(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.

(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.

(Table 1) Deuterium ratios, chloride content and hydrate volume of pore water and hydrate meltwater from ODP Site 164-996

Site 996 is located above the Blake Diapir where numerous indications of vertical fluid migration and the presence of hydrate existed prior to Ocean Drilling Program (ODP) Leg 164. Direct sampling of hydrates and visual observations of hydrate-filled veins that could be traced 30-40 cm along cores suggest a connection between fluid migration and hydrate formation. The composition of pore water squeezed from sediment cores showed large variations due to melting of hydrate during core recovery and influence of saline water from the evaporitic diapir below. Analysis of water released during hydrate decomposition experiments showed that the recovered hydrates contained significant amounts of pore water. Solutions of the transport equations for deuterium (d2H) and chloride (Cl-) were used to determine maximum (d2H) and minimum (Cl-) in situ concentrations of these species. Minimum in situ concentrations of hydrate were estimated by combining these results with Cl- and d2H values measured on hydrate meltwaters and pore waters obtained by squeezing of sediments, by the means of a method based on analysis of distances in the two-dimensional Cl- d2H space. The computed Cl- and d2H distribution indicates that the minimum hydrate amount solutions are representative of the actual hydrate amount. The highest and mean hydrate concentrations estimates from our model are 31% and 10% of the pore space, respectively. These concentrations agree well with visual core observations, supporting the validity of the model assumptions. The minimum in situ Cl- concentrations were used to constrain the rates of upward fluid migration. Simulation of all available data gave a mean flow rate of 0.35 m/k.y. (range: 0.125-0.5 m/k.y.).

DOD future energy resources : proceedings of workshops held at the National Defense University /

"The enclosed CD contains Adobe PDF files of this report and presentations delivered at two workshops on DOD future energy resources"--P. [2] of cover.

The drying of small drops of particulate slurries

The literature on the evaporation of drops of pure liquids, drops containing solids and droplet sprays has been critically reviewed. An experimental study was undertaken on the drying of suspended drops of pure water and aqueous sodium sulphate decahydrate with concentrations varying from 5 to 54. 1 wt. %. Individual drops were suspended from a glass filament balance in a 26 mm I.D. vertical wind tunnel, designed and constructed to supply hot de-humidified air, to simulate conditions encountered in commercial spray driers. A novel thin film thermocouple was developed to facilitate the simultaneous measurement of drop weight and core temperature. The heat conduction through the thermocouple was reduced because of its unique design; using essentially a single 50μ diameter nickel wire. For pure water drops, the Nusselt number was found to be a function of the Reynolds, Prandtl and Transfer numbers for a temperature range between 19 to 79°C.                  Nu = 2 + 0.19 (1/B)0.24 Re0.5 Pr0.33 Two distinct periods were observed during the drying of aqueous sodium sulphate decahydrate. The first period was characterised by the evaporation from a free liquid surface, whilst drying in the second period was controlled by the crust resistance. Fracturing of the crust occurred randomly but was more frequent at higher concentrations and temperatures. A model was proposed for the drying of slurry drops, based on a receding evaporation interface. The model was solved numerically for the variation of core temperature, drop weight and crust thickness as a function of time. Experimental results were in excellent agreement with the model predictions although at higher temperatures modifications to the model had to be made to accommodate the unusual behaviour of sodium sulphate slurries, i.e. the formation of hydrates.

Grewia polysaccharide gum as a pharmaceutical excipient

Grewia gum is obtained from the inner stem bark of the edible plant Grewia mollis Juss (Fam. Tiliaceae) which grows widely in the middle belt region of Nigeria, and is also cultivated. The dried and pulverised inner stem bark is used as a thickening agent in some food delicacies in that region of the country. This ability of the material to increase solution viscosity has generated a lot of interest and is the catalysing momentum for this research. Such materials have been used as stabilizers or suspending agents in cosmetics, foods and liquid medications, and as mucoadhesives and controlled release polymeric matrices in solid dosage forms. The physicochemical characterization of candidate excipients forms an essential step towards establishing suitability for pharmaceutical application. For natural gums, this usually requires isolation of the gum from the storage site by extraction processes. Grewia polysaccharide gum was extracted and dried using techniques such as air-drying, freeze-drying or spray-drying. Component analysis of the gum showed that it contains five neutral sugars: glucose, galactose, rhamnose, arabinose and xylose. The gum contains traces of elements such as zinc, magnesium, calcium and phosphorus. At low substance weight, the gum hydrates in aqueous medium swelling and dispersing to give a highly viscous dispersion with pseudoplasmic flow behaviour. The method by which drying is achieved can have significant effect on some physicochemical properties of the gum. Consequently, the intrinsic viscosity and molecular weight, and parameters of powder flow were shown to differ with the method of drying. The gum has good thermal stability. In comparison with established excipients, grewia gum may be preferable to gum Arabic or sodium carboxymethylcellulose as a suspending agent in ibuprofen suspension formulations. The release retardant property of the gum was superior to guar and Metolose® in ibuprofen matrices. Similarly, carboxy methylcellulose, Methocel®, gum Arabic or Metolose® may not be preferable to grewia gum when controlled release of a soluble drug like cimetidine is indicated. The mucoadhesive performance of the gum compared favourably with excellent mucoadhesives such as hydroxypropyl methylcellulose, carboxymethylcellulose, guar and carbopol 971 P.

