Hydrocarbon gas concentrations in sediments from ODP Leg 164 sites

Residual concentrations and distributions of hydrocarbon gases from methane to n-heptane were measured in sediments at seven sites on Ocean Drilling Program (ODP) Leg 164. Three sites were drilled at the Cape Fear Diapir of the Carolina Rise, and one site was drilled on the Blake Ridge Diapir. Methane concentrations at these sites result from microbial generation which is influenced by the amount of pore-water sulfate and possible methane oxidation. Methane hydrate was found at the Blake Ridge Diapir site. The other hydrocarbon gases at these sites are likely the product of early microbial processes. Three sites were drilled on a transect of holes across the crest of the Blake Ridge. The base of the zone of gas-hydrate occurrence was penetrated at all three sites. Trends in hydrocarbon gas distributions suggest that methane is microbial in origin and that the hydrocarbon gas mixture is affected by diagenesis, outgassing, and, near the surface, by microbial oxidation. Methane hydrate was recovered at two of these three sites, although gas hydrate is likely present at all three sites. The method used here for determining amounts of residual hydrocarbon gases has its limitations and provides poor assessment of gas distributions, particularly in the stratigraphic interval below about ~100 mbsf. One advantage of the method, however, is that it yields sufficient quantities of gas for other studies such as isotopic determinations.

Magnetic susceptibility parameters of ODP Leg 204 sites

In this paper, we present a rock magnetic data set produced for sediments from Hydrate Ridge recovered during Ocean Drilling Program Leg 204. Our data set is based on several artificially induced magnetic properties that can be used as a diagnostic for the presence of magnetic iron sulfides. The occurrence of magnetic iron sulfides within the gas hydrate stability zone in locations where gas hydrates are present seems to confirm previous interpretations linking formation of such minerals with generation of gas hydrate. Magnetic iron sulfides are also found at positions deeper than the gas hydrate stability zone. We suggest that these positions, which include intervals located just below the bottom-simulating reflector and also at deeper positions, may mark the former presence of gas hydrates that have been later dissociated as the gas hydrate stability zone moved upward through time. Detailed characterization of the magnetic iron sulfide mineralogy and comparison with sedimentological and geochemical data will be attempted for better determining the significance of magnetic iron sulfides in Hydrate Ridge sediments and their possible applications in the study of gas hydrates.

Absolute abundances of benthic foraminifers and stable isotopes from the Alvin dives 3709-3712

The presence of gas hydrates on the Blake Ridge diapir, northeastern Atlantic Ocean, offers an opportunity to study the impact of methane seepage on the ecology and geochemistry of benthic foraminifera in the late Holocene. Three push cores, covering a time span of ~ 1000 yrs, were retrieved from three distinct microhabitats at the top of the diapir at a water depth of ~ 2150 m: (i) sediments away from seepage (control core), (ii) sediments overlain by clusters of methanotrophic and thiotrophic bivalves, and (iii) chemoautotrophic microbial mats. The foraminiferal assemblages at the two seep sites are marked by a reduction in benthic foraminiferal species diversity, coupled with a near-absence of agglutinated species. However, an opportunistic population rise in CH4- or H2S-tolerant calcareous species (e.g., Globocassidulina subglobosa and Cassidulina laevigata) that utilize the abundant trophic resources at the seeps has led to an increase in the overall assemblage density there. The delta18O and delta13C values of three species of benthic foraminifera - Gyroidinoides laevigatus, Globocassidulina subglobosa, and Uvigerina peregrina - and the planktonic species Globorotalia menardii were acquired from all three cores. The benthic species from methane seeps yield delta13C values of 0.1 to - 4.2 (per mil VPDB), that are distinctly more 13C-depleted relative to the delta13C of 0.4 to - 1.0 (per mil VPDB) at the control (off seep) site. The species from a mussel-bed site exhibit more negative delta13C values than those from microbial mats, possibly reflecting different food sources and higher rate of anaerobic oxidation of methane. The positive delta13C values in the paired planktonic species suggest that authigenic carbonate precipitation did not overprint the observed 13C depletions. Hence the probable cause of negative delta13C of benthic foraminifera is primary calcification from Dissolved Inorganic Carbon (DIC) containing mixed carbon fractions from (a) highly 13C-depleted, microbially-oxidized methane and (b) a seawater source.

