Molecular and isotopic compositions of hydrocarbons at DSDP Site 76-533

In an investigation of gas hydrates in deep ocean sediments, gas samples from Deep Sea Drilling Project Site 533 on the Blake Outer Ridge in the northwest Atlantic were obtained for molecular and isotopic analyses. Gas samples were collected from the first successful deployment of a pressure core barrel (PCB) in a hydrate region. The pressure decline curves from two of the four PCB retrievals at in situ pressures suggested the presence of small amounts of gas hydrates. Compositional and isotopic measurements of gases from several points along the pressure decline curve indicated that (1) biogenic methane (d13C = -68 per mil; C1/C2 = 5000) was the dominant gas (>90%); (2) little fractionation in the C1/C2 ratio or the C carbon isotopic composition occurred as gas hydrates decomposed during pressure decline experiments; (3) the percent of C3, i-C4, and CO2 degassed increased as the pressure declined, indicating that these molecules may help stabilize the hydrate structure; (4) excess nitrogen was present during initial degassing; and (5) C1/C2 ratios and isotopic ratios of C gases were similar to those obtained from conventional core sampling. The PCB gas also contained trace amounts of saturated, acyclic, cyclic, and aromatic C5-C14 hydrocarbons, as well as alkenes and tetrahydrothiophenes. Gas from a decomposed specimen of gas hydrate had similar molecular and isotopic ratios to the PCB gas (d13C of -68 per mil for methane and a C1/C2 ratio of about 6000). Regular trends in the d13C of methane (about -95 to -60 per mil) and C1/C2 ratios (about 25000 to 2000) were observed with depth. Capillary gas chromatography (GC) and total scanning fluorescence measurements of extracted organic material were characteristic of hydrocarbons dominated by a marine source, though significant amounts of perylene were also present.

(Table 1) Stable isotope records of clathrite and water

Aragonitic clathrites are methane-derived precipitates that are found at sites of massive near-seafloor gas hydrate (clathrate) accumulations at the summit of southern Hydrate Ridge, Cascadia margin. These platy carbonate precipitates form inside or in proximity to gas hydrate, which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation. The clathrites record the preferential incorporation of 18O into the hydrate structure and hence the enrichment of 16O in the surrounding brine. We measured d18O values as high as 2.27 per mil relative to Peedee belemnite that correspond to a fluid composition of -1.18 per mil relative to standard mean ocean water. The same trend can be observed in Ca isotopes. Ongoing clathrite precipitation causes enrichment of the 44Ca in the fluid and hence in the carbonates. Carbon isotopes confirm a methane source for the carbonates. Our triple stable isotope approach that uses the three main components of carbonates (Ca, C, O) provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites. This approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation, thus recording the evolution of the geochemical environment of gas hydrate systems.

(Table 1) Results of pore water analyses, including boron content and boron isotope ratios

Drilling a transect of holes across the Costa Rica forearc during ODP Leg 170 demonstrated the margin wedge to be of continental, non accretionary origin, which is intersected by permeable thrust faults. Pore waters from four drillholes, two of which penetrated the décollement zone and reached the underthrust lower plate sedimentary sequence of the Cocos Plate, were examined for boron contents and boron isotopic signatures. The combined results show dilution of the uppermost sedimentary cover of the forearc, with boron contents lower than half of the present-day seawater values. Pore fluid "refreshening" suggests that gas hydrate water has been mixed with the sediment interstitial water, without profoundly affecting the d11B values. Fault-related flux of a deeply generated fluid is inferred from high B concentration in the interval beneath the décollement, being released from the underthrust sequence with incipient burial. First-order fluid budget calculations over a cross-section across the Costa Rica forearc indicate that no significant fluid transfer from the lower to the upper plate is inferred from boron fluid profiles, at least within the frontal 40 km studied. Expulsed lower plate pore water, which is estimated to be 0.26-0.44 km3 per km trench, is conducted efficiently along and just beneath the décollement zone, indicating effective shear-enhanced compaction. In the upper plate forearc wedge, dewatering occurs as diffuse transport as well as channelled flow. A volume of approximately 2 km3 per km trench is expulsed due to compaction and, to a lesser extent, lateral shortening. Pore water chemistry is influenced by gas hydrate instability, so that it remains unknown whether deep processes like mineral dehydration or hydrocarbon formation may play a considerable role towards the hinterland.

