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.

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.

Detailed analysis of the organic carbon content in sediment cores M0002 and M0004

During IODP Expedition 302 (Arctic Coring Expedition-ACEX), the first scientific drilling campaign in the permantly ice-covered central Arctic Ocean, a 430 m thick sequence of upper Cretaceaous to Quaternary sediments has been drilled. The lower half of this sequence is composed of organic-carbon-rich (black shale-type) sediments with total organic carbon contents of about 1-14%. Significant amounts of the organic matter preserved in these sediments is of algae-type origin and accumulated under anoxic/euxinic conditions. Here, for the first time detailed data on the source-rock potential of these black shales are presented, indicating that most of the Eocene sediments have a (fair to) good source-rock potential, prone to generate a gas/oil mixture. The source-rock potential of the Campanian and upper Paleocene sediments, on the other hand, is rather low. The presence of oil or gas already generated in situ, however, can be ruled out due to the immaturity of the ACEX sediments.

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.

Accumulation rates of bulk sediment and total organic carbon for Ontong Java Plateau sediments

Organic geochemical investigations were performed on sediments of Leg 130 to reconstruct the depositional environment of the Ontong Java Plateau. The Miocene to Quaternary sediments collected during the drilling campaign are characterized by extremely low organic carbon contents. As indicated by C/N ratios and Rock-Eval data, most of the organic matter is probably of marine origin. Based on mass-accumulation rates of organic carbon, the paleoproductivity for the Miocene-Pliocene and the late Pliocene-Pleistocene time intervals as well as the modern surface-water production were estimated. The productivity values of the surface sediments (25-59 gC/m2/yr) reflect the various influences of the equatorial upwelling cell on the different sites. The accumulation rates of organic carbon are generally low; however, they show a distinct increase at 8 Ma and a decrease at 2 Ma.

Carbon chemistry of ODP Leg 105 sites

The quantity and quality of organic carbon of Eocene to Holocene sediments from ODP Sites 645, 646, and 647 were investigated to reconstruct depositional environments. Results were based on organic-carbon and nitrogen determinations, Rock-Eval pyrolysis, and kerogen microscopy. The sediments at Site 645 in Baffin Bay are characterized by relatively high organic-carbon values, most of which range from 0.5% to almost 3%, with maximum values in the middle Miocene. Distinct maxima of organic-carbon accumulation rates occur between 18 and 12.5 Ma and between 3.4 and 0 Ma. At Sites 646 and 647 in the Labrador Sea, organic-carbon contents vary between 0.1% and 0.75%. Cyclic 'Milankovitch-type' changes in organic-carbon deposition imply climate-controlled mechanisms that cause these fluctuations. The composition of organic matter at Site 645 is dominated by terrigenous components throughout the entire sediment sequence. An increased content of marine organic carbon was recorded only in the late-middle Miocene. At Sites 646 and 647, the origin of the organic matter most probably is marine. Oceanic paleoproductivity values were estimated, based on the amount of marine organic carbon. During most of the Neogene time interval at Site 645, productivity was low, i.e., similar or less than that measured in Baffin Bay today. Higher values of up to 150 (200) gC/m**2/y may have occurred only in the Miocene. At Sites 646 and 647, mean paleoproductivity values vary between 90 and 170 gC/m**2/y; i.e., these are also similar to those measured in the Labrador Sea today. Lower values of 40 to 70 gC/m**2/y were estimated for the early Eocene and (middle) Miocene.

Radiocarbon dating, sedimentation rate, granulometry and organic carbon content of ODP Leg 182 sites

This data report presents sedimentological (grain size) and geochemical (X-ray diffraction, total organic carbon, accelerator mass spectrometry radiocarbon, and percent carbonate) information obtained from the western transect (Sites 1132, 1130, and 1134) and the eastern transect (Sites 1129, 1131, and 1127) in the Great Australian Bight during Leg 182. The purpose is to quantify changing rates of sediment accumulation and changes in sediment type from the late Pleistocene and Holocene, in order to relate these changes to the well-known sea level curve that exists for this time frame. Ultimately, these data can be used to more effectively interpret lithologic variations deeper in the Pleistocene succession, which most likely represent orbitally forced sea level events.

