Wave uplift pressures on horizontal platforms

The major objective of the study has been to investigate in detail the rapidly-varying peak uplift pressure and the slowly-varying positive and negative uplift pressures that are known to be exerted by waves against the underside of a horizontal pier or platform located above the still water level, but not higher than the crests of the incident waves.

In a "two-dimensional" laboratory study conducted in a 100-ft long by 15-in.-wide by 2-ft-deep wave tank with a horizontal smooth bottom, individually generated solitary waves struck a rigid, fixed, horizontal platform extending the width of the tank. Pressure transducers were mounted flush with the smooth soffit, or underside, of the platform. The location of the transducers could be varied.

The problem of a d equate dynamic and spatial response of the transducers was investigated in detail. It was found that unless the radius of the sensitive area of a pressure transducer is smaller than about one-third of the characteristic width of the pressure distribution, the peak pressure and the rise-time will not be recorded accurately. A procedure was devised to correct peak pressures and rise-times for this transducer defect.

The hydrodynamics of the flow beneath the platform are described qualitatively by a si1nple analysis, which relates peak pressure and positive slowly-varying pressure to the celerity of the wave front propagating beneath the platform, and relates negative slowly-varying pressure to the process by which fluid recedes from the platform after the wave has passed. As the wave front propagates beneath the platform, its celerity increases to a maximum, then decreases. The peak pressure similarly increases with distance from the seaward edge of the platform, then decreases.

Measured peak pressure head, always found to be less than five times the incident wave height above still water level, is an order of magnitude less than reported shock pressures due to waves breaking against vertical walls; the product of peak pressure and rise-time, considered as peak impulse, is of the order of 20% of reported shock impulse due to waves breaking against vertical walls. The maximum measured slowly-varying uplift pressure head is approximately equal to the incident wave height less the soffit clearance above still water level. The normalized magnitude and duration of negative pressure appears to depend principally on the ratio of soffit clearance to still water depth and on the ratio of platform length to still water depth.

Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

The relationships between fish assemblages and the amount of bottom horizontal beam exposed at California oil platforms: fish habitat preferences at man-made platforms and (by inference) at natural reefs

Between 1995 and 2002, we surveyed fish assemblages at seven oil platforms off southern and central California using the manned research submersible Delta. At each platform, there is a large horizontal beam situated at or near the sea floor. In some instances, shells and sediment have buried this beam and in other instances it is partially or completely exposed. We found that fish species responded in various ways to the amount of exposure of the beam. A few species, such as blackeye goby (Rhinogobiops nicholsii), greenstriped rockfish (Sebastes elongatus), and pink seaperch (Zalembius rosaceus) tended to avoid the beam. However, many species that typically associate with natural rocky outcrops, such as bocaccio (S. paucispinis), cowcod (S. levis), copper (S. caurinus), greenblotched (S. rosenblatti), pinkrose (S. simulator) and vermilion (S. miniatus) rockfishes, were found most often where the beam was exposed. In particular, a group of species (e.g., bocaccio, cowcod, blue (Sebastes mystinus), and vermilion rockfishes) called here the “sheltering habitat” guild, lived primarily where the beam was exposed and formed a crevice. This work demonstrates that the presence of sheltering sites is important in determining the species composition of man-made reefs and, likely, natural reefs. This research also indicates that adding structures that form sheltering sites in and around decommissioned platforms will likely lead to higher densities of many species typical of hard and complex structure.

Do oil and gas platforms off California reduce recruitment of bocaccio (Sebastes paucispinis) to natural habitat? An analysis based on trajectories derived from high-frequency radar

To investigate the possibility that oil and gas platforms may reduce recruitment of rockfishes (Sebastes spp.) to natural habitat, we simulated drift pathways termed “trajectories” in our model) from an existing oil platform to nearshore habitat using current measurements from high-frequency (HF) radars. The trajectories originated at Platform Irene, located west of Point Conception, California, during two recruiting seasons for bocaccio (Sebastes paucispinis): May through August, 1999 and 2002. Given that pelagic juvenile bocaccio dwell near the surface, the trajectories estimate transport to habitat. We assumed that appropriate shallow water juvenile habitat exists inshore of the 50-m isobath. Results from 1999 indicated that 10% of the trajectories represent transport to habitat, whereas 76% represent transport across the offshore boundary. For 2002, 24% represent transport to habitat, and 69% represent transport across the offshore boundary. Remaining trajectories (14% and 7% for 1999 and 2002, respectively) exited the coverage area either northward or southward along isobaths. Deployments of actual drifters (with 1-m drogues) from a previous multiyear study provided measurements originating near Platform Irene from May through August. All but a few of the drifters moved offshore, as was also shown with the HF radar-derived trajectories. These results indicate that most juvenile bocaccio settling on the platform would otherwise have been transported offshore and perished in the absence of a platform. However, these results do not account for the swimming behavior of juvenile bocaccio, about which little is known.

