Middle Eocene bulk sediment, benthic and planktic foraminiferal stable isotope values, and relative weight percent CaCO3 content from ODP Site 207-1260

Major ice sheets were permanently established on Antarctica approximately 34 million years ago, close to the Eocene/ Oligocene boundary, at the same time as a permanent deepening of the calcite compensation depth in the world's oceans. Until recently, it was thought that Northern Hemisphere glaciation began much later, between 11 and 5million years ago. This view has been challenged, however, by records of ice rafting at high northern latitudes during the Eocene epoch and by estimates of global ice volume that exceed the storage capacity of Antarctica at the same time as a temporary deepening of the calcite compensation depth 41.6 million years ago. Here we test the hypothesis that large ice sheets were present in both hemispheres 41.6 million years ago using marine sediment records of oxygen and carbon isotope values and of calcium carbonate content from the equatorial Atlantic Ocean. These records allow, at most, an ice budget that can easily be accommodated on Antarctica, indicating that large ice sheets were not present in the Northern Hemisphere. The records also reveal a brief interval shortly before the temporary deepening of the calcite compensation depth during which the calcite compensation depth shoaled, ocean temperatures increased and carbon isotope values decreased in the equatorial Atlantic. The nature of these changes around 41.6 million years ago implies common links, in terms of carbon cycling, with events at the Eocene/Oligocene boundary and with the 'hyperthermals' of the Early Eocene climate optimum. Our findings help to resolve the apparent discrepancy between the geological records of Northern Hemisphere glaciation and model results that indicate that the threshold for continental glaciation was crossed earlier in the Southern Hemisphere than in the Northern Hemisphere.

Macroturbidites of ODP Hole 103-641C

Barremian through uppermost Aptian strata from ODP Hole 641C, located upslope of a tilted fault block on the Galicia margin (northwest Spain), are syn-rift sediments deposited in the bathyal realm and are characterized by rapid sedimentation from turbidity currents and debris flows. Calcarenite and calcirudite turbidites contain shallow-water carbonate, terrigenous, and pelagic debris, in complete or partial Bouma sequences. These deposits contain abraded micritized bioclasts of reefal debris, including rudist fragments. The youngest turbidite containing shallow-water carbonate debris at Site 641 defines the boundary between syn-rift and post-rift sediments; this is also the boundary between Aptian and Albian sediments. Some Aptian turbidites are partially silicified, with pore-filling chalcedony and megaquartz. Adjacent layers of length-fast and -slow chalcedony are succeeded by megaquartz as the final pore-filling stage within carbonate reef debris. Temperatures of formation, calculated from the oxygen isotopic composition of the authigenic quartz, are relatively low for formation of quartz but are relatively warm for shallow burial depths. This quartz cement may be interpreted as a rift-associated precipitate from seawater-derived epithermal fluids that migrated along a fault associated with the tilted block and were injected into the porous turbidite beds. These warm fluids may have cooled rapidly and precipitated silica at the boundaries of the turbidite beds as a result of contact with cooler pore waters. The color pattern in the quartz cement, observed by cathodoluminescence and fluorescence techniques, and changes in the trace lement geochemistry mimic the textural change of the different quartz layers and indicates growth synchronism of the different quartz phases. Fluorescence petrography of neomorphosed low-Mg-calcite bioclasts in the silicified turbidites shows extensive zonation and details of replacive crystal growth in the bioclasts that are not observed by cathodoluminescence. Fluorescence microscopy also reveals a competitive growth history during neomorphism of the adjacent crystals in an altered carbonate bioclast. Barremian-Aptian background pelagic sediments from Hole 641C have characteristics similar to pelagic sediments from the Blake-Bahama Formation described by Jansa et al. (1979) from the western North Atlantic. Sediments at this site differ from the Blake-Bahama Formation type locality in that the Barremian-Aptian pelagic sediments have a higher percentage of dark calcareous claystone and some turbidites are silicified at Site 641. The stable isotopic composition of the pelagic marlstones from Site 641 is similar to those of other Berriasian-Aptian pelagic sediments from the Atlantic.

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.

Total organic carbon content, methane isotopic composition and hydrocarbon characteristics of ODP Leg 180 sites

The organic geochemistry of Sites 1108 and 1109 of the Woodlark Basin, offshore Papua New Guinea, was studied to determine whether thermally mature hydrocarbons were present in the penetrated section and, if present, whether they are genetically related to the penetrated "coaly" interval. Both the organic carbon and pyrolysis data indicate that there is no significant hydrocarbon source-rock potential at Site 1108. The hydrocarbons encountered during drilling appear to be indigenous and not migrated products or contaminants. In contrast, the coaly interval at Site 1109 contains zones with significant hydrocarbon-generation potential. Several independent lines of evidence indicate that the coaly sequence encountered at Site 1109 is thermally immature. The Site 1108 methane stable-carbon isotope composition does not display a clear trend with depth as would be expected if it was solely reflecting a maturation profile. The measured isotopic composition of methane has most probably been altered by fractionation during sample handling and storage. This fractionation would result in isotopically heavier values than would be obtained on free gas. The organic geochemical data gathered indicate that Site 1108 can be safely revisited and that the organic-rich sediments encountered at Site 1109 were not the source of the gas encountered at Site 1108.