The durability of glass fibre reinforced cements made with new cementitious matrices

Widespread use of glass fibre reinforced cement (GRC) has been impeded by concerns over its durability. Three degradation mechanisms are proposed - fibre corrosion, Ca(OHh precipitation and matrix densification - although their relative importance is debated. Matrices with reduced alkalinities and Ca(OH)2 contents are being developed; the aim of this study was to investigate their hydration and interaction with alkali-resistant fibres to determine the factors controlling their long-term durability, and assess the relevancy of accelerated ageing. The matrices studied were: OPC/calcium-sulphoaluminate cement plus metakaolin (C); OPC plus metakaolin (M); blast-furnace slag cement plus a micro-silica based additive (D); and OPC (O). Accelerated ageing included hot water and cyclic regimes prior to tensile testing. Investigations included pore solution expression, XRD, DTA/TG, SEM and optical petrography. Bond strength was determined from crack spacings using microstructural parameters obtained from a unique image analysis technique. It was found that, for the new matrices - pore solution alkalinities were lower; Ca(OH)2 was absent or quickly consumed; different hydrates were formed at higher immersion temperatures; degradation under 65°C immersion was an order of magnitude slower, and no interfilamental Ca(OH)2 was observed .It was concluded that: fibre weakening caused by flaw growth was the primary degradation mechanism and was successfully modelled on stress corrosion/static fatigue principles. OPC inferiority was attributed partly to its higher alkalinity but chiefly to the growth of Ca(OH)2 aggravating the degradation; and hot water ageing although useful in model formulation and contrasting the matrices, changed the intrinsic nature of the composites rather than simply accelerating the degradation mechanisms.

Polymer modified cement: hydration microstructure and diffusion properties

Investigations concentrated on the styrene butadiene rubber (SBR) latex and formulations included standard carboxylated and special carboxylated latexes. The aqueous component, containing the stabilisers and antifoaming agent but not the polymer solids, was also used. For comparison, limited investigations were carried out using other polymer types e.g. acrylic, ethylene-vinyl acetate (EVA), and redispersible powders rather than emulsions. The major findings were: 1) All latex systems investigated acted as retarders for cement hydration. The extent of retardation depends on the type of polymer. The mechanism for cement hydration may be changed, and excessive retardation influences properties. 2) Polymer modified cements exhibited either similar or coarser pore structures compared with unmodified cements. Results suggest that polymer mainly exists in a mixture of cement hydrates and polymer phase. Very little evidence was found for the formation of a distinct polymer film phase. 3) During the first few days of curing the polymer solids are removed from the pore solution and concentrations of OH-, Na+ and K+ are reduced. These observations are probably a result of polymer-cement surface interactions since there was no evidence of any chemical reactions or degradation of the polymer. 4) Improved diffusional resistance of modified cements depends on the ability to achieve adequate workability at low w/c ratio, rather than modification of matrix structure.

Paleoenvironments and geochemical signals from the late Barremian to the middle Aptian in a Tethyan marginal basin, northeast Spain: Implications for carbon sequestration in restricted basins