(Table 1) Crystal sizes of measured samples

Due to experimental difficulties grain size distributions of gas hydrate crystallites are largely unknown in natural samples. For the first time, we were able to determine grain size distributions of six natural gas hydrates for samples retrieved from the Gulf of Mexico and from Hydrate Ridge offshore Oregon from varying depths. High-energy synchrotron radiation provides high photon fluxes as well as high penetration depth and thus allows for investigation of bulk sediment samples. The gas hydrate crystallites appear to be (log-) normally distributed in the natural samples and to be of roughly globular shape. The mean grain sizes are in the range from 300-600 µm with a tendency for bigger grains to occur in greater depth, possibly indicating a difference in the formation age. Laboratory produced methane hydrate, starting from ice and aged for 3 weeks, shows half a log-normal curve with a mean value of ~40 µm. This one order-of-magnitude smaller grain sizes suggests that care must be taken when transposing grain-size sensitive (petro-)physical data from laboratory-made gas hydrates to natural settings.

Radon 222 excess measured on water bottle samples during HEINCKE cruise HE153

In the years 2000 and 2001 we measured methane concentrations exceeding up to two orders of magnitude the equilibrium with the atmosphere in the water column on the SW-Spitsbergen continental shelf. This methane anomaly extended from its centre on the shelf westwards over the upper slope and eastwards well into the inner basins of the two southernmost Spitsbergen fjords, the Hornsundfjord and the van Mijenfjord. Methane concentrations and stable carbon isotopic ratios varied between 2 and 240 nM, and between -53 per mill and -20 per mill VPDB, respectively. Methane in high concentrations was depleted in 13C whereas in low concentrations d13CCH4 values were highly variable. On the continental shelf we found that methane discharged from seeps on top of sandy and gravelly banks is isotopically heavier than methane escaping from troughs filled with silty and clayey sediments. These distinct isotopic signatures suggest that methane is gently released from several inter-granular seepages or micro-seepages widely spread over the shelf. A potential migration path for thermogenic or hydrate methane may be the Hornsund Fracture Zone, a south-north running reactivated fault system created by stretching of the continental crust. After discharge into the water column, local water currents fed by Atlantic water, coastal water, and freshwater outflows from the fjords further determine pathways and fate of the methane. We used d18Owater and 222Rn data to trace origin and advection of the local water masses and water mixing processes. Methane spreads predominantly along pycnoclines and by vertical mixing. During transport methane is influenced simultaneously by oxidation and dilution, as well as loss into the atmosphere. Together these processes cause the spatial variability of the anomaly and heterogeneity in d13CCH4 in this polar shelf environment.

(Table 1) Composition of pore water from ODP Site 997 holes A and B

Pore water extracted from sediments penetrated on Leg 164 of the Ocean Drilling Program at the Blake Ridge West. Atlantic were analyzed for acetate, total dissolved organic carbon, bromide and iodide, to help explain the occurrence of subsurface maxima in bacteria biomass and activity reported previously from a nearby site. The high concentrations of these organic matter decomposition by-products in the pore waters from sediments with moderate concentrations of sedimentary organic matter can convincingly be modelled as resulting from upward migration of pore water. The amount of acetate and unidentified DOC transported by the pore water contribute significantly to the pool of metabolizable carbon, and may be the most important substances in energetic terms.

(Table 1) Carbon, hydrocarbons and observations at DSDP Holes 67-497 and 67-498A

Gas hydrates are icelike materials that form when specific conditions of temperature, pressure, and gas composition are simultaneously satisfied. Among the first descriptions of gas hydrates under natural conditions was that of Hammerschmidt (1940), who found them in pipelines used to transport natural gas. Milton (1976) indicates that conditions are suitable for the presence of gas hydrates in areas affected by permafrost and cites studies suggesting that large quantities of gas exist in hydrate form.

Soft solution processing of cerium hydroxysulfate powders with different morphologies

Polycrystalline cerium hydroxysulfate powders have been prepared by soft solution processing using various basic solvents. The crystals prepared have varying morphologies, spherical and flaky, depending on the solvent used. The crystals obtained from distilled water-pyridine and aqueous ammonia solvent mixtures are spherical, whereas those obtained from mixtures of distilled water and ethylenediamine or hydrazine hydrate are flaky. All the crystalline cerium hydroxysulfate samples display luminescence properties. It was found that the flaky crystals generally show a much stronger luminescence than their spherical counterparts.

