Carbon isotopic composition of dissolved CO2, CO2 gas and methane in sediments from ODP Leg 172 sites

Carbon isotopic data of interstitial dissolved CO2 (CO2), CO2 gas, and methane show that a variety of microbial diagenetic processes produce the observed isotopic trends. Anaerobic methane oxidation (AMO) is an important process near the sulfate-methane interface (SMI) that strongly influences the isotopic composition of CO2 in the sulfate reduction and upper methanogenic zones, which in turn impacts methane isotopic composition. Dissolved CO2 and methane are maximally depleted in 13C near the SMI, where 13C values are as light as -31.8 and -101 PDB for CO2 and methane, respectively. CO2 reduction links the CO2 and methane pools in the methanogenic zone so that the carbon isotopic composition of both pools evolves in concert, generally showing increasing enrichments of 13C with increasing depth. These isotopic trends mirror those within other methane-rich continental rise sediments worldwide.

Hydrogen, carbon, and oxygen isotope ratios of interstitial fluides of ODP Leg 104 holes

Carbon, hydrogen, and oxygen isotope ratios determined on 32 squeezed interstitial fluid samples show remarkable variations with depth. For the most part these variations are related to diagenetic and alteration reactions taking place in the sediments, and in the underlying basalts. delta13C SumCO2 depth distributions at Sites 642 and 643 are the result of mixing of original SumCO2 of the paleo bottom water with SumCO2 released by remineralization of organic matter. At Site 644, where sulfate exhaustion occurs, the processes of methanogenesis by CO2 reduction and anaerobic methanotrophy strongly influence the delta13C SumCO2 distribution. Hydrogen and oxygen isotopes roughly covary, and become enriched in 16O and1H with depth. This effect is most pronounced at Sites 642 and 643, possibly due to the influence of the directly underlying basalts. Isotope depletions at Site 644 are much lower, corresponding to the greater sediment depth to basement. The alternative, that the O, H isotope shifts are due primarily to autochthonous diagenetic and exchange reactions, is not supported by the data available.

IODP Expedition 337, Shimokita Deep Coalbed Biosphere

Microbial life inhabits deeply buried marine sediments, but the extent of this vast ecosystem remains poorly constrained. Here we provide evidence for the existence of microbial communities in ~40° to 60°C sediment associated with lignite coal beds at ~1.5 to 2.5 km below the seafloor in the Pacific Ocean off Japan. Microbial methanogenesis was indicated by the isotopic compositions of methane and carbon dioxide, biomarkers, cultivation data, and gas compositions. Concentrations of indigenous microbial cells below 1.5 km ranged from <10 to ~10**4 cells cm**-3. Peak concentrations occurred in lignite layers, where communities differed markedly from shallower subseafloor communities and instead resembled organotrophic communities in forest soils. This suggests that terrigenous sediments retain indigenous community members tens of millions of years after burial in the seabed.

Abundance of mesozooplankton in the Mediterranean Sea during PELMED 1995 and PELMED 1996

The PELMED-ECOPEL dataset contains mesozooplankton data collected in 1995-1996 in the Gulf of Lion (North Western Mediterranean Sea) between 43°35' N, 2°50' E and 42°15' N, 6°15' E. Zooplankton taxonomy-related abundance per unit volume of the water column.

Isotopic composition of ground ice, ebullition gases and thermokarst lake water, North America

Thermokarst lakes are thought to have been an important source of methane (CH4) during the last deglaciation when atmospheric CH4 concentrations increased rapidly. Here we demonstrate that meltwater from permafrost ice serves as an H source to CH4 production in thermokarst lakes, allowing for region-specific reconstructions of dD-CH4 emissions from Siberian and North American lakes. dD CH4 reflects regionally varying dD values of precipitation incorporated into ground ice at the time of its formation. Late Pleistocene-aged permafrost ground ice was the dominant H source to CH4 production in primary thermokarst lakes, whereas Holocene-aged permafrost ground ice contributed H to CH4 production in later generation lakes. We found that Alaskan thermokarst lake dD-CH4 was higher (-334 ± 17 per mil) than Siberian lake dD-CH4 (-381 ± 18 per mil). Weighted mean dD CH4 values for Beringian lakes ranged from -385 per mil to -382 per mil over the deglacial period. Bottom-up estimates suggest that Beringian thermokarst lakes contributed 15 ± 4 Tg CH4 /yr to the atmosphere during the Younger Dryas and 25 ± 5 Tg CH4 /yr during the Preboreal period. These estimates are supported by independent, top-down isotope mass balance calculations based on ice core dD-CH4 and d13C-CH4 records. Both approaches suggest that thermokarst lakes and boreal wetlands together were important sources of deglacial CH4.