The hallmark of oceanic anoxic event 1a (OAE1a) (early Aptian ~125 Ma) corresponds to worldwide deposition of black shales with total organic carbon (TOC) content > 2% and a δ13C positive excursion up to ~5‰. OAE1a has been related to large igneous province volcanism and dissociation of methane hydrates during the Lower Cretaceous. However, the occurrence of atypical, coeval and diachronous organic-rich deposits associated with OAE1a, which are also characterized by positive spikes of the δ 13C in epicontinental to restricted marine environments of the Tethys Ocean, indicates localized responses decoupled from complex global forcing factors. ^ The present research is a high-resolution, multiproxy approach to assess the paleoenvironmental conditions that led to enhanced carbon sequestration from the late Barremian to the middle Aptian in a restricted, Tethyan marginal basin prior to and during OAE1a. I studied the lower 240 m of the El Pui section, Organyà Basin, Spanish Pyrenees. The basin developed as the result of extensional tectonism linked to the opening of the Atlantic Ocean. At the field scale the section consists of a sequence of alternating beds of cm – m-scale, medium-gray to grayish-black limestones and marlstones with TOC up to ~4%. ^ The results indicate that the lowest 85 m of the section, from latest Barremian -earliest Aptian, characterize a deepening phase of the basin concomitant with sustained riverine flux and intensified primary productivity. These changes induced a shift in the sedimentation pattern and decreased the oxygen levels in the water column through organic matter respiration and limited ventilation of the basin. ^ The upper 155 m comprising the earliest – late-early Aptian document the occurrence of OAE1a and its associated geochemical signatures (TOC up to 3% and a positive shift in δ13C of ~5‰). However, a low enrichment of redox-sensitive trace elements indicates that the basin did not achieve anoxic conditions. The results also suggest that a shallower-phase of the basin, coeval with platform progradation, may have increased ventilation of the basin at the same time that heightened sedimentation rates and additional input of organic matter from terrestrial sources increased the burial and preservation rate of TOC in the sediment.^

Modelagem e simulação da solubilidade de sais em sistemas aquosos com Monoetilenoglicol

Primary processing of natural gas platforms as Mexilhão Field (PMXL-1 ) in the Santos Basin, where monoethylene glycol (MEG) has been used to inhibit the formation of hydrates, present operational problems caused by salt scale in the recovery unit of MEG. Bibliographic search and data analysis of salt solubility in mixed solvents, namely water and MEG, indicate that experimental reports are available to a relatively restricted number of ionic species present in the produced water, such as NaCl and KCl. The aim of this study was to develop a method for calculating of salt solubilities in mixed solvent mixtures, in explantion, NaCl or KCl in aqueous mixtures of MEG. The method of calculating extend the Pitzer model, with the approach Lorimer, for aqueous systems containing a salt and another solvent (MEG). Python language in the Integrated Development Environment (IDE) Eclipse was used in the creation of the computational applications. The results indicate the feasibility of the proposed calculation method for a systematic series of salt (NaCl or KCl) solubility data in aqueous mixtures of MEG at various temperatures. Moreover, the application of the developed tool in Python has proven to be suitable for parameter estimation and simulation purposes

Volume averaging of multiphase flows with hydrate formation in subsea pipelines

In oil and gas pipeline operations, the gas, oil, and water phases simultaneously move through pipe systems. The mixture cools as it flows through subsea pipelines, and forms a hydrate formation region, where the hydrate crystals start to grow and may eventually block the pipeline. The potential of pipe blockage due to hydrate formation is one of the most significant flow-assurance problems in deep-water subsea operations. Due to the catastrophic safety and economic implications of hydrate blockage, it is important to accurately predict the simultaneous flow of gas, water, and hydrate particles in flowlines. Currently, there are few or no studies that account for the simultaneous effects of hydrate growth and heat transfer on flow characteristics within pipelines. This thesis presents new and more accurate predictive models of multiphase flows in undersea pipelines to describe the simultaneous flow of gas, water, and hydrate particles through a pipeline. A growth rate model for the hydrate phase is presented and then used in the development of a new three-phase model. The conservation equations of mass, momentum, and energy are formulated to describe the physical phenomena of momentum and heat transfer between the fluid and the wall. The governing equations are solved based on an analytical-numerical approach using a Newton-Raphson method for the nonlinear equations. An algorithm was developed in Matlab software to solve the equations from the inlet to the outlet of the pipeline. The developed models are validated against a single-phase model with mixture properties, and the results of comparative studies show close agreement. The new model predicts the volume fraction and velocity of each phase, as well as the mixture pressure and temperature profiles along the length of the pipeline. The results from the hydrate growth model reveal the growth rate and location where the initial hydrates start to form. Finally, to assess the impact of certain parameters on the flow characteristics, parametric studies have been conducted. The results show the effect of a variation in the pipe diameter, mass flow rate, inlet pressure, and inlet temperature on the flow characteristics and hydrate growth rates.