(Table 1) Stable oxygen isotope ratios of interstitial waters from ODP Sites 164-994 and 164-997

The d18O values of interstitial waters from Site 994 and Site 997 sediments, Blake Ridge, western Atlantic, tend to decrease with depth from 0.3 per mil to -0.5 per mil Standard Mean Ocean Water in the upper 200 mbsf, then fluctuate with significant positive spikes of Delta = 0.2 per mil - 0.5 per mil in the gas hydrate zone (200 to 450 mbsf), and finally increase from -0.4 per mil to -0.2 per mil toward 700 mbsf. Positive shifts of d18O IW in the gas hydrate zone are probably caused by the dissociation of gas hydrates originally contained in sediment cores. Gas hydrates recovered from the sites are enriched in 18O, d18O ranging between 2.7 per mil and 3.5 per mil. d18O values of gas hydrates and ambient interstitial waters give an oxygen isotopic fractionation factor of 1.0034-1.0040 at 12°-16°C and ~31 MPa (3 km below sea level). Based on this fractionation and observed isotopic anomalies in the gas hydrate zone, gas hydrates occupy 6% to 12% of pore-space volume within Blake Ridge sediments.

The SUGAR Toolbox - Version 7

The SUGAR Toolbox contains scripts coded in MATLAB for calculating various thermodynamic, kinetic, and geologic properties of substances occurring in the marine environment, particularly gas hydrate and seep systems. Brief descriptions of the toolbox scripts and some notes on the underlying basic theory as well as tables of additional property values can be found in the accompanying documentation.

Isotope analysis and heat flow measurements of Maria S. Merian cruise MSM21/4 on the western Svalbard margin

Methane hydrate is an ice-like substance that is stable at high-pressure and low temperature in continental margin sediments. Since the discovery of a large number of gas flares at the landward termination of the gas hydrate stability zone off Svalbard, there has been concern that warming bottom waters have started to dissociate large amounts of gas hydrate and that the resulting methane release may possibly accelerate global warming. Here, we can corroborate that hydrates play a role in the observed seepage of gas, but we present evidence that seepage off Svalbard has been ongoing for at least three thousand years and that seasonal fluctuations of 1-2°C in the bottom-water temperature cause periodic gas hydrate formation and dissociation, which focus seepage at the observed sites.

Gas, water and volume characteristics during controlled degassing experiments on ODP Leg 164 PCS cores

A pressurized core with CH4 hydrate or dissolved CH4 should evolve gas volumes in a predictable manner as pressure is released over time at isothermal conditions. Incremental gas volumes were collected as pressure was released over time from 29 pressure core sampler (PCS) cores from Sites 994, 995, 996, and 997 on the Blake Ridge. Most of these cores were kept at or near 0ºC with an ice bath, and many of these cores yielded substantial quantities of CH4. Volume-pressure plots were constructed for 20 of these cores. Only five plots conform to expected volume and pressure changes for sediment cores with CH4 hydrate under initial pressure and temperature conditions. However, other evidence suggests that sediment in these five and at least five other PCS cores contained CH4 hydrate before core recovery and gas release. Detection of CH4 hydrate in a pressurized sediment core through volume-pressure relationships is complicated by two factors. First, significant quantities of CH4-poor borehole water fill the PCS and come into contact with the core. This leads to dilution of CH4 concentration in interstitial water and, in many cases, decomposition of CH4 hydrate before a degassing experiment begins. Second, degassing experiments were conducted after the PCS had equilibrated in an ice-water bath (0ºC). This temperature is significantly lower than in situ values in the sediment formation before core recovery. Our results and interpretations for PCS cores collected on Leg 164 imply that pressurized containers formerly used by the Deep Sea Drilling Project (DSDP) and currently used by ODP are not appropriately designed for direct detection of gas hydrate in sediment at in situ conditions through volume-pressure relationships.

(Table T1) Dissolved sulfide concentration and d34S of dissolved sulfate and sulfide in pore waters of ODP Leg 204

We report dissolved sulfide sulfur concentrations and the sulfur isotopic composition of dissolved sulfate and sulfide in pore waters from sediments collected during Ocean Drilling Program Leg 204. Porewater sulfate is depleted rapidly as the depth to the sulfate/methane interface (SMI) occurs between 4.5 and 11 meters below seafloor at flank and basin locations. Dissolved sulfide concentration reaches values as high as 11.3 mM in Hole 1251E. Otherwise, peak sulfide concentrations lie between 3.2 and 6.1 mM and occur immediately above the SMI. The sulfur isotopic composition of interstitial sulfate generally becomes enriched in 34S with increasing sediment depth. Peak d34S-SO4 values occur just above the SMI and reach up to 53.1 per mil Vienna Canyon Diablo Troilite (VCDT) in Hole 1247B. d34S-Sigma HS values generally parallel the trend of d34S-SO4 values but are more depleted in 34S relative to sulfate, with values from -12.7 per mil to 19.3 per mil VCDT. Curvilinear sulfate profiles and carbon isotopic composition of total dissolved carbon dioxide at flank and basin sites strongly suggest that sulfate depletion is controlled by oxidation of sedimentary organic matter, despite the presence of methane gas hydrates in underlying sediments. Preliminary data from sulfur species are consistent with this interpretation for Leg 204 sediments at sites not located on or near the crest of Hydrate Ridge.

