Biphytane and stable carbon isotopic values of sugars and glycerol from ODP Hole 204-1245D and 201-1229A

The membrane lipids diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2G-GDGTs) in marine subsurface sediments are believed to originate from uncultivated benthic archaea, yet the production of 2G-GDGTs from subseafloor samples has not been demonstrated in vitro. In order to validate sedimentary biosynthesis of 2G-GDGTs, we performed a stable carbon isotope probing experiment on a subseafloor sample with six different 13C-labelled substrates (bicarbonate, methane, acetate, leucine, glucose and Spirulina platensis biomass). After 468 days of anoxic incubation, only glucose and S. platensis resulted in label uptake in lipid moieties of 2G-GDGTs, indicating incorporation of carbon from these organic substrates. The hydrophobic moieties of 2G-GDGTs showed minimal label incorporation, with up to 4 per mil 13C enrichment detected in crenarchaeol-derived tricyclic biphytane from the S. platensis-supplemented slurries. The 2G-GDGT-derived glucose or glycerol moieties also showed 13C incorporation (Dd13C = 18 - 38 per mil) in the incubations with glucose or S. platensis, consistent with a lipid salvage mechanism utilized by marine benthic archaea to produce new 2G-GDGTs. The production rates were nevertheless rather slow, even when labile organic matter was supplied. The 2G-GDGT turnover times of 1700 - 20 500 years were much longer than those estimated for subseafloor microbial communities, implying that sedimentary 2G-GDGTs as biomarkers of benthic archaea are cumulative records of past and present generations.

(Table 1) Oxygen and carbon isotope ratios of benthic foraminifera of DSDP Holes 12-119 and 48-401

We present here oxygen and carbon isotopic records of Eocene to Oligocene benthic foraminifera from two Bay of Biscay Deep Sea Drilling Project (DSDP) sites (119 and 401). d18O of benthic foraminifera increases 1.9 per mil from a middle Eocene minimum (Zones P10-P11) to an earliest Oligocene maximum (Zone NP21). Approximately 1.4 per mil of the increase in benthic foraminiferal d18O occurs during the late Eocene to earliest Oligocene (Zones P15/16-NP21). Previous results from other North Atlantic DSDP sites (400A and 398) have significantly lower d18O values of benthic foraminifera, some by as much as 2 per mil (Vergnaud-Grazzini et al., 1978; 1989, doi:10.2973/dsdp.proc.48.119.1979; Vergnaud-Grazzini, 1979, doi:10.2973/dsdp.proc.47-2.117.1979 ). We believe that these differences result from diagenetic alteration of the sediments in the deeper-buried Sites 400A and 398.

Stable isotope ratios from foraminfera in Kara Sea sediments

Ostracods secrete their valve calcite within a few hours or days, therefore, its isotopic composition records ambient environmental conditions of only a short time span. Hydrographic changes between the calcification of individuals lead to a corresponding range (max.-min.) in the isotope values when measuring several (>=5) single valves from a specific sediment sample. Analyses of living (stained) ostracods from the Kara Sea sediment surface revealed high ranges of >2per mil of d18O and d13C at low absolute levels (d18O: <3per mil, d13C: <-3per mil) near the river estuaries of Ob and Yenisei and low ranges of not, vert, similar1per mil at higher absolute levels (d18O: 2-5.4per mil, d13C: -3 per mil to -1.5per mil) on the shelf and in submarine paleo-river channels. Comparison with a hydrographic data base and isotope measurements of bottom water samples shows that the average and the span of the ostracod-based isotope ranges closely mirror the long-term means and variabilities (standard deviation) of bottom water temperature and salinity. The bottom hydrography in the southern part of the Kara Sea shows strong response to the river discharge and its extreme seasonal and interannual variability. Less variable hydrographic conditions are indicative for deeper shelf areas to the north, but also for areas near the river estuaries along submarine paleo-river channels, which act as corridors for southward flowing cold and saline bottom water. Isotope analyses on up to five single ostracod valves per sample in the lower section (8-7 cal. ka BP) of a sediment core north of Yenisei estuary revealed d18O and d13C values which on average are lower by 0.6? in both, d18O and d13C, than in the upper core section (<5 cal. ka BP). The isotope shifts illustrate the decreasing influence of isotopically light river water at the bottom as a result of the southward retreat of the Yenisei river mouth from the coring site due to global sea level rise. However, the ranges (max.-min.) in the single-valve d18O and d13C data of the individual core samples are similar in the upper and in the lower core section, although a higher hydrographic variability is expected prior to 7 cal. ka BP due to river proximity. This lack of variability indicates the southward flow of cold, saline water along a submarine paleo-river channel, formerly existing at the core location. Despite shallowing of the site due to sediment filling of the channel and isostatic uplift of the area, the hydrographic variability at the core location remained low during the Late Holocene, because the shallowing proceeded synchronously with the retreat of the river mouth due to the global sea level rise

