INVESTIGATION OF OCEAN ACOUSTICS USING AUTONOMOUS INSTRUMENTATION TO QUANTIFY THE WATER-SEDIMENT BOUNDARY PROPERTIES

Sound propagation in shallow water is characterized by interaction with the oceans surface, volume, and bottom. In many coastal margin regions, including the Eastern U.S. continental shelf and the coastal seas of China, the bottom is composed of a depositional sandy-silty top layer. Previous measurements of narrow and broadband sound transmission at frequencies from 100 Hz to 1 kHz in these regions are consistent with waveguide calculations based on depth and frequency dependent sound speed, attenuation and density profiles. Theoretical predictions for the frequency dependence of attenuation vary from quadratic for the porous media model of M.A. Biot to linear for various competing models. Results from experiments performed under known conditions with sandy bottoms, however, have agreed with attenuation proportional to f1.84, which is slightly less than the theoretical value of f2 [Zhou and Zhang, J. Acoust. Soc. Am. 117, 2494]. This dissertation presents a reexamination of the fundamental considerations in the Biot derivation and leads to a simplification of the theory that can be coupled with site-specific, depth dependent attenuation and sound speed profiles to explain the observed frequency dependence. Long-range sound transmission measurements in a known waveguide can be used to estimate the site-specific sediment attenuation properties, but the costs and time associated with such at-sea experiments using traditional measurement techniques can be prohibitive. Here a new measurement tool consisting of an autonomous underwater vehicle and a small, low noise, towed hydrophone array was developed and used to obtain accurate long-range sound transmission measurements efficiently and cost effectively. To demonstrate this capability and to determine the modal and intrinsic attenuation characteristics, experiments were conducted in a carefully surveyed area in Nantucket Sound. A best-fit comparison between measured results and calculated results, while varying attenuation parameters, revealed the estimated power law exponent to be 1.87 between 220.5 and 1228 Hz. These results demonstrate the utility of this new cost effective and accurate measurement system. The sound transmission results, when compared with calculations based on the modified Biot theory, are shown to explain the observed frequency dependence.

Magnetic resonance water proton relaxation in protein solutions and tissue: T(1rho) dispersion characterization.

BACKGROUND: Image contrast in clinical MRI is often determined by differences in tissue water proton relaxation behavior. However, many aspects of water proton relaxation in complex biological media, such as protein solutions and tissue are not well understood, perhaps due to the limited empirical data. PRINCIPAL FINDINGS: Water proton T(1), T(2), and T(1rho) of protein solutions and tissue were measured systematically under multiple conditions. Crosslinking or aggregation of protein decreased T(2) and T(1rho), but did not change high-field T(1). T(1rho) dispersion profiles were similar for crosslinked protein solutions, myocardial tissue, and cartilage, and exhibited power law behavior with T(1rho)(0) values that closely approximated T(2). The T(1rho) dispersion of mobile protein solutions was flat above 5 kHz, but showed a steep curve below 5 kHz that was sensitive to changes in pH. The T(1rho) dispersion of crosslinked BSA and cartilage in DMSO solvent closely resembled that of water solvent above 5 kHz but showed decreased dispersion below 5 kHz. CONCLUSIONS: Proton exchange is a minor pathway for tissue T(1) and T(1rho) relaxation above 5 kHz. Potential models for relaxation are discussed, however the same molecular mechanism appears to be responsible across 5 decades of frequencies from T(1rho) to T(1).

Water sorption/desorption in polyacid-modified composite resins for dentistry

The water sorption and desorption behaviour of three commercial polyacid-modified composite resins used in clinical dentistry have been studied in detail. Cured specimens of each material were subjected to two successive water uptake cycles in an atmosphere of 93% relative humidity, with one intervening desorption cycle in a desiccating atmosphere over concentrated sulfuric acid. Specimens were found to absorb and desorb water according Fick's law until Mt/M(infinity) values of approximately 0.5. Diffusion rates for uptake varied between cycles, ranging from 2.37-4.53 x 10(-9 )cm(2) s(-1) for 1st cycle to 0.85-2.72 x 10(-8 )cm(2 )s(-1) for 2nd cycle. Desorption rates were similar to those for 2nd cycle sorption, and ranged from 0.86 to 5.47 x 10(-8 )cm(2 )s(-1). Equilibration times for 1st cycle water uptake were greater than for 2nd cycle sorption and for desorption and overall the behaviour of polyacid-modified composites in a high humidity atmosphere was similar to that of conventional composites in water. It is concluded that the hydrophilic components of the former do not bring about an enhanced rate of water transport.