Molecular dynamics characterization of n-octyl-beta-D-glucopyranoside micelle structure in aqueous solution

n-Octyl-beta-D-glueopyranoside (OG) is a non-ionic glycolipid, which is used widely in biotechnical and biochemical applications. All-atom molecular dynamics simulations from two different initial coordinates and velocities in explicit solvent have been performed to characterize the structural behaviour of an OG aggregate at equilibrium conditions. Geometric packing properties determined from the simulations and small angle neutron scattering experiment state that OG micelles are more likely to exist in a non-spherical shape, even at the concentration range near to the critical micelle concentration (0.025 M). Despite few large deviations in the principal moment of inertia ratios, the average micelle shape calculated from both simulations is a prolate ellipsoid. The deviations at these time scales are presumably the temporary shape change of a micelle. However, the size of the micelle and the accessible surface areas were constant during the simulations with the micelle surface being rough and partially elongated. Radial distribution functions computed for the hydroxyl oxygen atoms of an OG show sharper peaks at a minimum van der Waals contact distance than the acetal oxygen, ring oxygen, and anomeric carbon atoms. This result indicates that these atoms are pointed outwards at the hydrophilic/hydrophobic interface, form hydrogen bonds with the water molecules, and thus hydrate the micelle surface effectively. (c) 2005 Elsevier Inc. All rights reserved.

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)(3)(circle)9H(2)O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N-2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.

Geochemical and Sr, Nd, Pb isotope investigation of the New Caledonia ophiolite

The New Caledonia ophiolite hosts one of the largest obducted mantle section in the world, hence providing a unique insight for the study of upper mantle processes. These mantle rocks belong to an “atypical” ophiolitic sequence, which is dominated by refractory harzburgites but it also includes minor spinel and plagioclase lherzolites. Upper crust is notably absent in the ophiolite, with the exception of some mafic-ultramafic cumulates cropping out in the southern part of the island. Although the New Caledonia ophiolite has been under investigation for decades, its ultra-depleted nature has made its characterization an analytical challenge, so that few trace element data are available, while isotopic data are completely missing. In this thesis a comprehensive geochemical study (major, trace element and Sr-Nd-Pb isotopes) of the peridotites and the associated intrusive mafic rocks from the New Caledonia ophiolite has been carried out. The peridotites are low-strain tectonites showing porphyroclastic textures. Spinel lherzolites are undepleted lithotypes, as attested by the presence of 7-8 vol% of Na2O and Al2O3-rich clinopyroxene (up to 0.5 wt% Na2O; 6.5 wt% Al2O3), Fo content of olivine (88.5-90.0 mol%) and low Cr# of spinel (13-17). Conversely, harzburgites display a refractory nature, proven by the remarkable absence of primary clinopyroxene, very high Fo content in olivine (90.9-92.9 mol%), high Mg# in orthopyroxene (89.8-94.2) and Cr# in spinel (39-71). REE contents show abyssal-type patterns for spinel lherzolites, while harzburgites display U-shaped patterns, typical of fore-arc settings. Spinel lherzolites REE compositions are consistent with relatively low degree (8-9%) of fractional melting of a DMM source, starting in the garnet stability field. Conversely, REE models for harzburgites indicate high melting degrees (20-25%) of a DMM mantle source under spinel faies conditions, consistent with hydrous melting in forearc setting. Plagioclase lherzolites exhibit melt impregnation microtextures, Cr- and TiO2-enriched spinels and REE, Ti, Y, Zr progressive increase with respect to spinel lherzolites. Impregnation models indicate that plagioclase lherzolites may derive from spinel lherzolites by entrapment of highly depleted MORB melts in the shallow oceanic lithosphere. Mafic intrusives are olivine gabbronorites with a very refractory composition, as attested by high Fo content of olivine (87.3-88.9 mol.%), very high Mg# of clinopyroxene (87.7-92.2) and extreme anorthitic content of plagioclase (An = 90-96 mol%). The high Mg#, low TiO2 concentrations in pyroxenes and the anorthitic composition of plagioclase point out an origin from ultra-depleted primitive magmas in a convergent setting. Geochemical trace element models show that the parental melts of gabbronorites are primitive magmas with striking depleted compositions, bearing only in part similarities with the primitive boninitic melts of Bonin Islands. The first Sr, Nd and Pb isotope data obtained for the New Caledonia ophiolite highlight the presence of DM mantle source variably modified by different processes. Nd-Sr-Pb isotopic ratios for the lherzolites (+6.98≤epsilon Ndi≤+10.97) indicate a DM source that suffered low-temperature hydrothermal reactions. Harzburgites are characterized by a wide variation of Sr, Nd and Pb isotopic values, extending from DM-type to EM2 compositions (-0.82≤ epsilon Ndi≤+17.55), suggesting that harzburgite source was strongly affected by subduction-related processes. Conversely, combined trace element and Sr-Nd-Pb isotopic data for gabbronorites indicate a derivation from a source with composition similar to Indian-type mantle, but affected by fluid input in subduction environment. These geochemical features point out an evolution in a pre-Eocenic marginal basin setting, possibly in the proximity of a transform fault, for the lherzolites. Conversely, the harzburgites acquired their main geochemical and isotopic fingerprint in subduction zone setting.