Stable carbon and oxygen isotope records of Cibicidoides wuellerstorfi in DSDP and ODP sites in the Atlantic and Pacific Ocean

Carbon isotopic records from benthic foraminifera are used to map patterns of deep ocean circulation between 3 and 2 million years ago, the interval when significant northern hemisphere glaciation began. The delta18O and delta13C data from four Atlantic sites (552, 607, 610, and 704) and one Pacific site (677) show that global cooling over this interval was associated with increased suppression of North Atlantic Deep Water (NADW) formation. However, the relative strength of NADW production was always greater than is observed during late Pleistocene glaciations when extreme decreases in NADW are observed in the deep North Atlantic. Our data indicate that an increase in the equator-to-pole temperature gradient associated with the onset of northern hemisphere glaciation did not intensify deepwater production in the North Atlantic but rather the opposite occurred. This is not unexpected as it is the "warm high-salinity" characteristic, rather than the "low temperature", of thermocline waters that is critical to the deepwater formation process in this region today.

Methane concentration and porewater acetate of sediment cores from the IODP Expedition 301 Site U1301

In deep subsurface sediments of the Juan de Fuca Ridge Flank, porewater acetate that is depleted in 13C relative to sedimentary organic matter indicates an acetogenic component to total acetate production. Thermodynamic calculations indicate common fermentation products or lignin monomers as potential substrates for acetogenesis. The classic autotrophic reaction may contribute as well, provided that dihydrogen (H2) concentrations are not drawn down to the thermodynamic thresholds of the energetically more favorable processes of sulfate reduction and methanogenesis. A high diversity of novel formyl tetrahydrofolate synthetase (fhs) genes throughout the upper half of the sediment column indicates the genetic potential for acetogenesis. Our results suggest that a substantial fraction of the acetate produced in marine sediment porewaters may derive from acetogenesis, in addition to the conventionally invoked sources fermentation and sulfate reduction.

Stable carbon and oxygen isotope record of foraminifera of IODP Site 303-1307

A major tipping point of Earth's history occurred during the mid-Pliocene: the onset of major Northern-Hemisphere Glaciation (NHG) and of pronounced, Quaternary-style cycles of glacial-to-interglacial climates, that contrast with more uniform climates over most of the preceding Cenozoic and continue until today (Zachos et al., 2001, doi:10.1126/science.1059412). The severe deterioration of climate occurred in three steps between 3.2 Ma (warm MIS K3) and 2.7 Ma (glacial MIS G6/4) (Lisiecki and Raymo, 2005, doi:10.1029/2004PA001071). Various models (sensu Driscoll and Haug, 1998, doi:10.1126/science.282.5388.436) and paleoceanographic records (intercalibrated using orbital age control) suggest clear linkages between the onset of NHG and the three steps in the final closure of the Central American Seaways (CAS), deduced from rising salinity differences between Caribbean and the East Pacific. Each closing event led to an enhanced North Atlantic meridional overturning circulation and this strengthened the poleward transport of salt and heat (warmings of +2-3°C) (Bartoli et al., 2005, doi:10.1016/j.epsl.2005.06.020). Also, the closing resulted in a slight rise in the poleward atmospheric moisture transport to northwestern Eurasia (Lunt et al., 2007, doi:10.1007/s00382-007-0265-6), which probably led to an enhanced precipitation and fluvial run-off, lower sea surface salinity (SSS), and an increased sea-ice cover in the Arctic Ocean, hence promoting albedo and the build-up of continental ice sheets. Most important, new evidence shows that the closing of the CAS led to greater steric height of the North Pacific and thus doubled the low-saline Arctic Throughflow from the Bering Strait to the East Greenland Current (EGC). Accordingly, Labrador Sea IODP Site 1307 displays an abrupt but irreversible EGC cooling of 6°C and freshening by ~2 psu from 3.25/3.16-3.00 Ma, right after the first but still reversible attempt of closing the CAS.