Kinetic studies of water uptake and loss in glass-ionomer cements

The water sorption and desorption behaviour of three commercial glass-ionomer cements used in clinical dentistry have been studied in detail. Cured specimens of each material were found to show slight but variable water uptake in high humidity conditions, but steady loss in desiccating ones. This water loss was found to follow Fick's law for the first 4-5 h. Diffusion coefficients at 22 degrees C were: Chemflex 1.34 x 10(-6) cm(2) s(-1), Fuji IX 5.87 x 10(-7) cm(2) s(-1), Aquacem 3.08 x 10(-6) cm(2) s(-1). At 7 degrees C they were: Chemflex 8.90 x 10(-7) cm(2) s(-1), Fuji IX 5.04 x 10(-7) cm(2) s(-1), Aquacem 2.88 x 10(-6) cm(2) s(-1). Activation energies for water loss were determined from the Arrhenius equation and were found to be Chemflex 161.8 J mol(-1), Fuji IX 101.3 J mol(-1), Aquacem 47.1 J mol(-1). Such low values show that water transport requires less energy in these cements than in resin-modified glass-ionomers. Fick's law plots were found not to pass through the origin. This implies that, in each case, there is a small water loss that does not involve diffusion. This was concluded to be water at the surface of the specimens, and was termed "superficial water". As such, it represents a fraction of the previously identified unbound (loose) water. Superficial water levels were: Chemflex 0.56%, Fuji IX 0.23%, Aquacem 0.87%. Equilibrium mass loss values were shown to be unaffected by temperature, and allowed ratios of bound:unbound water to be determined for all three cements. These showed wide variation, ranging from 1:5.26 for Chemflex to 1:1.25 for Fuji IX.

The kinetics of water loss from zinc phosphate and zinc polycarboxylate dental cements

The water desorption behaviour of three different zinc oxide dental cements (two polycarboxylates, one phosphate) has been studied in detail. Disc-shaped specimens of each material were prepared and allowed to lose water by being subjected to a low humidity desiccating atmosphere over concentrated sulfuric acid. In all three cements, water loss was found to follow Fick's second law for at least 6 h (until M(t)/M(infinity) values were around 0.5), with diffusion coefficients ranging from 6.03 x 10(-8 )cm(2 )s(-1) (for the zinc phosphate) to 2.056 x 10(-7 )cm(2 )s(-1) (for one of the zinc polycarboxylates, Poly F Plus). Equilibration times for desorption were of the order of 8 weeks, and equilibrium water losses ranged from 7.1% for zinc phosphate to 16.9% and 17.4% for the two zinc polycarboxylates.

Water transport in zinc oxy-chloride cements

The water uptake and water loss behaviour in three different formulations of zinc oxy-chloride cement have been studied in detail. Specimens of each material were subjected to a high humidity atmosphere (93% RH) over saturated aqueous sodium sulfate, and a low humidity desiccating atmosphere over concentrated sulfuric acid. In high humidity, the cement formulated from the nominal 75% ZnCl2 solutions gained mass, eventually becoming too sticky to weigh further. The specimens at 25% and 50% ZnCl2 by contrast lost mass by a diffusion process, though by 1 week the 50% cement had stated to gain mass and was also too sticky to weigh. In low humidity, all three cements lost mass, again by a diffusion process. Both water gain and water loss followed Fick's law for a considerable time. In the case of water loss under desiccating conditions, this corresponded to values of Mt/MĄ well above 0.5. However, plots did not go through the origin, showing that there was an induction period before true diffusion began. Diffusion coefficients varied from 1.56 x 10-5 (75% ZnCl2) to 2.75 x 10-5 cm2/s (50% ZnCl2), and appeared to be influenced not simply by composition. The drying of the 25% and 50% ZnCl2 cements in high humidity conditions occurred at a much lower rate, with a value of D of 2.5 x 10-8 cm2/s for the 25% ZnCl2 cement. This cement was found to equilibrate slowly, but total water loss did not differ significantly from that of the cements stored under desiccating conditions. Equilibration times for water loss in desiccating conditions were of the order of 2-4 hours, depending on ZnCl2 content; equilibrium water losses were respectively 28.8 [25% ZnCl2], 16.2 [50%] and 12.4 [75%] which followed the order of ZnCl2 content. It is concluded that the water transport processes are strongly influenced by the ZnCl2 content of the cement.