Calcium carbonate mineralogy and stable isotopic composition of Leg 182 sites, Great Australian Bight

An intensive stable isotopic investigation was conducted on sediments recovered from the Great Australian Bight during Ocean Drilling Program Leg 182 at Sites 1127, 1129, and 1131. The sites comprise a transect from the shelf edge to upper slope through a thick sequence of predominately Quaternary cool-water carbonate sediments. Detailed mineralogic and stable isotopic (d18O and d13C) analyses of sediments from a total of 306 samples are presented from all three sites.

Pore water isotopic ratios of CO2 and SO4, and sediment CH4 content of ODP Leg 164 sites

A unique set of geochemical pore-water data, characterizing the sulfate reduction and uppermost methanogenic zones, has been collected at the Blake Ridge (offshore southeastern North America) from Ocean Drilling Program (ODP) Leg 164 cores and piston cores. The d13C values of dissolved CO2 (sum CO2) are as 13C-depleted as -37.7 per mil PDB (Site 995) at the sulfate-methane interface, reflecting a substantial contribution of isotopically light carbon from methane. Although the geochemical system is complex and difficult to fully quantify, we use two methods to constrain and illustrate the intensity of anaerobic methane oxidation in Blake Ridge sediments. An estimate using a two-component mixing model suggests that ~24% of the carbon residing in the sum CO2 pool is derived from biogenic methane. Independent diagenetic modeling of a methane concentration profile (Site 995) indicates that peak methane oxidation rates approach 0.005 µmol/cm**3/yr, and that anaerobic methane oxidation is responsible for consuming ~35% of the total sulfate flux into the sediments. Thus, anaerobic methane oxidation is a significant biogeochemical sink for sulfate, and must affect interstitial sulfate concentrations and sulfate gradients. Such high proportions of sulfate depletion because of anaerobic methane oxidation are largely undocumented in continental rise sediments with overlying oxic bottom waters. We infer that the additional amount of sulfate depleted through anaerobic methane oxidation, fueled by methane flux from below, causes steeper sulfate gradients above methane-rich sediments. Similar pore water chemistries should occur at other methane-rich, continental-rise settings associated with gas hydrates.

Neodymium isotope ratios of fish debris from late Cretaceous black shales

Neodymium isotopes of fish debris from two sites on Demerara Rise, spanning ~4.5 m.y. of deposition from the early Cenomanian to just before ocean anoxic event 2 (OAE2) (Cenomanian-Turonian transition), suggest a circulation-controlled nutrient trap in intermediate waters of the western tropical North Atlantic that could explain continuous deposition of organic-rich black shales for as many as ~15 m.y. (Cenomanian-early Santonian). Unusually low Nd isotopic data (epsilon-Nd(t) ~-11 to ~-16) on Demerara Rise during the Cenomanian are confirmed, but the shallower site generally exhibits higher and more variable values. A scenario in which southwest-flowing Tethyan and/or North Atlantic waters overrode warm, saline Demerara bottom water explains the isotopic differences between sites and could create a dynamic nutrient trap controlled by circulation patterns in the absence of topographic barriers. Nutrient trapping, in turn, would explain the ~15 m.y. deposition of black shales through positive feedbacks between low oxygen and nutrient-rich bottom waters, efficient phosphate recycling, transport of nutrients to the surface, high productivity, and organic carbon export to the seafloor. This nutrient trap and the correlation seen previously between high Nd and organic carbon isotopic values during OAE2 on Demerara Rise suggest that physical oceanographic changes could be components of OAE2, one of the largest perturbations to the global carbon cycle in the past 150 m.y.