Stable isotope record of benthic and planktonic foraminifera in sediment cores of ODP Leg 177, Southern Ocean

While onboard ship during Leg 177, we used variations in sediment physical properties (mainly percent color reflectance) in conjunction with biomagnetostratigraphy to correlate among sites and predict the position of marine isotope stages (MISs) (e.g., see fig. F11 in Shipboard Scientific Party, 1999, p. 45). Our working assumption was that physical properties of Leg 177 sediments are controlled mainly by variations in carbonate content. Previous studies of Southern Ocean sediment cores have shown that carbonate concentrations are relatively high during interglacial stages and low during glacial stages at sites located within the Polar Frontal Zone (PFZ). Today, the PFZ marks a lithologic boundary in underlying sediment separating calcareous oozes to the north and silica-rich facies to the south (Hays et al., 1976). Although there is debate whether the position of the "physical" PFZ actually moved during glacial-interglacial cycles (Charles and Fairbanks, 1990; Matsumoto et al., 2001), the "biochemical" PFZ, as expressed by the CaCO3/opal boundary in sediments, certainly migrated north during glacials and south during interglacials. This gave rise to lithologic variations that are useful for stratigraphic correlation. At Leg 177 sites located north of the PFZ and at sublysoclinal depths, we expected the same pattern of carbonate variation because cores in the Atlantic basin are marked by increased carbonate dissolution during glacial periods and increased preservation during interglacials (Crowley, 1985).

Age models and stabile isotope ratios from SO35 cores

Stable isotope measurements on the planktonic foraminifer Globigerinoides ruber (white) have been carried out on a number of selected deep-seas sediment cores from the South Lau and Norlh Fiji Basins. The d18O-curves show good correlation with the inter-ocean oraphic correlation composite d18O-record of the standard reference section (Prell et al. 1986), which, in combination with the chronostratigraphic classifications of Herterich & Sarnthein (1984, modified) and Imbrie et al. 1984), allows a detailed dating of the sedimentary sequences. The deepest layers in core no. 119 (southern Lau Basin) could be assigned to Isotope Stage 24. Measurements made on bulk carbonate in two cores show a much higher glacial-interglacial amplitude, allowing the general identification of the conventional oxygen isotope stages. The d13C-values of the benthic foraminifer Cibicidoides wuellerstorfi show progressively lighter values northwards reflecting an increasing contribution of the isotopically lighter CO2 from the remineralisation of organic matter during the general northward movement of the deep water masses. Cyclicities in the sedimentation rates were observed in core nos. 117 and 119 (both southern Lau Basin) where the interglacials exhibit higher levels than the glacials. Calculated new or export paleoproductivity show that the glacials had higher productivity in the euphotic zone. From the oxygen isotope stratigraphy, the five ash layers in core nos. 117 and 119 could be dated as about 530 ka B.P. in Stage 14, 695 ka B.P. in Stage 18, 775 ka B.P. in Stage 21, 790 ka B.P. and 825 ka B.P. in Stage 22. Carbonate dissolution occurred during stages 5, 8 and 10 to 12.

Age determination and stable isotope record of foraminifera of sediment core SO82_5-2

Surface and deepwater paleoclimate records in Irminger Sea core SO82-5 (59°N, 31°W) and Icelandic Sea core PS2644 (68°N, 22°W) exhibit large fluctuations in thermohaline circulation (THC) from 60 to 18 calendar kyr B.P., with a dominant periodicity of 1460 years from 46 to 22 calendar kyr B.P., matching the Dansgaard-Oeschger (D-O) cycles in the Greenland Ice Sheet Project 2 (GISP2) temperature record [Grootes and Stuiver, 1997, doi:10.1029/97JC00880]. During interstadials, summer sea surface temperatures (SSTsu) in the Irminger Sea averaged to 8°C, and sea surface salinities (SSS) averaged to ~36.5, recording a strong Irminger Current and Atlantic THC. During stadials, SSTsu dropped to 2°-4°C, in phase with SSS drops by ~1-2. They reveal major meltwater injections along with the East Greenland Current, which turned off the North Atlantic deepwater convection and hence the heat advection to the north, in harmony with various ocean circulation and ice models. On the basis of the IRD composition, icebergs came from Iceland, east Greenland, and perhaps Svalbard and other northern ice sheets. However, the southward drifting icebergs were initially jammed in the Denmark Strait, reaching the Irminger Sea only with a lag of 155-195 years. We also conclude that the abrupt stadial terminations, the D-O warming events, were tied to iceberg melt via abundant seasonal sea ice and brine water formation in the meltwater-covered northwestern North Atlantic. In the 1/1460-year frequency band, benthic ?18O brine water spikes led the temperature maxima above Greenland and in the Irminger Sea by as little as 95 years. Thus abundant brine formation, which was induced by seasonal freezing of large parts of the northwestern Atlantic, may have finally entrained a current of warm surface water from the subtropics and thereby triggered the sudden reactivation of the THC. In summary, the internal dynamics of the east Greenland ice sheet may have formed the ultimate pacemaker of D-O cycles.