Southern Ocean CO2 uptake and buffer factor from model run 2012-2100, with links to model results

The Southern Ocean is a key region for global carbon uptake and is characterised by a strong seasonality with the annual CO2 uptake being mediated by biological carbon draw-down in summer. Here, we show that the contribution of biology to CO2 uptake will become even more important until 2100. This is the case even if biological production remains unaltered and can be explained by the decreasing buffer capacity of the ocean as its carbon content increases. The same amount of biological carbon draw-down leads to a more than twice as large reduction in CO2 (aq) concentration and hence to a larger CO2 gradient between ocean and atmosphere that drives the gas-exchange. While the winter uptake south of 44°S changes little, the summer uptake increases largely and is responsible for the annual mean response. The combination of decreasing buffer capacity and strong seasonality of biological carbon draw-down introduces a strong and increasing seasonality in the anthropogenic carbon uptake.

Geochemistry of abyssal peridotites from ODP Hole 209-1274A

Aqueous dihydrogen (H2,aq) is produced in copious amounts when seawater interacts with peridotite and H2O oxidizes ferrous iron in olivine to ferric iron in secondary magnetite and serpentine. Poorly understood in this process is the partitioning of iron and its oxidation state in serpentine, although both impose an important control on dihydrogen production. We present results of detailed petrographic, mineral chemical, magnetic and Mößbauer analyses of partially to fully serpentinized peridotites from the Ocean Drilling Program (ODP) Leg 209, Mid-Atlantic Ridge (MAR) 15°N area. These results are used to constrain the fate of iron during serpentinization and are compared with phase equilibria considerations and peridotite-seawater reaction path models. In samples from Hole 1274A, mesh-rims reveal a distinct in-to-out zoning from brucite at the interface with primary olivine, followed by a zone of serpentine + brucite ± magnetite and finally serpentine + magnetite in the outermost mesh-rim. The compositions of coexisting serpentine (Mg# 95) and brucite (Mg# 80) vary little throughout the core. About 30-50% of the iron in serpentine/brucite mesh-rims is trivalent, irrespective of subbasement depth and protolith (harzburgite versus dunite). Model calculations suggest that both partitioning and oxidation state of iron are very sensitive to temperature and water-to-rock ratio during serpentinization. At temperatures above 330 °C the dissolution of olivine and coeval formation of serpentine, magnetite and dihydrogen depends on the availability of an external silica source. At these temperatures the extent of olivine serpentinization is insufficient to produce much hydrogen, hence conditions are not reducing enough to form awaruite. At T < 330 °C, hydrogen generation is facilitated by the formation of brucite, as dissolution of olivine to form serpentine, magnetite and brucite requires no addition of silica. The model calculations suggest that the iron distribution observed in serpentine and brucite is consistent with formation temperatures ranging from <150 to 250 °C and bulk water-to-rock ratios between 0.1 and 5. These conditions coincide with peak hydrogen fugacities during serpentinization and are conducive to awaruite formation during main stage serpentinization. The development of the common brucite rims around olivine is either due to an arrested reaction olivine -> brucite -> serpentine + brucite, or reflects metastable olivine-brucite equilibria developing in the strong gradient in silica activity between orthopyroxene (talc-serpentine) and olivine (serpentine-brucite).

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.

(Table 2) Abundance and biomass of zooplankton in the eastern Black Sea in the beginning of September 1996

On the basis of analyses of samples collected in the eastern Black Sea in September 1996 trends of increase in surface zooplankton biomass and general decrease in Mnemiopsis biomass were revealed.

isotopic composition of gases and interstitial fluides of ODP Site 104-644

Pleistocene- to middle Miocene-age sediment was drilled at Site 341 (67? 20.1'N, 6? 06.6'E) on the inner Voring Plateau during Leg 38 of the Deep Sea Drilling Project (DSDP). In 1985, the Ocean Drilling Program (ODP) returned to the inner Wring Plateau near Site 341 and drilled a new hole at Site 644 (66° 40.7'N, 4° 34.6'E) as part of a transect to study Norwegian Sea paleoenvironments. In Hole 341, gas expansion pockets formed in cores which were recovered from depths below 50 m. This gas was characterized as predominantly methane with delta13C values in the range of -87 to -77 per mil (Morris, 1976, doi:10.2973/dsdp.proc.38.124.1976). At Site 644, sediment gas and pore-water samples were obtained to study the geochemistry of methanogenesis. Of particular interest is the possibility that methane hydrate might be present in these sediments.

(Table 2) Abundance and biomass of zooplankton in the eastern Black Sea in the beginning of September 1996

On the basis of analyses of samples collected in the eastern Black Sea in September 1996 trends of increase in surface zooplankton biomass and general decrease in Mnemiopsis biomass were revealed.