Concentrations and carbon isotopic compositions of organic and inorganic compounds in sediment porewaters at IODP Site U1329

Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, d13C values of acetate span a wide range from -46.0 per mill to -11.0 per mill vs. VPDB and change systematically with sediment depth. In contrast, d13C values of both the bulk dissolved organic carbon (DOC) (-21.6 ± 1.3 per mill vs. VPDB) and the low-molecular-weight compound lactate (-20.9 ± 1.8 per mill vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1 per mill depleted and up to 9.1 per mill enriched in 13C. Broadly, 13C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while 13C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO2-reduction can coexist with methanogenic CO2-reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron-accepting process. Further, the isotopic relationship suggests a relative increase in acetate flow to acetoclastic methanogenesis with depth although its contribution to total methanogenesis is probably small. Our study demonstrates how the stable carbon isotope biogeochemistry of acetate can be used to identify pathways of microbial carbon turnover in subsurface environments. Our observations also raise new questions regarding the factors controlling acetate turnover in marine sediments.

High-resolution marine record of sediment core MD99-2343 in the Balearic Sea

The IMAGES core MD99-2343, recovered from a sediment drift north of the island of Minorca, in the north-western Mediterranean Sea, holds a high-resolution sequence that is perfectly suited to study the oscillations of the overturning system of the Western Mediterranean Deep Water (WMDW). Detailed analysis of grain-size and bulk geochemical composition reveals the sensitivity of this region to climate changes at both orbital and centennial-millennial temporal scales during the last 50 kyr. The dominant orbital pattern in the K/Al record indicates that sediment supply to the basin was controlled by the insolation evolution at 40°N, which forced changes in the fluvial regime, with more efficient sediment transport during insolation maxima. This orbital control also modulated the long-term pattern of the WMDW intensity as illustrated by the silt/clay ratio. However, deep convection was particularly sensitive to climatic changes at shorter time-scales, i.e. to centennial-millennial glacial and Holocene oscillations that are well documented by all the paleocurrent intensity proxies (Si/Al, Ti/Al and silt/clay ratios). Benthic isotopic records (d13C and d18O) show a Dansgaard-Oeschger (D-O) pattern of variability of WMDW properties, which can be associated with changing intensities of the deep currents system. The most prominent reduction on the WMDW overturning was caused by the post-glacial sea level rise. Three main scenarios of WMDW overturning are revealed: a strong mode during D-O Stadials, a weak mode during D-O Interstadials and an intermediate mode during cooling transitions. In addition, D-O Stadials associated with Heinrich events (HEs) have a very distinct signature as the strong mode of circulation, typical for the other D-O Stadials, was never reached during HE due to the surface freshening induced by the inflowing polar waters. Consequently, the WMDW overturning system oscillated around the intermediate mode of circulation during HE. Though surface conditions were more stable during the Holocene, the WMDW overturning cell still reacted synchronously to short-lived events, as shown by increments in the planktonic d18O record, triggering quick reinforcements of the deep water circulation. Overall, these results highlight the sensitivity of the WMDW to rapid climate change which in the recent past were likely induced by oceanographic and atmospheric reorganizations in the North Atlantic region.

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.