Carbon and Nitrogen concentrations and isotopic composition of ODP Site 170-1040 and Leg 205 sites

We determined the C and N concentrations and isotopic compositions of sediments in the prism sampled during Ocean Drilling Program Legs 170 and 205 offshore Costa Rica, with the goals of evaluating sediment sources and extents of diagenesis and identifying any effects of infiltrating fluids on the sedimentary C and N. The sediments from Leg 170 Site 1040 contain 0.85-1.96 wt% total organic carbon (TOC) with Vienna Peedee belemnite (VPDB) d13CVPDB from -26.3 per mil to -22.5 per mil, and 832-2221 ppm total nitrogen (TN) with d15Nair from +3.5 per mil to +6.6 per mil. Sediment TN concentrations and d15N values show dramatic downhole increases within the uppermost 130 m of the section and more gradual downhole decreases from 130 meters below seafloor (mbsf) to the base of the décollement at ~370 mbsf. Concentrations and isotopic compositions of TOC are relatively uniform within the entire section, showing some minor perturbation within the décollement zone. In the uppermost 100 m, upsection increases in TN concentrations at constant TOC concentrations produce significant increases in atomic TOC/TN ratios from ~8 to ~18. Carbonate (calcite) contents in the wedge sediments are generally low (<4 wt%), but the d13C and Vienna standard mean ocean water (VSMOW) d18OVSMOW values vary significantly from -26.1 per mil to +4.1 per mil and from +30.0 per mil to +35.3 per mil, respectively. Concentrations and isotopic compositions of TOC and TN for sediments from Leg 205 Sites 1254 and 1255 overlap well with C-N data for sediments from the same depth intervals obtained during Leg 170 at Site 1040.

Low-molecular-weight hydrocarbons in sediments at DSDP Sites 89-585 and 89-586

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 38 shipboard sealed, deep-frozen core samples of Deep Sea Drilling Project Sites 585 (East Mariana Basin) and 586 (Ontong-Java Plateau) were determined by a gas stripping-thermovaporization method. Total concentrations, which represent the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediment, vary from 20 to 630 ng/g of rock at Site 585 (sub-bottom depth range 332-868 m). Likewise, organic-carbon normalized yields range from 3*10**4 to 9*10**5 ng/g Corg, indicating that the organic matter is still in the initial, diagenetic evolutionary stage. The highest value (based on both rock weight and organic carbon) is measured in an extremely organic-carbon-poor sample of Lithologic Subunit VB (Core 585-30). In this unit (504-550 m) several samples with elevated organic-carbon contents and favorable kerogen quality including two thin "black-shale" layers deposited at the Cenomanian/Turonian boundary (not sampled for this study) were encountered. We conclude from a detailed comparison of light hydrocarbon compositions that the Core 585-30 sample is enriched in hydrocarbons of the C2-C8 molecular range, particularly in gas compounds, which probably migrated from nearby black-shale source layers. C2-C8 hydrocarbon yields in Site 586 samples (sub-bottom depth range 27-298 m) did not exceed 118 ng/g of dry sediment weight (average 56 ng/g), indicating the immaturity of these samples.

Distribution of organic carbon in surface sediments covered during SONNE cruise SO184

