increased deepening marked by the onset of major glauconitic deposition and inception of energetic bottom-water currents. Phase C, 33.5-30.2 Ma: further deepening to bathyal depths, with episodic erosion by increasingly energetic bottom-water currents. Phase D, <30.2 Ma: establishment of stable, open-ocean, warm-temperate, oligotrophic settings characterized by siliceous-carbonate ooze deposition. Our combined evidence indicates that this early Oligocene Tasmanian Gateway deepening initially produced an eastward flow of relatively warm surface waters from the Australo-Antarctic Gulf into the southwestern Pacific Ocean. This "proto-Leeuwin" current fundamentally differs from previous regional reconstructions of eastward flowing cool water (e.g., a "proto-ACC") during the early Oligocene and thereby represents an important new constraint for reconstructing regional- to global-scale dynamics for this major global change event.

Mineralogical (bulk rock and clay fraction) and stable isotope composition (d13C, d18O) of Aptian deposits of the Bir Oum Ali succession, central Tunisia

Alternations between siliciclastic, carbonate and evaporitic sedimentary systems, as recorded in the Aptian mixed succession of southern Tunisia, reflect profound palaeoceanographic and palaeoclimatic changes in this area of the southern Tethyan margin. The evolution from Urgonian-type carbonates (Berrani Formation, lower Aptian) at the base of the series, to intervals dominated by gypsum or detrital deposits in the remainder of the Aptian is thought to result from the interplay between climate change and tectonic activity that affected North Africa. Based on the evolution of clay mineral assemblages, the early Aptian is interpreted as having been dominated by slightly humid conditions, since smectitic minerals are observed. Near the early to late Aptian boundary, the onset of a gypsiferous sedimentation is associated with the appearance of palygorskite and sepiolite, which supports the installation of arid conditions in this area of the southern Tethyan margin. The evaporitic sedimentation may have also been promoted by the peculiar tectonic setting of the Bir Oum Ali area during the Aptian, where local subsidence may have been tectonically enhanced linked to the opening of northern and central Atlantic. Stress associated with the west and central African rift systems may have triggered the development of NW-SE, hemi-graben structures. Uplifted areas may have constituted potential new sources for clastic material that has been subsequently deposited during the late Aptian. Chemostratigraphic (d13C) correlation of the Bir Oum Ali succession with other peri-Tethyan regions complements biostratigraphic findings, and indicates that a potential expression of the Oceanic Anoxic Event (OAE) 1a may be preserved in this area of Tunisia. Although the characteristic negative spike at the base of this event is not recognized in the present study, a subsequent, large positive excursion with d13C values is of similar amplitude and absolute values to that reported from other peri-Tethyan regions, thus supporting the identification of isotopic segments C4-C7 of the OAE1a. The absence of the negative spike may be linked to either non preservation or non deposition: the OAE1a occurred in a global transgressive context, and since the Bir Oum Ali region was located in the innermost part of the southern Tethyan margin during most of the Aptian, stratigraphic hiatuses may have been longer than in other regions of the Tethys. This emphasizes the importance of integrating several stratigraphic disciplines (bio-, chemo- and sequence stratigraphy) when performing long-distance correlation.

Biogeochemical, sedimentological and isotopic sediment record of Lake Dojran

A Late Glacial to Holocene sediment sequence (Co1260, 717 cm) from Lake Dojran, located at the boarder of the F.Y.R. of Macedonia and Greece, has been investigated to provide information on climate variability in the Balkan region. A robust age-model was established from 13 radiocarbon ages, and indicates that the base of the sequence was deposited at ca. 12 500 cal yr BP, when the lake-level was low. Variations in sedimentological (H2O, TOC, CaCO3, TS, TOC/TN, TOC/TS, grain-size, XRF, d18Ocarb, d13Ccarb, d13Corg) data were linked to hydro-acoustic data and indicate that warmer and more humid climate conditions characterised the remaining period of the Younger Dryas until the beginning of the Holocene. The Holocene exhibits significant environmental variations, including the 8.2 and 4.2 ka cooling events, the Medieval Warm Period and the Little Ice Age. Human induced erosion processes in the catchment of Lake Dojran intensified after 2800 cal yr BP.

(Table 1) Concentrations and isotopic ratios of sulfur and carbon in acid conglomerates from DSDP Hole 57-439

The sulfur content of one rhyolite and four dacite conglomerates was found to be low - from 9 to 97 ppm - similar to that of Quaternary andesites and basalts of the Japanese Islands. However, the d34S values of these samples are unexpectedly high - +23 to +35 per mill - relative to troilite from the Canon Diablo meteorite. The sulfide/sulfate ratios vary among the five samples from 0 to 13. No significant isotope fractionation seems to exist between sulfate and sulfide sulfurs. Carbon in these samples is predominantly in the form of carbonate (and probably CO2). It ranges in concentration from 128 to 721 ppm and in d13C from -2.5 to -20.7 per mill relative to PDB.