Isotope composition of dolomite, calcite and pore-waters of ODP Leg 210 samples

Early diagenetic dolomite beds were sampled during the Ocean Drilling Programme (ODP) Leg 201 at four reoccupied ODP Leg 112 sites on the Peru continental margin (Sites 1227/684, 1228/680, 1229/681 and 1230/685) and analysed for petrography, mineralogy, d13C, d18O and 87Sr/86Sr values. The results are compared with the chemistry, and d13C and 87Sr/86Sr values of the associated porewater. Petrographic relationships indicate that dolomite forms as a primary precipitate in porous diatom ooze and siliciclastic sediment and is not replacing the small amounts of precursor carbonate. Dolomite precipitation often pre-dates the formation of framboidal pyrite. Most dolomite layers show 87Sr/86Sr-ratios similar to the composition of Quaternary seawater and do not indicate a contribution from the hypersaline brine, which is present at a greater burial depth. Also, the d13C values of the dolomite are not in equilibrium with the d13C values of the dissolved inorganic carbon in the associated modern porewater. Both petrography and 87Sr/86Sr ratios suggest a shallow depth of dolomite formation in the uppermost sediment (<30 m below the seafloor). A significant depletion in the dissolved Mg and Ca in the porewater constrains the present site of dolomite precipitation, which co-occurs with a sharp increase in alkalinity and microbial cell concentration at the sulphate-methane interface. It has been hypothesized that microbial 'hot-spots', such as the sulphate-methane interface, may act as focused sites of dolomite precipitation. Varying d13C values from -15 per mil to +15 per mil for the dolomite are consistent with precipitation at a dynamic sulphate-methane interface, where d13C of the dissolved inorganic carbon would likewise be variable. A dynamic deep biosphere with upward and downward migration of the sulphate-methane interface can be simulated using a simple numerical diffusion model for sulphate concentration in a sedimentary sequence with variable input of organic matter. Thus, the study of dolomite layers in ancient organic carbon-rich sedimentary sequences can provide a useful window into the palaeo-dynamics of the deep biosphere.

Inorganic carbon and geochemistry measurements from landfast sea ice in Resolute Passage, Nunavut, Canada, as part of the Arctic-ICE project, May - June 2010

We conducted a six-week investigation of the sea ice inorganic carbon system during the winter-spring transition in the Canadian Arctic Archipelago. Samples for the determination of sea ice geochemistry were collected in conjunction with physical and biological parameters as part of the 2010 Arctic-ICE (Arctic - Ice-Covered Ecosystem in a Rapidly Changing Environment) program, a sea ice-based process study in Resolute Passage, Nunavut. The goal of Arctic-ICE was to determine the physical-biological processes controlling the timing of primary production in Arctic landfast sea ice and to better understand the influence of these processes on the drawdown and release of climatically active gases. The field study was conducted from 1 May to 21 June, 2010.

First results of SONNE cruise SO121

The Red Sea is a very young ocean, and is one of the most interesting areas on Earth (ocean in statu nascendi). It is the only ocean where hydrothermal activity associated with ore formation occurs in a sterile environment (anoxic, hot, saline). In addition, its geographical position means that it is predestined to record the monsoonal history of the region in detailed sedimentary sequences. The major aim of the present project is to investigate the dynamics of hydrothermal systems in selected Deeps (Atlantis-II, Discovery, Kebrit, Al Wajh), Additional palaeoceanographic and microbiological questions should also be addressed. Specific aims are: 1. To study the hydrographic changes in individual Deeps (hydrothermal region Atlantis-II) and to investigate the causes of the temperature increase in the last few years (increased heat flow - higher temperature of the brine supply - higher brine flow rates?). 2.a. To document the influence of the hydrothermal systems on the sedimentary organic matter in the Deeps. In particular, the thermogenic production and migration of hydrocarbons in the sediments will be studied. The complex formation mechanisms (bacterial, thermogenic) of short-chain hydrocarbons (trace gases) will also be examined, 2.b. in addition, the polar and macromolecular fraction in samples from the various deeps will be studied in order to elucidate the formation, structure and source of the macromolecular oil fraction. 3. To clarify the palaeoceanographic conditions, sea-level changes and the climatic history (relationship of the circulation system and nutrient supply to the monsoon) of the southern Red Sea. 4. To separate microorganisms from the brines and to characterise them in terms of their metabolic physiology and ecology, and to describe their taxonomy.

