Stable isotopes and ages from sediment core FR01/97-12, Tasman Sea

Deep-sea sediment core FR1/97 GC-12 is located 990 mbsl in the northern Tasman Sea, southwest Pacific, where Antarctic Intermediate Water (AAIW) presently impinges the continental slope of the southern Great Barrier Reef. Analysis of carbon (d13C) and oxygen (d18O) isotope ratios on a suite of planktonic and benthic foraminifera reveals rapid changes in surface and intermediate water circulation over the last 30 kyr. During the Last Glacial Maximum, there was a large d13C offset (1.1 per mil) between the surface-dwelling planktonic foraminifera and benthic species living within the AAIW. In contrast, during the last deglaciation (Termination 1), the d13C(planktonic-benthic) offset reduced to 0.4 per mil prior to an intermediate offset (0.7 per mil) during the Holocene. We suggest that variations in the dominance and direction of AAIW circulation in the Tasman Sea, and increased oceanic ventilation, can account for the rapid change in the water column d13C(planktonic-benthic) offset during the glacial-interglacial transition. Our results support the hypothesis that intermediate water plays an important role in propagating climatic changes from the polar regions to the tropics. In this case, climatic variations in the Southern Hemisphere may have led to the rapid ventilation of deep water and AAIW during Termination 1, which contributed to the postglacial rise in atmospheric CO2.

Age model of ODP Hole 107-654A

It has long been speculated that glacio-eustatic sea level drop may have caused or contributed to the isolation and consequent desiccation of the Mediterranean in the late Miocene (the 'Messinian salinity crisis'). Ocean Drilling Program site 654 on the Sardinia margin of the Tyrrhenian Sea is the first deep-sea drill site to penetrate through upper Messinian evaporites into lower Messinian/upper Tortonian open marine sediments, and thus offers a unique opportunity to date the onset of the salinity crisis. A reexamination of the magnetostratigraphic, biostratigraphic, and stable isotope-stratigraphic constraints on the preevaporite sediments of site 654 has yielded two possible ages for the contact between salinity crisis sediments and the underlying normal marine sediments. One magnetostratigraphic interpretation plus the biostratigraphically determined position of the Tortonian/Messinian boundary imply a date of about 6.2 Ma for the youngest presalinity crisis sediments. An alternative magnetostratigraphic interpretation plus the carbon isotope stratigraphy imply a date of about 5.2 Ma. The younger of these dates coincides with a delta18O spike in open ocean sediments [Keigwin, 1987 doi:10.1029/PA002i006p00639], which is attributed to increased ice volume.

Methane concentration profiles and isotopic composition of sediment cores from the Black Sea

We present high resolution profiles for the methane concentration and the carbon isotope composition of methane from surface sediments and from the sediment-water transition in the Black Sea. At shallow water sites methane migrates from the sediment into the water column, and the magnitude of this upward migrating flux depends on the depth of the sulfate-methane transition (SMT) in the sediment. The isotope data reveal that the sediments at shallow water sites are a source for methane depleted in 13C relative to the isotope composition of methane in the water column. At deep water sites the methane concentration first decreases with depth in the sediment to reach lowest values at the Unit I to Unit II transition. Below this transition the concentration increases again. Numerical modeling of methane concentration and isotope data shows that high methane oxidation rates occur in the surface sediment layer, indicating that the removal of methane in the surface sediments is not related to the anaerobic oxidation of methane coupled to sulfate reduction that occurs a few meters deep in the sediment, at the SMT. Instead, near-surface methane consumption in the euxinic Black Sea sediments appears to be related to lithological stratification. Furthermore, a map of the diffusive methane fluxes in the Black Sea surface sediments indicates that approximately half of the Black Sea seafloor acts as a sink for methane and thus limits the flux of methane to the atmosphere.

Faunal turnovers in the central Pacific benthic foraminifera during the Paleocene-Eocene thermal maximum

Although it is well known that the Paleocene/Eocene thermal maximum (PETM) coincided with a major benthic foraminiferal extinction event, the detailed pattern of the faunal turnover has not yet been clarified. Our high-resolution benthic foraminiferal and carbon isotope analyses at the low latitude Pacific Ocean Shatsky Rise have revealed the following record of major faunal transitions: (1) An initial turnover which involved the benthic foraminiferal extinction event (BFE). The BFE, marked by a sharp transition from Pre-extinction fauna to Disaster fauna represented by small-sized Bolivina gracilis, expresses the onset of the PETM and the abrupt extinction of about 30% of taxa. This faunal transition lasted about 45-74 kyr after the initiation of the PETM and was followed by: (2) the appearance of Opportunistic fauna represented by Quadrimorphina profunda, which existed for about 74-91 kyr after the initiation of the PETM. These two faunas, which appeared after the extinction event, are characterized by low diversity and dwarfism, possibly due to lowered oxygen condition and decreased surface productivity. The second pronounced turnover involved the gradual recovery from Opportunistic Fauna to the establishment of Recovery fauna, which coincided with the recovery about 83-91 kyr after its initiation.