Main components and isotopic composition of gases from mineral waters of the Taman Peninsula and Caucasus

Helium isotope composition as an indicator of the mantle-derived component was studied in gases from mineral springs, stratal waters, and mud volcanoes developed west of the Teberda River valley (10 objects) and two springs in the central segment of the Greater Caucasus orogen between the active El'brus and Kazbek volcanoes. In the western segment of the orogen ratios of 3He/4He = R_corr vary from 46x10**-8 to 114x10**-8 (from 0.33 to 0.81 R_atm, where R_atm = 1.4x10**-6 is the atmospheric ratio). They are substantially lower relative to ratios in the vicinity of El'brus and Kazbek and close to those in samples from the central segment (from 70x10**-8 to 134x10**-8 (from 0.50 to 0.96 R_atm), as well as to ratios previously recorded in the Caucasian Mineral Waters (CMW) area. Moreover, concentration of 3He in them is notably higher than its crustal radiogenic level characteristic of mud volcanoes in the Taman Peninsula, where 3He/4He varies from 1.4x10**-8 to 2.8x10**-8 (from 0.01 to 0.02 R_atm). Nitrogen-methane gas from northern piedmonts of the western Caucasus also contains nonatmogenic components including radiogenic 40Ar (40Ar/36Ar = 900), excessive nitrogen (~87% of total N2 concentration in sample) and mantle He. These data specify distribution of mantle derivates along the orogen strike and age of intrusive magmatic activity in its different segments.

Stable oxygen and carbon isotope ratios of foraminifera from Oligocene to Miocene sediments of DSDP Hole 39-354 from Ceara Rise, West Altlantic (Table 1)

The oxygen- and carbon-isotope compositions of planktic and benthic foraminifera and calcareous nannofossils from Middle Oligocene-Early Miocene Equatorial Atlantic sediments (DSDP Site 354) indicate two important paleoceanographic changes, in the Late Oligocene (foraminiferal Zone P.21) and in the Early Miocene (foraminiferal Zone N.5). The first change, reflected by a delta18O increase of 1.45? in Globigerina venezuelana, affected only intermediate pelagic and not surface, deep or bottom waters. The second change affected surface and intermediate waters, whereas deep and bottom waters showed only minor fluctuations. In the case of the former the isotope effect of the moderate ice accumulation on the Antarctic continent is amplified in the Equatorial Atlantic by changes in the circulation pattern. The latter paleoceanographic change, reflected by a significant increase in 18O in both planktic and benthic forms (about 1.0? and 0.5?, respectively), may have been caused by ice volume increase and temperature decrease. Both oxygen- and carbon-isotope compositions indicate a marked depth-habitat stratification for planktic foraminifera and calcareous nannofossils. Three different dwelling groups are recognized: shallow Globigerinoides, Globoquadrina dehiscens, Globorotalia mayeri and nannofossils; intermediate Globigerina venezuelana; and deep Catapsydrax dissimilis. The comparison of foraminifera and calcareous nannofossils suggests that the isotopic compositions of nannofossils are generally controlled by the same parameters which control the isotopic composition of shallow-dwelling foraminifera, but the former are more enriched in 18O.

Age determination and sedimentology of sediment core Lz1101 from the Melles Lake

A lacustrine sediment core from Store Koldewey, northeast Greenland, was biogeochemically, biologically and sedimentologically investigated in order to reconstruct long- and short-term climatic and environmental variability. The chronology of the uppermost 189 cm of the record is based on ten 14C AMS age determinations of aquatic mosses. The record covers almost the entire Holocene and revealed changes on multidecadal to centennial scales. Dating of the oldest mosses shows that lacustrine biogenic productivity already began at around 11 cal. kyr BP. This age pre-dates the onset of biogenic productivity in other lakes on Store Koldewey by about 2 kyr. In spite of the early onset of biogenic production organic matter accumulation remained low and minerogenic sedimentation dominated. At about 9.5 cal. kyr BP moss, sulphur, organic carbon and biogenic silica content started to increase, indicating that the environment stabilized and the biogenic production in the lake adjusted to more preferable conditions. Subsequently, the biogenic productivity experienced repeated changes and varied both on long- and short-term scales. The long-term trend shows a maximum during the early Holocene thus responding to increased temperatures during the Holocene Thermal Maximum. Superimposed on the long-term trend, biogenic productivity also experienced repeated short-term fluctuations that match partly the NGRIP temperatures. The most pronounced decrease of biogenic productivity occurred at around 8.2 cal. kyr BP. Perennial lake ice coverage resulting from low temperatures is supposed to have caused decreased lacustrine biogenic productivity. From the middle Holocene to the present repeated decreases of productivity occurred that could be related to periods with severe sea-ice conditions of the East Greenland Current. Besides the dependence on air temperature it therefore demonstrates the sensitivity of lacustrine biogenic productivity in coastal high arctic areas to short-term cold spells that are mediated by the currents emanating from the Arctic Ocean. However, the data also emphasize the difficulties associated with the interpretation of lacustrine records.

Table 1. Pressure, temperature and isotope ratios between H2O and CO2 for all experiments

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on d13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of d18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in d18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that d18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50°C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that d18O values of CO2 were on average 36.4±2.2 per mil (1 sigma, n=15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5 per mil for the experimental temperatures of 50°C. By using 18O enriched water for the experiments it was demonstrated that changes in the d18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in d18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the d18O values of CO2 and water are sufficiently distinct.