Mean snow accumulation rate, and mean methane sulfonate, chloride and nitrate concentration in snow pits and firn cores of Dronning Maud Land

We quantified postdepositional losses of methane sulfonate (MSA-), nitrate, and chloride at the European Project for Ice Coring in Antarctica (EPICA) drilling site in Dronning Maud Land (DML) (75°S, 0°E). Analyses of four intermediate deep firn cores and 13 snow pits were considered. We found that about 26 ± 13% of the once deposited nitrate and typically 51 ± 20% of MSA- were lost, while for chloride, no significant depletion could be observed in firn older than one year. Assuming a first order exponential decay rate, the characteristic e-folding time for MSA- is 6.4 ± 3 years and 19 ± 6 years for nitrate. It turns out that for nitrate and MSA- the typical mean concentrations representative for the last 100 years were reached after 5.4 and 6.5 years, respectively, indicating that beneath a depth of around 1.2-1.4 m postdepositional losses can be neglected. In the area of investigation, only MSA- concentrations and postdepositional losses showed a distinct dependence on snow accumulation rate. Consequently, MSA- concentrations archived at this site should be significantly dependent on the variability of annual snow accumulation, and we recommend a corresponding correction. With a simple approach, we estimated the partial pressure of the free acids MSA, HNO3, and HCl on the basis of Henry's law assuming that ionic impurities of the bulk ice matrix are localized in a quasi-brine layer (QBL). In contrast to measurements, this approach predicts a nearly complete loss of MSA-, NO3 - , and Cl-.

Table 1 Microorganisms, identified with DOGE analysis. 16S rDNA sequences, obtained from sequencing of DOGE bands, were assigned to the corresponding microorganisms

Microorganisms play an important role in the transformation of material within the earth's crust. The storage of CO2 could affect the composition of inorganic and organic components in the reservoir, consequently influencing microbial activities. To study the microbial induced processes together with geochemical, petrophysical and mineralogical changes, occurring during CO2 storage, long-term laboratory experiments under simulated reservoir P-T conditions were carried out. Clean inner core sections, obtained from the reservoir region at the CO2 storage site in Ketzin (Germany) from a depth of about 650 m, were incubated in high pressure vessels together with sterile synthetic formation brine under in situ P-T conditions of 5.5 MPa and 40°C. A 16S rDNA based fingerprinting method was used to identify the dominant species in DNA extracts of pristine sandstone samples. Members of the alpha- and beta-subdivisions of Proteobacteria and the Actinobacteria were identified. So far sequences belonging to facultative anaerobic, chemoheterotrophic bacteria (Burkholderia fungorum, Agrobacterium tumefaciens) gaining their energy from the oxidation of organic molecules and a genus also capable of chemolithoautotrophic growth (Hydrogenophaga) was identified. During CO2 incubation minor changes in the microbial community composition were observed. The majority of microbes were able to adapt to the changed conditions. During CO2 exposure increased concentrations of Ca**2+, K**+, Mg**2+ and SO4**2- were observed. Partially, concentration rises are (i) due to equilibration between rock pore water and synthetic brine, and (ii) between rock and brine, and are thus independent on CO2 exposure. However, observed concentrations of Ca**2+, K**+, Mg**2+ are even higher than in the original reservoir fluid and therefore indicate mineral dissolution due to CO2 exposure.

(Table T2) Sulfur isotopes of pore water from ODP Leg 201 sites

Fifty-seven interstitial water samples from six sites (Ocean Drilling Program Sites 1225-1229 and 1231) in the eastern equatorial Pacific Ocean and the Peru margin were analyzed for the stable sulfur isotopic composition (34S/32S) of dissolved sulfate along with major and minor ions. With the exception of Site 1231, sulfate from the interstitial fluids (d34S values as much as 89 per mil vs. the SF6-based Vienna-Canyon Diablo troilite standard) is found at depth to be enriched in 34S with respect to modern seawater sulfate (d34S = ~21 per mil), indicating that microbial sulfate reduction (MSR) took place to different extents at all investigated sites. Deeper sediments at Sites 1228 and 1229 are additionally influenced by diffusion of a sulfate-rich brine that has already undergone sulfate reduction. The intensity of MSR depends on the availability of substrate (organic matter), sedimentation conditions, and the active bacterial community structure. Formation of isotopically heavy diagenetic barite at the sulfate-methane transition zone is expected at Sites 1227 (one front), 1229 (two fronts), and probably Site 1228. At Site 1231, the constant sulfur isotopic composition of sulfate and concentrations of minor pore water ions indicate that suboxic (essentially iron and manganese oxide based) diagenesis dominates and no net MSR occurs.