Temperature measurements, gas chemistry, and gas hydrates of the Dvurechenskii mud volcano

The sediment temperature distribution at mud volcanoes provides insights into their activity and into the occurrence of gas hydrates. If ambient pressure and temperature conditions are close to the limits of the gas hydrate stability field, the sediment temperature distribution not only limits the occurrence of gas hydrates, but is itself influenced by heat production and consumption related to the formation and dissociation of gas hydrates. Located in the Sorokin Trough in the northern Black Sea, the Dvurechenskii mud volcano (DMV) was in the focus of detailed investigations during the M72/2 and M73/3a cruises of the German R/V Meteor and the ROV Quest 4000 m in February and March 2007. A large number of in-situ sediment temperature measurements were conducted from the ROV and with a sensor-equipped gravity corer. Gas hydrates were sampled in pressurized cores using a dynamic autoclave piston corer (DAPC). The thermal structure of the DMV suggests a regime of fluid flow at rates decreasing from the summit towards the edges of the mud volcano, accompanied by intermittent mud expulsion at the summit. Modeled gas hydrate dissociation temperatures reveal that the gas hydrates at the DMV are very close to the stability limits. Changes in heat flow due to variable seepage rates probably do not result in changes in sediment temperature but are compensated by gas hydrate dissociation and formation.

Methane fluxes and carbonate deposits at eastern Mediterranean cold seeps

High acoustic seafloor-backscatter signals characterize hundreds of patches of methane-derived authigenic carbonates and chemosynthetic communities associated with hydrocarbon seepage on the Nile Deep Sea Fan (NDSF) in the Eastern Mediterranean Sea. During a high-resolution ship-based multibeam survey covering a ~ 225 km**2 large seafloor area in the Central Province of the NDSF we identified 163 high-backscatter patches at water depths between 1500 and 1800 m, and investigated the source, composition, turnover, flux and fate of emitted hydrocarbons. Systematic Parasound single beam echosounder surveys of the water column showed hydroacoustic anomalies (flares), indicative of gas bubble streams, above 8% of the high-backscatter patches. In echosounder records flares disappeared in the water column close to the upper limit of the gas hydrate stability zone located at about 1350 m water depth due to decomposition of gas hydrate skins and subsequent gas dissolution. Visual inspection of three high-backscatter patches demonstrated that sediment cementation has led to the formation of continuous flat pavements of authigenic carbonates typically 100 to 300 m in diameter. Volume estimates, considering results from high-resolution autonomous underwater vehicle (AUV)-based multibeam mapping, were used to calculate the amount of carbonate-bound carbon stored in these slabs. Additionally, the flux of methane bubbles emitted at one high-backscatter patch was estimated (0.23 to 2.3 × 10**6 mol a**-1) by combined AUV flare mapping with visual observations by remotely operated vehicle (ROV). Another high-backscatter patch characterized by single carbonate pieces, which were widely distributed and interspaced with sediments inhabited by thiotrophic, chemosynthetic organisms, was investigated using in situ measurements with a benthic chamber and ex situ sediment core incubation and allowed for estimates of the methane consumption (0.1 to 1 × 10**6 mol a**-1) and dissolved methane flux (2 to 48 × 10**6 mol a**-1). Our comparison of dissolved and gaseous methane fluxes as well as methane-derived carbonate reservoirs demonstrates the need for quantitative assessment of these different methane escape routes and their interaction with the geo-, bio-, and hydrosphere at cold seeps.

(Table T1) Carbon contents, alkenone concentrations, alkenone unsaturation index, and SST in sediments of ODP Leg 190 sites

We have preliminarily generated the downcore records of total organic carbon (TOC) content, total alkenone concentration, alkenone unsaturation index, and the estimated sea-surface temperature (SST) in the northern three sites (Sites 1175, 1176, and 1178) of the Muroto Transect, Nankai Trough. The TOC content will be used for the evaluation of the burial of organic matter, which plays a role in the generation of natural gas and the formation of gas hydrate in this region. The downcore records of alkenone SST will benefit studies for the paleoceanography of the northwestern Pacific. Because those sites are located in the main path of the Kuroshio Current, the records provide the temperature change of the Kuroshio water, which is an end-member water mass in the northwestern Pacific.

