(Tables 1, 3) Component composition of organic particles in samples from ODP Site 131-808

Analysis of the palynofacies and miospore thermal alteration indices (TAI) of sediments from ODP Site 808 in the Nankai Trough was undertaken to determine (1) the source, depositional environment, and diagenesis of organic matter in the accreted sediments, and (2) the thermal structure and history of the prism and its relationship to fluid flow. Using the Hartax classification system, two palynofacies were recognized in the sedimentary sequence. Facies 1 occurs within the upper 600 m of trench-wedge turbidites (sedimentation rate > 1 km/m.y.) and contains >50% inertite particles. The rest of the assemblage is dominated by well-preserved phytoclasts and contains small amounts of poorly preserved phytoclasts and well-preserved scleratoclasts. Facies 2 occurs within the Shikoku Basin hemipelagites (600-1300 m below seafloor; sedimentation rate <150 m/m.y.) and contains over two-thirds inertite particles. The rest of the assemblage is dominated by poorly preserved phytoclasts. Miospores and marine phytoplankton compose only a small percentage of both palynofacies. Degraded organic matter is most noticeable in Facies 2, whereas its presence in Facies 1 is overshadowed by the high influx of well-preserved primary organic matter. Most of the degraded organic matter and inertite is interpreted to be reworked. Some of the degraded organic matter may be primary, and may have experienced more biodegradation and thermal alteration in Facies 2 than in Facies 1. TAI values indicate an immature stage of organic maturation (< 2) down to about 900 mbsf. Below this, samples show an increase with depth to a mature stage, reaching peak levels of about 3 just above basement. Samples from within the thrust fault and decollement zones do not show levels of maturity significantly greater than those of surrounding samples, leaving uncertain whether hot fluids have migrated along these fault boundaries in the past.

NMR microscopy: A tool for measuring monomer diffusion in supercritical CO2

The diffusion of styrene into linear low density polyethylene in a solution of supercritical CO2 was investigated using NMR microimaging. For both pure styrene and styrene dissolved in supercritical CO2, the diffusion was found to follow Fickian kinetics. Supercritical CO2 was found to enhance the rate and extent of diffusion of styrene into the substrate by up to three times under the conditions of this investigation, compared to pure styrene. NMR imaging was used to measure the concentration profiles of the styrene penetrants in real time, and the results were fitted to a Fickian model for diffusion. At a CO2 pressure of 150 bar and temperature of 40 degrees C, the diffusion coefficient of a 30 wt-% solution of styrene into LLDPE was calculated to be 1 X 10(-11) m(2). s(-1). This is significantly faster than the diffusion coefficient measured for pure styrene diffusion at 40 degrees C (3 x 10(-12) m(2). s(-1)). The diffusion coefficients determined by gravimetric analysis were slightly higher than those determined by the imaging method. This was probably due to residual styrene and/or polystyrene adhering to the surface of the films in the gravimetric technique.

The oxidation behaviour of sintered iron

The oxidation behaviour of porous, sintered iron was studied by thermo-gravimetric analysis (TGA), at temperatures between 300oC and 700oC, in a flowing atmosphere of 20% O2/80% N2. Samples for TGA tests were compacted from pure iron powder, at 150MPa to 550MPa, and vacuum sintered at 1120oC. The mass gain of samples during oxidation was recorded continuously for a period of 24 hours. It was found that the oxidation mass gain of PM samples depended on the permeability of the pore structure and the temperature. At low temperatures, the oxidising gas was able to permeate through the pore structure, causing the oxidation of a large active surface area. At high temperatures the active surface area was smaller, because oxygen diffusing into the pore structure, from the external atmosphere, was adsorbed by pore surfaces close to the external surface of the compact. Although the weight of the external oxide scale on compacts increased with increasing oxidation temperature, the absence of oxide in the core porosity in compacts oxidised at higher temperatures resulted in smaller mass gains than were observed for compacts oxidised at lower temperatures. The heat generated by the oxidation of the large active surface areas of porous samples was studied by thermo-calorimetric analysis (TCA). It was determined that this phenomenon could raise the core temperature of samples significantly above the ambient furnace temperature, and affecting the morphology of the oxide scale formed. The effects (on oxidation behaviour at 500oC) of small, elemental alloy additions of Al, Cu, P and Si to pure iron powder were studied. It was found that elements that promote pore rounding during sintering caused a significant reduction in the mass gain rate of the PM alloys, compared to the PM pure iron. The oxidation resistance due to these elements prevented pore closure by oxide growth, so that the active surface area of these PM alloys remained high. The PM alloys were also studied by thermo-mechanical analysis (TMA, dilatometry), to determine their dimensional stability during sintering and subsequent elevated temperature service. The oxidation experiment was augmented with optical and electron microscopy, and X-ray analysis of alloy and scale compositions.

Genetic and environmentally derived variation in the cell wall composition of miscanthus and implications for thermo-chemical conversion

Fifteen Miscanthus genotypes grown in five locations across Europe were analysed to investigate the influence of genetic and environmental factors on cell wall composition. Chemometric techniques combining near infrared reflectance spectroscopy and conventional chemical analyses were used to construct calibration models for determination of acid detergent lignin, acid detergent fibre, and neutral detergent fibre from sample spectra. The developed equations were shown to predict cell wall components with a good degree of accuracy and significant genetic and environmental variation was identified. The influence of nitrogen and potassium fertiliser on the dry matter yield and cell wall composition of M. x giganteus was investigated. A detrimental affect on feedstock quality was observed to result from application of these inputs which resulted in an overall reduction in concentrations of cell wall components and increased accumulation of ash within the biomass. Pyrolysis-gas chromatography-mass spectrometry and thermo-gravimetric analysis indicates that genotypes other than the commercially cultivated M. x giganteus have potential for use in energy conversion processes and in the bio-refining. The yields and quality parameters of the pyrolysis liquids produced from Miscanthus compared favourably with that produced from SRC willow and produced a more stable pyrolysis liquid with a higher lower heating value. Overall, genotype had a more significant effect on cell wall composition than environment. This indicates good potential for dissection of this trait by QTL analysis and also for plant breeding to produce new genotypes with improved feedstock characteristics for energy conversion.

