Mineralogical and stable isotope analyses of carbonates from the eastern Black Sea

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

Mineralogical, geochemical, and lipid biomarker study of cabonate precipitates at station GeoB9908-1

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low d13C values measured on carbonates (-41 to -32 per mill V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. d18O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly 18O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.

Global macrozoobenthos production and energy budget data base V150731, with link to database

I developed a new model for estimating annual production-to-biomass ratio P/B and production P of macrobenthic populations in marine and freshwater habitats. Self-learning artificial neural networks (ANN) were used to model the relationships between P/B and twenty easy-to-measure abiotic and biotic parameters in 1252 data sets of population production. Based on log-transformed data, the final predictive model estimates log(P/B) with reasonable accuracy and precision (r2 = 0.801; residual mean square RMS = 0.083). Body mass and water temperature contributed most to the explanatory power of the model. However, as with all least squares models using nonlinearly transformed data, back-transformation to natural scale introduces a bias in the model predictions, i.e., an underestimation of P/B (and P). When estimating production of assemblages of populations by adding up population estimates, accuracy decreases but precision increases with the number of populations in the assemblage.

Stable carbon and oxygen isotope record of planktonic foraminifera across the Paleocene-Eocene boundary

The early Cenozoic marine carbon isotopic record is marked by a long-term shift from high d13C values in the late Paleocene to values that are 2 to 3 lower in the early Eocene. The shift is recorded in fossil carbonates from each ocean basin and represents a large change in the distribution of 12C between the ocean and other carbon reservoirs. Superimposed upon this long-term shift are several distinct carbon isotopic negative excursions that are also recorded globally. These carbon isotopic 'events' near the Paleocene-Eocene boundary provide strati-graphic information that can facilitate intersite correlations between marine and non-marine sequences. Here we present a detailed marine carbon isotopic stratigraphy across the Paleocene-Eocene boundary that is constrained by calcareous nannofossil and planktonic foraminifera bio-stratigraphy and magnetostratigraphy. We show that several distinct carbon isotopic changes are recorded in uppermost Paleocene and lowermost Eocene marine biogenic carbonate sediments. At least one of these isotopic changes in the ocean's carbon isotopic composition was transmitted to terrestrial carbon reservoirs, including plant biomass via atmospheric CO2. As a consequence of this exchange of 12C between the ocean and terrestrial carbon reservoirs, it is possible to use carbon isotope stratigraphy to correlate the uppermost Paleocene and lowermost Eocene non-fossiliferous terrestrial sediments of the Paris Basin with marine sequences.

Averages and ranges of paleoenvironmental proxy records of ODP Hole 108-658C (Table 1)

Several high-resolution proxy environmental records have been obtained for the last 35 kyr from ODP Hole 658C, a well-studied site ca. 200 km off Cap Blanc, NW Africa. The collective assessment based on the marine proxies (UK'37 SST, contents of TOC and chlorins, Upwelling Radiolarian Index and the percentage of Florisphaera profunda), surprisingly indicates that the last glacial maximum (LGM) was characterized by warmer sea surface temperature (SST), weaker upwelling, and lower marine productivity, compared with the preceding older glacial and subsequent deglaciation periods. Of the terrigenous proxies, the mean grain size of the non-carbonate fraction and the terrigenous alkane content indicate that wind strength and aridity were high. The weaker upwelling at the 658 site during the LGM may have resulted from changes in the strength and direction of the wind systems and/or shifts in the position and geometry of the upwelling cell.

Organic geochemistry and sedimentology of lower to mid-Cretaceous at DSDP Leg 77 Holes

Analyses of 40 carbonate core samples - 27 from Site 535, 12 from Site 540, and 1 from Site 538A - have confirmed many of the findings of the Shipboard Scientific Party. The samples, all but one Early to mid-Cretaceous in age (Berriasian to Cenomanian), reflect sequences of cyclically anoxic and oxic depositional environments. They are moderately to very dark colored, dominantly planar-parallel, laminated lime mudstones. Most show the effects of intense mechanical compaction. Visual kerogen characteristics and conventional Rock-Eval parameters indicate that these deep basinal carbonates contain varying mixtures of thermally immature kerogen derived from both marine and terrigenous precursors. However, variations in kerogen chemistry are evident upon analysis of the pyrolysis mass spectral data in conjunction with the other geochemical analyses. Particularly diagnostic is the reduction index, Rl, a measure of H2S produced during pyrolysis. Total organic carbon, TOC, ranges from 0.6 to 6.6%, with an overall average of 2.4%. Average TOCs for these fine-grained mudstones are: late Eocene 2.5% (1 sample), Cenomanian 2.2% (6), Albian 2.0% (10), Aptian 1.3% (1), Barremian-Hauterivian 2.8% (11), late Valanginian 4.8% (3), Berriasian-early Valanginian 1.6% (7). Most of the carbonates have source-potential ratings of fair to very good of predominantly oil-prone to mixed kerogen, with only a few gas-prone samples. The ratings correlate well with the inferred depositional environments, i.e., whether oxic or anoxic. Several new organic-geochemical parameters, especially Rl, based on pyrolysis mass spectrometry of powdered whole-rock samples, support this view. Tar from fractures in laminated to bioturbated limestones of Unit IV (late Valanginian) at 535-58-4, 19-20 cm (530 m sub-bottom) appears to be mature, biodegraded, and of migrated rather than on site indigenous origin.

Hydrological and meteorological records from the Vernagtferner Basin - Vernagtbach station, for the years 2002 to 2012

In November 2001, two separate Campbell loggers ("Meteologger" and "Hydrologger", both type CR23X) were installed at the Vernagtbach site in the Oetztal Alps, Austria (Latitude: 46.85; Longitude: 10.82; Elevation: 2640 m). On these loggers, 10-minutes centred averages for the meteorological data and 5-minutes centred averages for the hydrological data are recorded. The meteorological parameters comprise air temperature, humidity of the air, air pressure, four radiation components, wind direction and speed, precipitation and snow height. For air temperature, two records are published, recorded with a ventilated and an unventilated Pt-100 in a Stevenson screen; for precipitation, three time series are available: (I) the cumulative record of a weighing gauge for the whole year, (II) single events derived from (I), and (III) single events from a tipping bucket; (II) and (III) are only provided for the period 1, May to 31, October of each year. Wind records are also given with a time step of one hour, as only these records include several statistics of speed and direction. Hydrological parameters are recorded on the "Hydrologger", they comprise water stage, discharge, water temperature and electrolytic conductivity of the water. An identifying number gives the kind of instrument used in the water stage time series. Daily photographs of the glacier are provided and analysed with respect to precipitation type.