Theranostic Fibers for Simultaneous Imaging and Drug Delivery

New methods for creating theranostic systems with simultaneous encapsulation of therapeutic, diagnostic, and targeting agents are much sought after. This work reports for the first time the use of coaxial electrospinning to prepare such systems in the form of core–shell fibers. Eudragit S100 was used to form the shell of the fibers, while the core comprised poly(ethylene oxide) loaded with the magnetic resonance contrast agent Gd(DTPA) (Gd(III) diethylenetriaminepentaacetate hydrate) and indomethacin as a model therapeutic agent. The fibers had linear cylindrical morphologies with clear core–shell structures, as demonstrated by electron microscopy. X-ray diffraction and differential scanning calorimetry proved that both indomethacin and Gd(DTPA) were present in the fibers in the amorphous physical form. This is thought to be a result of intermolecular interactions between the different components, the presence of which was suggested by infrared spectroscopy. In vitro dissolution tests indicated that the fibers could provide targeted release of the active ingredients through a combined mechanism of erosion and diffusion. The proton relaxivities for Gd(DTPA) released from the fibers into tris buffer increased (r1 = 4.79–9.75 s–1 mM–1; r2 = 7.98–14.22 s–1 mM–1) compared with fresh Gd(DTPA) (r1 = 4.13 s–1 mM–1 and r2 = 4.40 s–1 mM–1), which proved that electrospinning has not diminished the contrast properties of the complex. The new systems reported herein thus offer a new platform for delivering therapeutic and imaging agents simultaneously to the colon.

Strontium isotopes and sedimentology of a marine Triassic succession (upper Ladinian) of the westernmost Tethys, Spain

Chemical Stratigraphy, or the study of the variation of chemical elements within sedimentary sequences, has gradually become an experienced tool in the research and correlation of global geologic events. In this paper 87Sr/ 86Sr ratios of the Triassic marine carbonates (Muschelkalk facies) of southeast Iberian Ranges, Iberian Peninsula, are presented and the representative Sr-isotopic curve constructed for the upper Ladinian interval. The studied stratigraphic succession is 102 meters thick, continuous, and well preserved. Previous paleontological data from macro and micro, ammonites, bivalves, foraminifera, conodonts and palynological assemblages, suggest a Fassanian-Longobardian age (Late Ladinian). Although diagenetic minerals are present in small amounts, the elemental data content of bulk carbonate samples, especially Sr contents, show a major variation that probably reflects palaeoenvironmental changes. The 87Sr/86Sr ratios curve shows a rise from 0.707649 near the base of the section to 0.707741 and then declines rapidly to 0.707624, with a final values rise up to 0.70787 in the upper part. The data up to meter 80 in the studied succession is broadly concurrent with 87Sr/86Sr ratios of sequences of similar age and complements these data. Moreover, the sequence stratigraphic framework and its key surfaces, which are difficult to be recognised just based in the facies analysis, are characterised by combining variations of the Ca, Mg, Mn, Sr and CaCO3 contents

Stable carbon isotope ratios and accumulation rates of organic carbon and nutrients of DSDP Hole 79-545 (Appendix A)

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world ~112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate ~25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere-land-ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (~45,000 yr) period of ~0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns 2003, doi:10.1098/rsta.2003.1240] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 * 10**18 g methane carbon (delta13C=-60 ?), equivalent to about 10% to the total modern gas hydrate inventory, generated the delta13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over ~25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

Nanoindentation Relaxation Study and Micromechanics of Cement-Based Materials

Ce travail évalue le comportement mécanique des matériaux cimentaires à différentes échelles de distance. Premièrement, les propriétés mécaniques du béton produit avec un bioplastifiant à base de microorganismes efficaces (EM) sont etudiées par nanoindentation statistique, et comparées aux propriétés mécaniques du béton produit avec un superplastifiant ordinaire (SP). Il est trouvé que l’ajout de bioplastifiant à base de produit EM améliore la résistance des C–S–H en augmentant la cohésion et la friction des nanograins solides. L’analyse statistique des résultats d’indentation suggère que le bioplastifiant à base de produit EM inhibe la précipitation des C–S–H avec une plus grande fraction volumique solide. Deuxièmement, un modèle multi-échelles à base micromécanique est dérivé pour le comportement poroélastique de la pâte de ciment au jeune age. L’approche proposée permet d’obtenir les propriétés poroélastiques requises pour la modélisation du comportoment mécanique partiellement saturé des pâtes de ciment viellissantes. Il est montré que ce modèle prédit le seuil de percolation et le module de Young non drainé de façon conforme aux données expérimentales. Un metamodèle stochastique est construit sur la base du chaos polynomial pour propager l’incertitude des paramètres du modèle à travers plusieurs échelles de distance. Une analyse de sensibilité est conduite par post-traitement du metamodèle pour des pâtes de ciment avec ratios d’eau sur ciment entre 0.35 et 0.70. Il est trouvé que l’incertitude sous-jacente des propriétés poroélastiques équivalentes est principalement due à l’énergie d’activation des aluminates de calcium au jeune age et, plus tard, au module élastique des silicates de calcium hydratés de basse densité.