The intermediate pyrolysis and catalytic steam reforming of brewers spent grain

Brewers spent grain (BSG) is a widely available feedstock representing approximately 85% of the total by-products generated in the brewing industry. This is currently either disposed of to landfill or used as cattle feed due to its high protein content. BSG has received little or no attention as a potential energy resource, but increasing disposal costs and environmental constraints are now prompting the consideration of this. One possibility for the utilisation of BSG for energy is via intermediate pyrolysis to produce gases, vapours and chars. Intermediate pyrolysis is characterised by indirect heating in the absence of oxygen for short solids residence times of a few minutes, at temperatures of 350-450 °C. In the present work BSG has been characterised by chemical, proximate, ultimate and thermo-gravimetric analysis. Intermediate pyrolysis of BSG at 450 °C was carried out using a twin coaxial screw reactor known as Pyroformer to give yields of char 29%, 51% of bio-oil and 19% of permanent gases. The bio-oil liquid was found to separate in to an aqueous phase and organic phase. The organic phase contained viscous compounds that could age over time leading to solid tars that can present problems in CHP application. The quality of the pyrolysis vapour products before quenching can be upgraded to achieve much improved suitability as a fuel by downstream catalytic reforming. A Bench Scale batch pyrolysis reactor has then been used to pyrolyse small samples of BSG under a range of conditions of heating rate and temperature simulating the Pyroformer. A small catalytic reformer has been added downstream of the reactor in which the pyrolysis vapours can be further cracked and reformed. A commercial reforming nickel catalyst was used at 500, 750 and 850 °C at a space velocity about 10,000 L/h with and without the addition of steam. Results are presented for the properties of BSG, and the products of the pyrolysis process both with and without catalytic post-processing. Results indicate that catalytic reforming produced a significant increase in permanent gases mainly (H2 and CO) with H2 content exceeding 50 vol% at higher reforming temperatures. Bio-oil yield decreased significantly as reforming temperature increased with char remaining the same as pyrolysis condition remained unchanged. The process shows an increase in heating value for the product gas ranging between 10.8-25.2 MJ/m as reforming temperature increased. © 2012 Elsevier B.V. All rights reserved.

The influence of surface functionalization of activated carbon on palladium dispersion and catalytic activity in hydrogen oxidation

Stone-fruit activated carbon (SAC) and modified versions containing acidic oxygen and basic nitrogen groups have been used to prepare palladium catalysts by wet impregnation. Carbon supports and catalysts are investigated by thermo-gravimetric analysis, TPD, oxygen chemisorption, TEM and XPS. The influence of the nature of the functional groups on the dispersion and oxidation state of palladium and its activity in hydrogen oxidation is investigated. Pd dispersion is found to increase with the basic strength of functional groups on the support. XPS reveals that introduction of amine groups in SAC results in an increased proportion of Pd0, resistant to re-oxidation. Palladium catalysts supported on activated carbon modified by diethylamine groups are found to exhibit the highest metal dispersion and greatest activity in hydrogen oxidation. © 2007 Elsevier B.V. All rights reserved.

Geochemistry on manganese nodules from the central Pacific

During Cruise VA 04/2 of the R. V. Valdivia in 1972, numerous samples were collected of manganese nodules, sodiments, and the pore water of the Sediments in the area betwoen 6° N and 11° N and between 149° W and 154° W in the Central Pacific. This paper reports on the geochemical study of 70 manganese nodules from 12 stations (box-core and dredge samples). The nodules Irom a single Station vary considerably in diemical composition. These variations are of the same magnitude as the variations in nodule composition over the entire survey area. The ratios of manganese to nickel, copper, and zinc show good positive correlation as do the ratios of iron to lead and, to a lesser extent, of iron to cobalt. No correlation was found between the environment of the manganese nodules and their metal content. Three internal zones, the outer. intermediate, and core zones, of some nodules were studied in detail. Trends of differences of Chemical composition from surface to core were found for numerous elements and elemental ratios.

Short-term temporal and spatial variations in physical, optical and biogeochemical parameters in June of 2013 in Alfacs Bay (NW Mediterranean)

With the aim of analyzing the complex physical and biogeochemical interactions at high temporal and spatial resolution in the complex estuarine waters of Alfacs Bay, a beam attenuation-based approach was used as optical proxy of different biogeochemical variables. Thus, the dataset contains the attenuation proxies as well as laboratory results from the analysis of water samples, which were used to validate our approach. In addition, the major physical forcing in the Bay was also measured.

(Table 1) Chemical composition of ethmodiscus oozes from the Indian Ocean

A study was made of mineral composition of sand- and silt-sized fractions of recent clastic (riftogenic) sediments and solidified deposits collected from the bottom of the Romanche Trench during the first voyage of R/V Akademik Kurchatov. Similarity between mineral compositions of sediments and bedrocks (ultrabasites, gabbroids, diabases) was established. This similarity is a basis for considering the mineral complex of the deposits that have been derived from the bedrocks of the trench slopes, and have formed due to their submarine denudation accompanied by tectonic crushing. The same mineral composition was found in pieces of older consolidated deposits; this suggests that conditions of sedimentation similar to those at recent times have existed for a long time in the Romanche Trench.