Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.

Molecular and isotopic properties of gases from ODP Holes of ODP Leg 204

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C2+ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO2 and H2S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.

(Table T1) Composition of clay minerals from ODP Leg 204 sediments

This report describes the results of semiquantitative analysis of clay mineral composition by X-ray diffraction. The samples consist of hemipelagic mud and mudstone cored from Hydrate Ridge during Leg 204 of the Ocean Drilling Program. We analyzed oriented aggregates of the clay-sized fractions (<2 µm) to estimate relative percentages of smectite, illite, and chlorite (+ kaolinite). For the most part, stratigraphic variations in clay mineral composition are modest and there are no significant differences among the seven sites that were included in the study. On average, early Pleistocene to Holocene trench slope and slope basin deposits contain 29% smectite, 31% illite, and 40% chlorite (+ kaolinite). Late Pliocene to early Pleistocene strata from the underlying accretionary prism contain moderately larger proportions of smectite with average values of 38% smectite, 27% illite, and 35% chlorite (+ kaolinite). There is no evidence of clay mineral diagenesis at the depths sampled. The expandability of smectite is, on average, equal to 64%, and there are no systematic variations in expandability as a function of burial depth or depositional age. The absence of clay mineral diagenesis is consistent with the relatively shallow sample depths and corresponding maximum temperatures of only 24°-33°C.

Sapientia, 1998, Vol. LIII, nº 204 (número completo)

Contenido: El tiempo como medida de la primera esfera en la Física de Aristóteles / Marcelo L. Imperiale – Verdad, tiempo y justicia. Un tema de la filosofía de Anselmo de Canterbury / Ubaldo Pérez Paoli – La aportación de Tomás de Aquino a la filosofía de la justicia / Carlos Ignacio Massini Correas – Libertad y naturaleza: la voluntad como naturaleza y como razón según Tomás de Aquino / Guillermo Eduardo Spiegel Sosa – La representación como desvelamiento en Tomás de Aquino / Patrica Moya C. – Las condiciones de una nueva teoría del ente natural tras la condena de 1277. La Physica de Walter Burley y sus peculiaridades / Olga L. Larre – Gewibheit und Wahrheit. Descartes’ Grundlegung der Ersten Philosophie / Wilhelm Metz – La noción aristotélico-tomista de verdad y su interpretación en “El ser y el tiempo” de Martin Heidegger / Silvana Filippi – Subjetivistas radicales y hermenéutica en la escuela austríaca de economía / Ricardo F. Crespo – Examen de los principios de la bioética contemporánea predominantes / Camilo Tale – Sguardi sulla fine dei tempi e sulle cose ultime. A proposito Della struttura escatologica del cristianísimo / Vittorio Possenti – Naturaleza teleológica: articulación entre ser, deber ser y virtud / Jorge Peña Vial -- ¿Qué es un doctor de la Iglesia? / Francisco Canals Vidal – Anotaciones sobre la recepción y la crítica de la metafísica tomista en el pensamiento contemporáneo / Mario Enrique Sacchi – Notas y comentarios -- Bibliografía

Primary cosmic-ray positrons and negatrons in 1968 at energies between 11 and 204 MeV

The cosmic-ray positron and negatron spectra between 11 and 204 MeV have been measured in a series of 3 high-altitude balloon flights launched from Fort Churchill, Manitoba, on July 16, July 21, and July 29, 1968. The detector system consisted of a magnetic spectrometer utilizing a 1000-gauss permanent magnet, scintillation counters, and a lucite Čerenkov counter.

Launches were timed so that the ascent through the 100 g/cm² level of residual atmosphere occurred after the evening geomagnetic cutoff transition. Data gathered during ascent are used to correct for the contribution of atmospheric secondary electrons to the flux measured at float altitude. All flights floated near 2.4 g/cm².

A pronounced morning intensity increase was observed in each flight. We present daytime positron and negatron data which support the interpretation of the diurnal flux variation as a change in the local geomagnetic cutoff. A large diurnal variation was observed in the count rate of positrons and negatrons with magnetic rigidities less than 11 MV and is evidence that the nighttime cutoff was well below this value.

Using nighttime data we derive extraterrestrial positron and negatron spectra. The positron-to-total-electron ratio which we measure indicates that the interstellar secondary, or collision, source contributes ≾50 percent of the electron flux within this energy interval. By comparing our measured positron spectrum with the positron spectrum calculated for the collision source we derive the absolute solar modulation for positrons in 1968. Assuming negligible energy loss during modulation, we derive the total interstellar electron spectrum as well as the spectrum of directly accelerated, or primary, electrons. We examine the effect of adiabatic deceleration and find that many of the conclusions regarding the interstellar electron spectrum are not significantly altered for an assumed energy loss of up to 50 percent of the original energy.

Internationale Jungheringsuntersuchungen auf der Georges-Bank 204

86. Reise FFS "Anton Dohrn", 13. Februar - 9. April 1978

Polymerization of 1,3-butadiene with VO(P-204)(2) and VO(P-507)(2) activated by alkylaluminum

The oxovanadium phosphonates (VO(P-204)(2) and VO(P-507)(2)) activated by various alkylaluminums (AlR3, R = Et, i-Bu, n-Oct; HAIR(2), R = Et, i-Bu) were examined in butadiene (Bd) polymerization. Both VO(P-204)(2) and VO(P-507)(2) showed higher activity than those of classical vanadium-based catalysts (e.g. VOCl3, V(acac)(3)). Among the examined catalysts, the VO(P-204)(2)/Al(Oct)(3) system (I) revealed the highest catalytic activity, giving the poly(Bd) bearing M-n of 3.76 x 10(4) g/mol, and M-w/M-n ratio of 2.9, when the [Al]/[V] molar ratio was 4.0 at 40 degrees C. The polymerization rate for I is of the first order with respect to the concentration of monomer. High thermal stability of I was found, since a fairly good catalytic activity was achieved even at 70 degrees C (polymer yield > 33%); the M-n value and M-w/M-n, ratio were independent of polymerization temperature in the range of 40-70 degrees C. By IR and DSC, the poly(Bd)s obtained had high 1,2-unit content (> 65%) with atactic configuration. The 1,2-unit content of the polymers obtained by I was nearly unchanged, regardless of variation of reaction conditions, i.e. [Al]/[V], ageing time, and reaction temperature, indicating the high stability of stereospecificity of the active sites.