A probabilistic approach to assess hydrate formation and design preventive measures

Formation of hydrates is one of the major flow assurance problems faced by the oil and gas industry. Hydrates tend to form in natural gas pipelines with the presence of water and favorable temperature and pressure conditions, generally low temperatures and corresponding high pressures. Agglomeration of hydrates can result in blockage of flowlines and equipment, which can be time consuming to remove in subsea equipment and cause safety issues. Natural gas pipelines are more susceptible to burst and explosion owing to hydrate plugging. Therefore, a rigorous risk-assessment related to hydrate formation is required, which assists in preventing hydrate blockage and ensuring equipment integrity. This thesis presents a novel methodology to assess the probability of hydrate formation and presents a risk-based approach to determine the parameters of winterization schemes to avoid hydrate formation in natural gas pipelines operating in Arctic conditions. It also presents a lab-scale multiphase flow loop to study the effects of geometric and hydrodynamic parameters on hydrate formation and discusses the effects of geometric and hydrodynamic parameters on multiphase development length of a pipeline. Therefore, this study substantially contributes to the assessment of probability of hydrate formation and the decision making process of winterization strategies to prevent hydrate formation in Arctic conditions.

(Table 1) Ratio of hydroxy-GDGT vs. the total core GDGT was calculated based on the detection of hydroxy-GDGT

Hydroxylated glycerol dialkyl glycerol tetraethers (hydroxy-GDGTs) were detected in marine sediments of diverse depositional regimes and ages. Mass spectrometric evidence, complemented by information gleaned from two-dimensional (2D) 1H-13C nuclear magnetic resonance (NMR) spectroscopy on minute quantities of target analyte isolated from marine sediment, allowed us to identify one major compound as a monohydroxy-GDGT with acyclic biphytanyl moieties (OH-GDGT-0). NMR spectroscopic and mass spectrometric data indicate the presence of a tertiary hydroxyl group suggesting the compounds are the tetraether analogues of the widespread hydroxylated archaeol derivatives that have received great attention in geochemical studies of the last two decades. Three other related compounds were assigned as acyclic dihydroxy-GDGT (2OH-GDGT-0) and monohydroxy-GDGT with one (OH-GDGT-1) and two cyclopentane rings (OH-GDGT-2). Based on the identification of hydroxy-GDGT core lipids, a group of previously reported unknown intact polar lipids (IPLs), including the ubiquitously distributed H341-GDGT (Lipp J. S. and Hinrichs K. -U. (2009) Structural diversity and fate of intact polar lipids in marine sediments. Geochim. Cosmochim. Acta 73, 6816-6833), and its analogues were tentatively identified as glycosidic hydroxy-GDGTs. In addition to marine sediments, we also detected hydroxy-GDGTs in a culture of Methanothermococcus thermolithotrophicus. Given the previous finding of the putative polar precursor H341-GDGT in the planktonic marine crenarchaeon Nitrosopumilus maritimus, these compounds are synthesized by representatives of both cren- and euryarchaeota. The ubiquitous distribution and apparent substantial abundance of hydroxy-GDGT core lipids in marine sediments (up to 8% of total isoprenoid core GDGTs) point to their potential as proxies.

Concentrations of major and minor constituents of samples from the lower end of the cores from the eastern Mediterranean Sea (Table 2)

The pore water chemistry of mud volcanoes from the Olimpi Mud Volcano Field and the Anaximander Mountains in the eastern Mediterranean Sea have been studied for three major purposes: (1) modes and velocities of fluid transport were derived to assess the role of (upward) advection, and bioirrigation for benthic fluxes. (2) Differences in the fluid chemistry at sites of Milano mud volcano (Olimpi area) were compiled in a map to illustrate the spatial heterogeneity reflecting differences in fluid origin and transport in discrete conduits in near proximity. (3) Formation water temperatures of seeping fluids were calculated from theoretical geothermometers to predict the depth of fluid origin and geochemical reactions in the deeper subsurface. No indications for downward advection as required for convection cells have been found. Instead, measured pore water profiles have been simulated successfully by accounting for upward advection and bioirrigation. Advective flow velocities are found to be generally moderate (3-50 cm/y) compared to other cold seep areas. Depth-integrated rates of bioirrigation are 1-2 orders of magnitude higher than advective flow velocities documenting the importance of bioirrigation for flux considerations in surface sediments. Calculated formation water temperatures from the Anaximander Mountains are in the range of 80 to 145 °C suggesting a fluid origin from a depth zone associated with the seismic decollement. It is proposed that at that depth clay mineral dehydration leads to the formation and advection of fluids reduced in salinity relative to sea water. This explains the ubiquitous pore water freshening observed in surface sediments of the Anaximander Mountain area. Multiple fluid sources and formation water temperatures of 55 to 80 °C were derived for expelled fluids of the Olimpi area.