Chemical and strontium isotopic compositions of interstitial waters from sediments of ODP Site 135-841

The depth variations in the major chemical components dissolved in interstitial waters from the Tonga margin (ODP Site 841) are much more pronounced than those usually observed in deep-sea sediments. The extensive alteration of volcanic Miocene sediments to secondary minerals such as analcime, clays, and thaumasite forms a CaCl2-rich brine. The brine results from a high exchange of Ca to Na, K, and Mg and an increase in Cl concentrations due to removal of H2O from the fluid during the authigenesis of hydrous minerals. The formation of thaumasite could have partly controlled the concentration of dissolved SO4, HCO3, and Ca in the Miocene sediments. The strontium isotopic signature of the interstitial water suggests that alteration of the volcanic Miocene sediments occurred a long time after sedimentation. A transient diffusion model indicates that molecular diffusion was not prevented by lithologic barriers and that the formation of secondary minerals in the Miocene sediment occurred over a short period of time (e.g.,

Stable oxygen isotope record of epibenthic foraminifera and water samples of the Arctic Ocean

We determined d18OCib values of live (Rose Bengal stained) and dead epibenthic foraminifera Cibicidoides wuellerstorfi, Cibicides lobatulus, and Cibicides refulgens in surface sediment samples from the Arctic Ocean and the Greenland, Iceland, and Norwegian seas (Nordic Sea). This is the first time that a comprehensive d18OCib data set is generated and compiled from the Arctic Ocean. For comparison, we defined Atlantic Water (AW), upper Arctic Bottom Water (uABW), and Arctic Bottom Water (ABW) by their temperature/salinity characteristics and calculated mean equilibrium calcite d18Oequ from summer sea-water d18Ow and in situ temperatures. As a result, in the Arctic environment we compensate for Cibicidoides- and Cibicides-specific offsets from equilibrium calcite of -0.35 and -0.55 per mil, respectively. After this taxon-specific adjustment, mean d18OCib values plausibly reflect the density stratification of principle water masses in the Nordic Sea and Arctic Ocean. In addition, mean d18OCib from AW not only significantly differs from mean d18OCib from ABW, but also d18OCib from within AW differentiates in function of provenience and water mass age. Furthermore, in shallow waters brine-derived low d18Ow can significantly lower the d18OCib of Cibicides spp. and thus d18OCib may serve as a paleobrine indicator. There is no statistically significant difference, however, between deeper water masses mean d18OCib of the Nordic Sea, and of the Eurasian and Amerasian basins, and no influence of low-d18Ow brines is recorded in Recent uABW and ABW d18OCib of C. wuellerstorfi. This may be due to dilution of a low-d18Ow brine signal in the deep sea, and/or to preferential incorporation of relatively high-d18Ow brines from high-salinity shelves. Although our data encompass environments with seasonal sea-ice and brine formation supposed to ultimately ventilate the deep Arctic Ocean, d18OCib from uABW and ABW do not indicate negative excursions. This may challenge hypotheses that call for enhanced Arctic brine release to explain negative benthic d18O spikes in deep-sea sediments from the late Pleistocene North Atlantic Ocean.

(Table 1) Sea ice and snow characteristics and heat fluxes observed during R/V Aurora Australis cruise to East Antarctica in September/October 2007

The properties of snow on East Antarctic sea ice off Wilkes Land were examined during the Sea Ice Physics and Ecosystem Experiment (SIPEX) in late winter of 2007, focusing on the interaction with sea ice. This observation includes 11 transect lines for the measurement of ice thickness, freeboard, and snow depth, 50 snow pits on 13 ice floes, and diurnal variation of surface heat flux on three ice floes. The detailed profiling of topography along the transects and the d18O, salinity, and density datasets of snow made it possible to examine the snow-sea-ice interaction quantitatively for the first time in this area. In general, the snow displayed significant heterogeneity in types, thickness (mean: 0.14 +- 0.13 m), and density (325 +- 38 kg/m**3), as reported in other East Antarctic regions. High salinity was confined to the lowest 0.1 m. Salinity and d18O data within this layer revealed that saline water originated from the surface brine of sea ice in 20% of the total sites and from seawater in 80%. From the vertical profiles of snow density, bulk thermal conductivity of snow was estimated as 0.15 W/K/m on average, only half of the value used for numerical sea-ice models. Although the upward heat flux within snow estimated with this value was significantly lower than that within ice, it turned out that a higher value of thermal conductivity (0.3 to 0.4 W/K/m) is preferable for estimating ice growth amount in current numerical models. Diurnal measurements showed that upward conductive heat flux within the snow and net long-wave radiation at the surface seem to play important roles in the formation of snow ice from slush. The detailed surface topography allowed us to compare the air-ice drag coefficients of ice and snow surfaces under neutral conditions, and to examine the possibility of the retrieval of ice thickness distribution from satellite remote sensing. It was found that overall snow cover works to enhance the surface roughness of sea ice rather than moderate it, and increases the drag coefficient by about 10%. As for thickness retrieval, mean ice thickness had a higher correlation with ice surface roughness than mean freeboard or surface elevation, which indicates the potential usefulness of satellite L-band SAR in estimating the ice thickness distribution in the seasonal sea-ice zone.