Sediments were sampled and oxygen profiles of the water column were determined in the Indian Ocean off west and south Indonesia in order to obtain information on the production, transformation, and accumulation of organic matter (OM). The stable carbon isotope composition (d13Corg) in combination with C/N ratios depicts the almost exclusively marine origin of sedimentary organic matter in the entire study area. Maximum concentrations of organic carbon (Corg) and nitrogen (N) of 3.0% and 0.31%, respectively, were observed in the northern Mentawai Basin and in the Savu and Lombok basins. Minimum d15N values of 3.7 per mil were measured in the northern Mentawai Basin, whereas they varied around 5.4 per mil at stations outside this region. Minimum bottom water oxygen concentrations of 1.1 mL L**1, corresponding to an oxygen saturation of 16.1%, indicate reduced ventilation of bottom water in the northern Mentawai Basin. This low bottom water oxygen reduces organic matter decomposition, which is demonstrated by the almost unaltered isotopic composition of nitrogen during early diagenesis. Maximum Corg accumulation rates (CARs) were measured in the Lombok (10.4 g C m**-2 yr**-1) and northern Mentawai basins (5.2 g C m**-2 yr**-1). Upwelling-induced high productivity is responsible for the high CAR off East Java, Lombok, and Savu Basins, while a better OM preservation caused by reduced ventilation contributes to the high CAR observed in the northern Mentawai Basin. The interplay between primary production, remineralisation, and organic carbon burial determines the regional heterogeneity. CAR in the Indian Ocean upwelling region off Indonesia is lower than in the Peru and Chile upwellings, but in the same order of magnitude as in the Arabian Sea, the Benguela, and Gulf of California upwellings, and corresponds to 0.1-7.1% of the global ocean carbon burial. This demonstrates the relevance of the Indian Ocean margin off Indonesia for the global OM burial.

Carbon and oxygen stable isotope composition of bulk sediment and abundance of Braarudospahaera in ODP Site 122-762 (Table 1)

Nannofossil assemblages enriched in Braarudosphaera occur in lower Oligocene to lower Miocene sediments at Ocean Drilling Program Sites 762 and 763 on the central Exmouth Plateau. Braarudosphaerids appear here rather abruptly in the lower Oligocene (in Zone NP21). They reach their greatest numbers in the lower Oligocene (in Zones NP22 and NP23), where they comprise up to 10% of some samples. Braarudosphaera bigelowii is the overwhelmingly dominant species, occurring together with rare specimens of B. discula and Micrantholithus pinguis. The holococcoliths Peritrachelina joidesa and Lantemithus minutus are also associated with the Braarudosphaera enrichment. There are two populations of B. bigelowii: one of normal size (10-14 µm) and one of large specimens (20-22 µm). The larger braarudosphaerids are more common than the smaller forms. Braarudosphaera-rich sediments are absent at Wombat Plateau sites during the same time interval. We attribute this to latitudinal control, because the Wombat sites are about 4° north of the central Exmouth Plateau sites. We believe that the occurrence of braarudosphaerids is related to an Oligocene to early Miocene oceanographic event on the Exmouth Plateau. We suspect that mid-ocean up welling of cool, low-salinity, nutrient-rich water along a divergent zone created the Braarudosphaera-nch sediments in the South Atlantic and Indian oceans.

Stable oxygen and carbon isotope ratios of Pliocene benthic foraminifera in the Atlantic Ocean

Large changes in benthic foraminiferal delta180 and delta13C occurred during the Pliocene (between 3.0 and 2.0 Ma) at Hole 665A. Oxygen isotopic compositions increased to maximum values at 2.4 Ma, correlating with an 18O enrichment observed at Hole 552A and other locations (Shackleton et al., 1984). As at Hole 606 (Keigwin, 1986), however, maximum delta180 values at 2.4 Ma were not as great as at Hole 552A, and enrichments in delta180 also occurred before 2.4 Ma. We believe that the section representing sediments from 2.5 to 2.7 or 2.8 Ma is missing at Hole 552A because of incomplete core recovery. Consequently, the older delta180 increases are not found at Hole 552A. Benthic foraminiferal delta13C values are much lower at Hole 665A than at Hole 552A, approaching the low values observed in the Pliocene Pacific Ocean. This geographic distribution of delta13C suggests that, like late Quaternary glaciations, the equatorial Atlantic Ocean was dominated during the Pliocene by deep water that originated in the Southern Ocean and had chemical characteristics very similar to the Pacific Ocean. Reduced O2 values were probably associated with low delta13C values and contributed to increased preservation of organic carbon during enriched 180 intervals of the Pliocene equatorial Atlantic.