Synthesis and characterization of triazolotriazines

The Dimroth rearrangement in ring-fused 1,2,4-triazoles has been reviewed in detail in Part I and the synthesis of all known triazolo-triazines is described in Part II. Experimental investigations concerned the establishinent of the skeletal arrangement of a variety of triazolotriazines formed by several synthetic routes. Interaction of 3-amino-5-hydrazino-12,4-triazole and benzilafforded 2-amino-6, 7-diphenyl-1, 2,4-triazolo[ 5, 1-c-]-1,2,4-triazine,whereas cyclization of 5,6-diphenyl-3-hydrazino-1,2,4-triazine withcyanogen bromide resulted in the isomeric 3-amino-6,7-diphenyl,-1,2,4-triazolo [4, 3-b]-1,2,4-triazine: both amines were deaminated with amyl nitrite in boiling tetrahydrofuran without rearrangement of the heterocyclic skeleton. 6,7-Diphenyl-1,2,4-triazolo[5,1-cJ-1,2.4-triazine, synthesized from 3-hydrazino-1,2,4-triazole and benzil, formed a covalent hydrate which could be detected spectroscopically in solution, and a covalemt methanolate and ethanolate which could be isolated. A new route to 3-amino-5-hydrazino-pyrazole is described and cyclization to 7-amino-3,4-diphenyl-pyrazolo[ 5,1-.c]-1,2,4-triazine was achieved with benzil. The diazonium nitrate of 3-amino-1,2,4-triazole coupled with ethyl cyanoacetate to yield a mixture of two geometrical isomers of ethyl 2-(2H-1,2,4-triazol-3-ylhydrazono) cyanoacetate.Recrystallization of the crude coupling mixture from aqueous ethanol gave a single hydra-zone which cyclized predominantly to ethyl 7-amino-1,2,4-triazolo[5,1-c]-1,2,4-triazine-6-carboxylate in acid conditions and 6-cyano-1,2,4-triazolo[ 5,1-c]-1,2,4~triazin-7(4H)-one under basic conditions. The nature of the cyclizing medium also controlled the cyclization of .the (pyrazol-ylhydrazono) cyanoacetate hut the corresponding (tetrazol- ylhydrazono) cyanoacetate gave only ethyl 7-aminotetrazolo[ 5,1-cJ-1,2,4- -triazine-6-carboxylate. 2-( 2H-1,2,4-Triazol-3-:ylhydrazono) malonitrile cyclized unambiguously to 7-amino-6-cyano-1,2,4-triazolo-[ 5,1-c]-1,2,4- triazine. Drastic hydrolysis of ethyl 2-(2H-1,2,4-triazol-3-yllhydrazono)-cyanoacetate, ethyl 7-amino-1, 2,4-triazolo[ 5,1-c]-1,2,4-triazine-6-carboxylate, 6-cyano-1,2,4-triazolo[ 5,1-c]-1,2,4-triazin-7{ 4H)-one and 7-amino-6- cyano-1,2,4-triazolo[5,1-c]-1,2,4-triazine gave a hydrate of 1,2,4-triazo1o[5,1-c ]-1,2,4-triazin-7(4H)-one. Mass spectral fragmentations of 7-aminoazolo-[5,1-c]-1,2,4-triazinesconfirm that the azole ring is more stable than the 1,2,4-triazine ring on electron impact.

Monte Carlo and molecular dynamics simulations of methane in potassium montmorillonite clay hydrates at elevated pressures and temperatures

The structure and dynamics of methane in hydrated potassium montmorillonite clay have been studied under conditions encountered in sedimentary basin and compared to those of hydrated sodium montmorillonite clay using computer simulation techniques. The simulated systems contain two molecular layers of water and followed gradients of 150 barkm-1 and 30 Kkm-1 up to a maximum burial depth of 6 km. Methane particle is coordinated to about 19 oxygen atoms, with 6 of these coming from the clay surface oxygen. Potassium ions tend to move away from the center towards the clay surface, in contrast to the behavior observed with the hydrated sodium form. The clay surface affinity for methane was found to be higher in the hydrated K-form. Methane diffusion in the two-layer hydrated K-montmorillonite increases from 0.39×10-9 m2s-1 at 280 K to 3.27×10-9 m2s-1 at 460 K compared to 0.36×10-9 m2s-1 at 280 K to 4.26×10-9 m2s-1 at 460 K in Na-montmorillonite hydrate. The distributions of the potassium ions were found to vary in the hydrates when compared to those of sodium form. Water molecules were also found to be very mobile in the potassium clay hydrates compared to sodium clay hydrates. © 2004 Elsevier Inc. All All rights reserved.