(Table 1) Chemical composition of interstitial waters from the area of gas hydrate generation, Sea of Okhotsk

Distributions of halogens (Cl, Br and I) in interstitial waters from sediments containing methane hydrate and in water of the hydrate itself are presented. High concentrations of halogens do not occur in interstitial waters from sediments that contain gas hydrates. The main reason for their low concentrations is the poverty of organic matter in sediments.

Strontium and boron geochemistry of ODP sites at Hydrate Ridge, eastern Pacific Ocean

ODP Leg 204, which drilled at Hydrate Ridge, provides unique insights into the fluid regime of an accretionary complex and delineates specific sub-seafloor pathways for fluid transport. Compaction and dewatering due to smectite-illite transition increase with distance from the toe of the accretionary prism and bring up fluids from deep within the accretionary complex to sampled depths (<= 600 mbsf). These fluids have a distinctly non-radiogenic strontium isotope signature indicating reaction with the oceanic basement. Boron isotopes are also consistent with a deep fluid source that has been modified by desorption of heavy boron as clay minerals change from smectite to illite. One of three major horizons serves as conduit for the transport of mainly fluid. Our results enable us to evaluate fluid migration pathways that play important roles on massive gas hydrate accumulations and seepage of methane-rich fluids on southern Hydrate Ridge.

(Table T1) Gas hydrate fabric and dipping angles of ODP Leg 204 sediments

The sediments of Hydrate Ridge/Cascadia margin contain extensive amounts of gas hydrate. A total of 57 sediment samples including gas hydrate were preserved in liquid nitrogen and have been imaged using computerized tomography to visualize hydrate distribution and shape. The analysis gives evidence that gas hydrate in vein and veinlet structures is the predominant shape in the deeper gas hydrate stability zone with dipping angles from 30° to 90°(vertical).

(Table 1) Grain size results, statistical parameters and magnetic susceptibility values of disturbed sediments from ODP holes 204-1249C and 204-1245B

Soupy and mousse-like fabrics are disturbance sedimentary features that result from the dissociation of gas hydrate, a process that releases water. During the core retrieval process, soupy and mousse-like fabrics are produced in the gas hydrate-bearing sediments due to changes in pressure and temperature conditions. Therefore, the identification of soupy and mousse-like fabrics can be used as a proxy for the presence of gas hydrate in addition to other evidence, such as pore water freshening or anomalously cool temperature. We present here grain-size results, mineralogical composition and magnetic susceptibility data of soupy and mousse-like samples from the southern Hydrate Ridge (Cascadia accretionary complex) acquired during Leg 204 of the Ocean Drilling Program. In order to study the relationship between sedimentary texture and the presence of gas hydrates, we have compared these results with the main textural and compositional data available from the same area. Most of the disturbed analyzed samples from the summit and the western flank of southern Hydrate Ridge show a mean grain size coarser than the average mean grain size of the hemipelagic samples from the same area. The depositional features of the sediments are not recognised due to disturbance. However, their granulometric statistical parameters and distribution curves, and magnetic susceptibility logs indicate that they correspond to a turbidite facies. These results suggest that gas hydrates in the southern Hydrate Ridge could form preferentially in coarser grain-size layers that could act as conduits feeding gas from below the BSR. Two samples from the uppermost metres near the seafloor at the summit of the southern Hydrate Ridge show a finer mean grain-size value than the average of hemipelagic samples. They were located where the highest amount of gas hydrates was detected, suggesting that in this area the availability of methane gas was high enough to generate gas hydrates, even within low-permeability layers. The mineralogical composition of the soupy and mousse-like sediments does not show any specific characteristic with respect to the other samples from the southern Hydrate Ridge.

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 from the Bush Hill region in the Gulf of Mexico and from ODP Leg 204 at the Hydrate Ridge offshore Oregon

The grain sizes of gas hydrate crystallites are largely unknown in natural samples. Single grains are hardly detectable with electron or optical microscopy. For the first time, we have used high-energy synchrotron diffraction to determine grain sizes of six natural gas hydrates retrieved from the Bush Hill region in the Gulf of Mexico and from ODP Leg 204 at the Hydrate Ridge offshore Oregon from varying depth between 1 and 101 metres below seafloor. High-energy synchrotron radiation provides high photon fluxes as well as high penetration depth and thus allows for investigation of bulk sediment samples. Gas hydrate grain sizes were measured at the Beam Line BW 5 at the HASYLAB/Hamburg. A 'moving area detector method', originally developed for material science applications, was used to obtain both spatial and orientation information about gas hydrate grains within the sample. The gas hydrate crystal sizes appeared to be (log-)normally distributed in the natural samples. All mean grain sizes lay in the range from 300 to 600 µm with a tendency for bigger grains to occur in greater depth. Laboratory-produced methane hydrate, aged for 3 weeks, showed half a log-normal curve with a mean grain size value of c. 40 µm. The grains appeared to be globular shaped.

Time controlled photo-oxidation of polyolefins by polymer bound additives

A variety of iron compounds containing vinyl or thiol functional groups (used as photoactivators) have been synthesised and some of these were successfully bound to both polyethylene and polypropylene backbones during processing in the presence of peroxide and interlinking agent. Concentrates (masterbatches) of the photoactivators in PP and PE were prepared and the pro-oxidant effect of the diluted masterbatches in absence and presence of an antioxidant was evaluated. An antioxidant photoactivator (FeDNC ) was found to sensitise the photoactivity of pro-oxidants (Metone A / Metone M) whereas an antioxidant (ZnDNC) was found to stabilise the polymer (PP and PE) containing both of these combinations. It was observed that the lower concentration of FeDNC sensitises the stability of the polymer containing very small concentration of NiDNC whereas higher concentration of FeDNC stabilises the polymer (LDPE) containing same amount of NiDNC compared to FeDNC alone. The photostability of unstabilised PP containing FeAc could be varied by varying the concentration of ZnDEC. Both the induction period and the UV - life time of the polymer increased by increasing concentration of ZnDEC. It is suggested that ligand exchange reaction may take place between FeAc and ZnDNC. A polymer bound UV stabiliser (HAEB) and a thermal stabiliser (DBBA) were used with a non extractable photoactivator (FeAc) in PP. Small concentrations of the stabilisers (HAEB and DBBA) in combination with the photoactivator (FeAc) sensitise the polymer. The antioxidant present in commercial polymer (LDPE and PP) was found to be of a hindered phenol type, which was found to antagonise with ZnDNC when used in combination with the photoactivators.