Total organic carbon content and isorenieratene concentrations from three holes of ODP Leg 160

Carotenoids were analysed in ca. 1-cm thick subsamples of three laterally time-equivalent sapropels from a west-east transect of the eastern Mediterranean Basin to study euxinic periods during Pliocene sapropel formation. The amount of intact isorenieratene (summed all-trans and cis isomers), ranged from non-detectable at the base and top of a sapropel up to 140 µg/g sediment in the central parts. Isorenieratene accumulation rates at the central and western site are remarkably similar and increase sharply to levels of up to 3.0 mg/m**2/ yr in the central part of the sapropel and then drop to low levels. This pattern indicates an expansion of euxinic conditions reaching into the photic zone, followed by deepening of the chemocline during deposition of this Pliocene sapropel. The sapropel from the easternmost site of the basin, which contains less organic carbon, shows much lower isorenieratene accumulation rates and even absence of isorenieratene in the central part of the sapropel. Ba/Al ratios indicate enhanced palaeoproductivity during sapropel formation, supporting previously proposed models, according to which increased productivity is the driving force for the generation of euxinic conditions.

Deep thermohaline Circulation in the low-latitude Atlantic during the Last Glacial

Present-day low-latitude eastern and western Atlantic basins are geochemically distinct below the sill depth of the Mid-Atlantic Ridge. While Antarctic Bottom Water (AABW) circulates freely in the western Atlantic, flow into the eastern Atlantic is restricted below 4 km which results in filling the abyssal depths of this basin with water of geochemical similarity to nutrient depleted North Atlantic Deep Water. Using carbon isotopes and Cd/Ca ratios in benthic foraminifera we reconstruct the geochemistry of these basins during the last glacial maximum. Results indicate that deep eastern and western Atlantic basins became geochemically identical during the last glacial. This was achieved by shoaling of the upper surface of AABW above the sill depth of the Mid-Atlantic Ridge, which allowed bottom waters in both basins to be filled with the same water mass. Although AABW became the dominant water mass in the deep eastern Atlantic basin during the glacial, Holocene-glacial delta13C-PO4 shifts in this basin are in Redfield proportions, unlike the disproportionate Holocene-glacial delta13C-PO4 shifts observed in the Southern Ocean. By examining the composition of deep and intermediate waters throughout the Atlantic, we show that this effect was induced by a change in gradient of the delta13C-PO4 deepwater mixing line during glacial times. Evidence from high-latitude planktonic data suggests that the change in gradient of the deepwater mixing line was brought about through a significant reduction in the thermodynamic effect on Southern Ocean surface waters. By using coupled delta13C-PO4 data to constrain the composition of end member water masses in the glacial Atlantic, we conclude that deep waters in the low-latitude glacial Atlantic were composed of a mixture of northern and southern source waters in a ratio of 1:3.

Isotopic composition of oxygen, carbon, and sulfur in interstitial water and cores at DSDP Leg 59 Holes

Comprehensive isotopic studies based on data from the Deep Sea Drilling Project have elucidated numerous details of the low- and high-temperature mechanisms of interaction between water and rocks of ocean crustal seismic Layers 1 and 2. These isotopic studies have also identified climatic changes during the Meso-Cenozoic history of oceans. Data on the abundance and isotopic composition of sulfur in the sedimentary layer as well as in rocks of the volcanic basement are more fragmentary than are oxygen and carbon data. In this chapter we specifically concentrate upon isotopic data related to specific features of the mechanisms of low-temperature interaction of water with sedimentary and volcanogenic rocks. The Leg 59 data provide a good opportunity for such lithologic and isotopic studies, because almost 600 meters of basalt flows and sills interbedded with tuffs and volcaniclastic breccias were cored during the drilling of Hole 448A. Moreover, rocks supposedly exposed to hydrothermal alteration play an important role at the deepest horizons of that mass. Sulfur isotopic studies of the character of possible biogenic processes of sulfate reduction in sediments are another focus, as well as the nature and origin of sulfide mineralization in Layer-2 rocks of remnant island arcs. Finally, oxygen and carbon istopic analyses of biogenic carbonates in the cores also enabled us to investigate the effects of changing climatic conditions during the Cenozoic. These results are compared with previous data from adjacent regions of the Pacific Ocean. Thus this chapter describes results of isotopic analyses of: oxygen and sulfur of interstitial water; oxygen and carbon of sedimentary carbonates and of calcite intercalations and inclusions in tuffs and volcaniclastic breccias interbedded with basalt flows; and sulfur of sulfides in these rocks.