Geochemistry of karst headwaters

This study investigated CO2 degassing and related carbon isotope fractionation effects in the Wiesent River that drains a catchment in the karst terrain of the Fraconian Alb, Southern Germany. The river was investigated by physico-chemical and stable isotope analyses of water and dissolved inorganic carbon during all seasons in 2010 along 65 km long downstream transects between source and mouth. This data set contains the results of field and solute parameters (temperature, conductivity, pH, total alkalinity, total CO2, and pCO2) and stable isotope analyses (d2H-H2O, d18O-H2O, d13C-DIC) for the Wiesent River and major tributaries.

Planktonic foraminifera of ODP Hole 107-654A

The late Miocene sediments of the Tyrrhenian ODP Site 654 encompass a deepening sequence which begins with glauconite shallow water sands followed by a rapid transition to deep water sediments and culminates with dolomitic mudstones associated with Messinian evaporites. The sequence compares well with the so-called 'Sahelian cycle' and with post-orogenic cycles recognized in peninsular Italy and Sicily. The studied interval, consisting of 55 m thick nannofossil oozes, belongs to the Globorotalia suterae subzone and lower part of the Globorotalia conomiozea Zone, indicating late Tortonian and early Messinian age, respectively. Biomagnetostratigraphic correlation assigns the Tortonian/ Messinian boundary an age of 6.44-6.45 Ma. In addition, six main events have been recognized, based on the range of keeled globorotaliids and coiling direction changes of keeled and unkeeled globorotaliids, which have been correlated to the geomagnetic time-scale. Comparison with North Atlantic sites and land sections of the Guadalquivir basin and northern Morocco provides good correlations with the events documented in these areas. In particular, Event IV, which predates the FO of Globorotalia conomiozea, may be used to recognize the Tortonian/Messinian boundary in extra-Mediterranean areas where G. conomiozea is missing. Variations in the distribution of different species of Globigerinoides are related to changes in the surficial marine environment. Although no clear trends can be recognized on the oxygen and carbon isotope records of Globigerinoides obliquus, the parallelism between the occurrence of low salinity species (G. sacculifer) and peaks of low 5180 values, as well as that of normal salinity species (G. obliquus) and peaks of high d18O values, suggests strong local changes of environmental conditions. The high amplitude of the fluctuations of d18O values suggests important variations in the salinity of the Tyrrhenian Sea, related to a rapidly changing water budget. The major feature of the carbon isotope record is a large decrease between 7.0 and 6.95 Ma, which therefore predates the 6.2 Ma global 'carbon shift'.

Compositional and isotopic data on core MD84641

The organic carbon isotopic record of the sapropels(S1 and S3-S10) and intercalated marl oozes has been determined in a 12-m piston core from the eastern Mediterranean. The d13C_organic values are systematically lighter (mean=-21.0±0.82 per mil) in all sapropels and heavier (mean=-18.8±1.07 per mil) in the marl oozes. These differences are not due to variable marine and terrestrial organic matter mixtures because all values are heavier than modern plankton in the Mediterranean, there is no relationship between the C_organic/N ratios and the isotopic values, and published information on the abundance and distribution of organic biomarkers shows that terrestrial material constitutes a minor fraction of the total organic matter. Temperature effects on isotope fractionation are also discounted because the change in d13C_organic values between glacial and interglacial horizons is in the opposite sense. Diagenesis, which can produce relatively small changes in the carbon isotopic composition of sedimentary organic matter under certain circumstances, is unlikely to have caused the observed differences because this mechanism would cause an enrichmet in 12C, implying that all values were even heavier originally, and there is no secular trend in the d13C_organic record. The observed differences in d13C_organic between the two lithologies are probably produced by changes in the isotopic composition and the concentration of dissolved CO2. First, freshwater flooding during the formation of the sapropels caused the isotopic composition of the dissolved inorganic carbon in the surface waters of the Mediterranean to become lighter because of the 13C deficiency in fresh waters. Hence photosynthesis would have produced isotopically lighter organic material. Second, changes in atmospheric pCO2 between glacial and interglacial periods, as shown by the Vostok ice core, caused marked changes in the concentration of free dissolved CO2 in the mixed layer; lower values during glacial maxima caused a smaller fractionation of the carbon isotopes by phytoplankton, whereas levels were less limiting during the interglacials. Concentrations of dissolved CO2 could also have been much higher during the deposition of the sapropels because of the supply of regenerated CO2 to the mixed layer by upwelling, and this could have further lightened the d13C_organic values in the sapropels themselves. Carbon isotope records may provide an alternative method for estimating atmospheric pCO2 levels over longer time periods than can be obtained from ice cores.