Valorización de la naturaleza y disputa por el territorio en la Provincia de Santa Cruz

Desde los inicios de la colonización europea, la historia de la Patagonia es la trayectoria de la ocupación para la puesta en valor de la riqueza de sus bienes naturales en el suelo, subsuelo y en su extenso litoral marítimo. Asentados primero en la explotación del ovino, luego del petróleo, el gas y el carbón y recientemente de la pesca, la minería metalífera y el turismo internacional, los territorios de las actuales provincias de Santa Cruz, del Chubut y de Tierra del Fuego, al igual que sus pares trasandinos de las regiones de Aysén y Magallanes, son espacios ricos en recursos. Para la puesta en valor de los territorios por parte del capital, hacen falta dos condiciones básicas: la existencia de bienes naturales y la presencia de fuerza de trabajo, las cuales, dependiendo de la actividad, pueden o no estar presentes. En algunos casos, se hace necesario adecuar estos espacios mediante equipamientos e infraestructuras, la atracción de trabajadores de diversa calificación y la presencia estatal, en un doble proceso de expansión geográfica y acumulación por desposesión que asegure la valorización en general. En estos territorios, periféricos desde el punto de vista espacial, cada proceso de valorización particular exigió una combinación de apropiación, habilitación y organización del territorio específicas. En el presente artículo se apunta, en primer lugar, a presentar sintéticamente los procesos históricos de valorización de la naturaleza de la región, para luego analizar la actual situación del proceso en el territorio y los conflictos resultantes. En una segunda parte, teniendo en cuenta las tendencias mundiales de alta demanda de bienes naturales, se expondrán los escenarios futuros más probables en caso de acentuarse el actual modelo extractivo y rentista

Valorización de la naturaleza y disputa por el territorio en la Provincia de Santa Cruz

Desde los inicios de la colonización europea, la historia de la Patagonia es la trayectoria de la ocupación para la puesta en valor de la riqueza de sus bienes naturales en el suelo, subsuelo y en su extenso litoral marítimo. Asentados primero en la explotación del ovino, luego del petróleo, el gas y el carbón y recientemente de la pesca, la minería metalífera y el turismo internacional, los territorios de las actuales provincias de Santa Cruz, del Chubut y de Tierra del Fuego, al igual que sus pares trasandinos de las regiones de Aysén y Magallanes, son espacios ricos en recursos. Para la puesta en valor de los territorios por parte del capital, hacen falta dos condiciones básicas: la existencia de bienes naturales y la presencia de fuerza de trabajo, las cuales, dependiendo de la actividad, pueden o no estar presentes. En algunos casos, se hace necesario adecuar estos espacios mediante equipamientos e infraestructuras, la atracción de trabajadores de diversa calificación y la presencia estatal, en un doble proceso de expansión geográfica y acumulación por desposesión que asegure la valorización en general. En estos territorios, periféricos desde el punto de vista espacial, cada proceso de valorización particular exigió una combinación de apropiación, habilitación y organización del territorio específicas. En el presente artículo se apunta, en primer lugar, a presentar sintéticamente los procesos históricos de valorización de la naturaleza de la región, para luego analizar la actual situación del proceso en el territorio y los conflictos resultantes. En una segunda parte, teniendo en cuenta las tendencias mundiales de alta demanda de bienes naturales, se expondrán los escenarios futuros más probables en caso de acentuarse el actual modelo extractivo y rentista

Climate proxies in sediment core MD95-2010

High-amplitude, rapid climate fluctuations are common features of glacial times. The prominent changes in air temperature recorded in the Greenland ice cores (Dansgaard et al., 1993, doi:10.1038/339532a0; Grootes et al., 1993 doi:10.1038/366552a0) are coherent with shifts in the magnitude of the northward heat flux carried by the North Atlantic surface ocean (Bond et al., 1993, doi:10.1038/365143a0; Bond and Lotti, 1995, doi:10.1126/science.267.5200.1005); changes in the ocean's thermohaline circulation are a key component in many explanations of this climate flickering (Broecker, 1997, doi:10.1126/science.278.5343.1582). Here we use stable-isotope and other sedimentological data to reveal specific oceanic reorganizations during these rapid climate-change events. Deep water was generated more or less continuously in the Nordic Seas during the latter part of the last glacial period (60 to 10 thousand years ago), but by two different mechanisms. The deep-water formation occurred by convection in the open ocean during warmer periods (interstadials). But during colder phases (stadials), a freshening of the surface ocean reduced or stopped open-ocean convection, and deep-water formation was instead driven by brine-release during sea-ice freezing. These shifting magnitudes and modes nested within the overall continuity of deep-water formation were probably important for the structuring and rapidity of the prevailing climate changes.