Travel Characteristics of Marine Anglers Using Oil and Gas Platforms in the Central Gulf of Mexico

This study was designed to evaluate the travel characteristics of avid marine anglers off Louisiana in the Central Gulf of Mexico. It focuses on the complex marine travel patterns involving the extensive assemblage of oil and gas structures. In an intercept approach, marine recreationalf isherman were asked to identify near and offshore travel patterns on the day of the interview. Information was also solicited regarding how respondents selected and located fishing destinations as well as what method of fishing was undertaken that day. Petroleum platforms were a principal fishing destination, and platform anglers traveled an average distance of 75.5 km (40.7 n.mi.) to and from offshore fishing locations. In fishing an average of 6.5 platforms per trip, these anglers traveled about 21.3 km (11.5 n.mi.) between the first and last platform visited. Mean total distances for platform anglers were 96 km (51.8 n.mi). Travel distances for bay, nearshore, and bluewater anglers were also obtained.

SBLOCK: A framework for efficient stencil-based PDE solvers on multi-core platforms

We present a new software framework for the implementation of applications that use stencil computations on block-structured grids to solve partial differential equations. A key feature of the framework is the extensive use of automatic source code generation which is used to achieve high performance on a range of leading multi-core processors. Results are presented for a simple model stencil running on Intel and AMD CPUs as well as the NVIDIA GT200 GPU. The generality of the framework is demonstrated through the implementation of a complete application consisting of many different stencil computations, taken from the field of computational fluid dynamics. © 2010 IEEE.

Evaluation of the functionality of biodegradable polymeric platforms for drug delivery systems

We present the development of a drug-loaded triple-layer platform consisting of thin film biodegradable polymers, in a properly designed form for the desired gradual degradation. Poly(dl-lactide-co-glycolide) (PLGA (65:35), PLGA (75:25)) and polycaprolactone (PCL) were grown by spin coating technique, to synthesize the platforms with the order PCL/PLGA (75:25)/PLGA (65:35) that determine their degradation rates. The outer PLGA (65:35) layer was loaded with dipyridamole, an antiplatelet drug. Spectroscopic ellipsometry (SE) in the Vis-far UV range was used to determine the nanostructure, as well as the content of the incorporated drug in the as-grown platforms. In situ and real-time SE measurements were carried out using a liquid cell for the dynamic evaluation of the fibrinogen and albumin protein adsorption processes. Atomic force microscopy studies justified the SE results concerning the nanopores formation in the polymeric platforms, and the dominant adsorption mechanisms of the proteins, which were defined by the drug incorporation in the platforms. © 2013 Elsevier B.V. All rights reserved.

Feasibility of combined wind-wave energy platforms

The European Union has set out an ambitious 20% target for renewable energy use by 2020. It is expected that this will be met mainly by wind energy. Looking towards 2050, reductions in greenhouse gas emissions of 80-95% are to be sought. Given the issues securing this target in the transport and agriculture sectors, it may only be possible to achieve this target if the power sector is carbon neutral well in advance of 2050. This has permitted the vast expansion of offshore renewables, wind, wave and tidal energy. Offshore wind has undergone rapid development in recent years however faces significant challenges up to 2020 to ensure commercial viability without the need for government subsidies. Wave energy is still in the very early stages of development so as yet there has been no commercial roll out. As both of these technologies are to face similar challenges in ensuring they are a viable alternative power generation method to fossil fuels, capitalising on the synergies is potentially a significant cost saving initiative. The advent of hybrid solutions in a variety of configurations is the subject of this thesis. A singular wind-wave energy platform embodies all the attributes of a hybrid system, including sharing space, transmission infrastructure, O&M activities and a platform/foundation. This configuration is the subject of this thesis, and it is found that an OWC Array platform with multi-MegaWatt wind turbines is a technically feasible, and potentially an economically feasible solution in the long term. Methods of design and analysis adopted in this thesis include numerical and physical modelling of power performance, structural analysis, fabrication cost modelling, simplified project economic modelling and time domain reliability modelling of a 210MW hybrid farm. The application of these design and analysis methods has resulted in a hybrid solution capable of producing energy at a cost between €0.22/kWh and €0.31/kWh depending on the source of funding for the project. Further optimisation through detailed design is expected to lower this further. This thesis develops new and existing methods of design and analysis of wind and wave energy devices. This streamlines the process of early stage development, while adhering to the widely adopted Concept Development Protocol, to develop a technically and economically feasible, combined wind-wave energy hybrid solution.