Organic geochemistry records from two Palaeocene-Eocene Thermal Maximum sections in Denmark

Analysis of sediments deposited at different latitudes around the world during the Palaeocene-Eocene Thermal Maximum (PETM; ~56 Ma) have revealed a globally profound warming phase, regionally varying from 5-8 °C. Such records from Europe have not yet been obtained. We studied the variations in sea surface and continental mean annual air temperatures (SST and MAT, respectively) and the distribution patterns and stable carbon isotopes of higher plant derived n-alkanes in two proximal PETM sections (Fur and Store Bælt, Denmark) from the epicontinental North Sea Basin. A negative carbon isotope excursion (CIE) of 4-7 per mil was recorded in land plant derived n-alkanes, similar to what has been observed for other PETM sections. However, differences observed between the two proximal sites suggest that local factors, such as regional vegetation and precipitation patterns, also influenced the CIE. The presence of S-bound isorenieratene derivatives at the onset of the PETM and increased organic carbon contents points to a rapid shift in depositional environment; from well oxygenated to anoxic and sulfidic. These euxinic conditions are comparable with those during the PETM in the Arctic Ocean. SSTs inferred from TEX86 show relatively low temperatures followed by an increase of ~7 °C across the PETM. At the Fur section, a remarkably similar temperature record was obtained for MAT using the MBT'/CBT proxy. However, the MAT record of the Store Bælt section did not reveal this warming.

Mineralogy, grain size composition, bulk carbonate isotopic ratios and ages of ODP Site 182-1128 sediments

This report presents mineralogic and geochemical data from Ocean Drilling Program Leg 182 Site 1128 in the Great Australian Bight. Clay mineralogy is dominated by mixed-layer illite-smectite, followed by minor amounts of kaolinite and illite, with intervals of pure smectite. Carbonate mineralogy is exclusively low-Mg calcite, except for one interval of dolomite in lower Oligocene sediments. Carbonate increases significantly in upper Eocene sediments, decreases through the lower Oligocene, then increases again in the Neogene. Quartz is present as a minor component that covaries inversely with carbonate. High-resolution sampling associated with Chron 13 normal (early Oligocene) reveals high-frequency (~23 k.y.) fluctuations in clay mineralogy and carbonate abundance and a positive oxygen and carbon isotope excursion (in bulk carbonates) related to Antarctic glaciation.

Hydrocarbon gar in sediments of the Costa Rica ubduction zone

At the active continental margin off Costa Rica substantial amounts of hydrocarbon gases are encountered in sediments. The molecular composition (C1-C3) of free hydrocarbon gas as well as the isotopic composition (d13C of methane and ethane and D of methane) was analysed on core samples (ranging between 50 and 380 m depth) collected at sites 1040-1043 which was drilled during ODP Leg 170. In addition, the molecular composition of the C1-C3 hydrocarbons and the d13C composition of C1 and C2 hydrocarbons was determined on adsorbed gas from selected depth intervals at Site 1041 (50-380 mbsf). The molecular composition, and stable carbon and hydrogen isotope signature of low molecular weight hydrocarbons from core sediments and gas pockets indicate that most of the gas was generated by microbial CO2-reduction. Beside d13C values of about -80 per mil for methane (which is typical for microbially- generated methane) extremely light d13C values of -55 per mil were measured for ethane. The carbon isotope composition of methane and ethane, as well as the C1/(C2+C3) ratio display distinct trends with increasing depth. Gas mixing calculations indicate that the percentage of thermally-generated ethane increases from 10% at about 75 mbsf to almost 80% at 380 mbsf. The fraction of thermogenic methane in this depth interval is calculated to range from 0.03 to 1.8% of the total methane. The small contribution of thermogenic methane would increase the d13C value by <1 per mil. Therefore, the increase of d13C of methane (by about 12 per mil) with depth cannot be explained by gas mixing alone. Instead, the observed d13C trend is caused by successive isotope depletion of the methane precursor within the sedimentary organic matter due to progressing microbial gas generation.

Organic geochemistry of Cretaceous black shales

Organic-carbon-rich 'black shales' and adjacent organic-carbon-poor rocks from three different Cretaceous settings encountered during ODP Leg 103 have been studied by organic geochemical methods. Rock-Eval analysis, carbon isotope data, and lipid biomarkers show organic matter to contain varying proportions of marine and continental materials. In Hauterivian-Barremian organic-carbon-rich marlstone turbidites, large amounts of land-derived organic matter are found. Aptian-Albian black-colored shales are interspersed within green claystones, from which they differ by containing more marine organic matter. An abbreviated layer of black shale from the Cenomanian/Turonian boundary is dominated by well-preserved marine organic matter. Downslope transport and rapid reburial within a predominantly oxygenated deep-water setting created most of these examples of black shales, except for the Cenomanian-Turonian deposits in which deep-water anoxia may have been involved.

Geochemistry of Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian-Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, d13Corg values lie mostly between -30 per mil and -27 per mil, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low d13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian-Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.