Cross-Border Environmental Governance and EC Law

This article examines the nature and scope of emerging cross-border participatory rights under European Community environmental law. It reviews the legal and political forces that have stimulated the development of such rights and also the specific nature of the rights conferred by three major legislative initiatives: the Community Directives on Environmental Impact Assessment, Integrated Pollution Prevention and Control, and the Water Framework Directive. The article concludes with a case study on Ireland which assesses the likely significance of these cross-border participatory rights for transboundary environmental governance in Ireland.

An investigation of possible mechanisms of the water-gas shift reaction over a ZrO2-supported Pt catalyst

The present work investigates the reactivity of the surface species observable by in situ DRIFTS formed over a Pt/ZrO2 during the water-gas shift (WGS) reaction. A DRIFTS cell/mass spectrometer system was operated at the chemical steady state during isotopic transients to yield information about the true nature (i.e., main reaction intermediate or spectators) of adsorbates. Only carbonyl and formate species were observed by DRIFTS under reaction conditions; the surface coverage of carbonate species was negligible. Isotopic transient kinetic analyses revealed that formates exchanged uniformly according to a first-order law, suggesting that most formates observed by DRIFTS were of the same reactivity. In addition, the time scale of the exchange of the reaction product CO2 was significantly shorter than that of the surface formates. Therefore, a formate route based on the formates as detected by DRIFTS can be ruled out as the main reaction pathway in the present case. The number of precursors of the reaction product CO2 was smaller than the number of surface Pt atoms, suggesting that carbonyl species or some \

Under-water scene investigation using ground penetrating radar (GPR) in the search for a sunken jet ski, Northern Ireland

A search for a submerged jet ski and the lost limb of its driver involved in a collision with a speedboat was made in a shallow lake in Northern Ireland. The location of both was crucial to establishing events at the time of the accident. Local intelligence suggested both objects were likely to be partially-buried by lacustrine silt. To avoid sediment churning, this required non-invasive, completely non-destructive assessment and mapping of the scene. A MALA RAMAC ground-penetrating radar system (GPR) mounted on floats for surveying from walkways and jetties or placed in a small rubber dinghy for offshore profiling was used. A grid was established and each line surveyed with 100, 200 and 400MHz antennae. In waters over 6m deep GPR data showed the form of the lake floor but excessive ringing occurred in the data. In waters less than 6m deep ringing diminished on both 100 and 200MHz data, the latter displaying the best trade-off between depth penetration and horizontal object resolution. 400MHz data failed to be of use in waters over 2m deep and at these depths showed only limited improvement of image quality compared to 200MHz data. Surface objects such as a wooden walkway caused interference on 200 and 400MHz data when antennae were oriented both normal and parallel to survey direction; this may be a function of the low attenuation of radar waves in freshwater, allowing excellent lateral and vertical radar wave penetration. On 200MHz data the damaged jet-ski was clearly imaged in a location that contradicted the speedboat driver's account of the accident.

Remediation technologies for heavy metal contaminated ground water

This is a major review work on ground water remediation since the earlier work of Mulligan et al published in 2001 in Engineering Geology Journal. This work resulted from the joint research project of QUB and University of Malaya on iron removal from groundwater for public water supply.

Limitations of instantaneous water quality sampling in surface-water catchments: Comparison with near-continuous phosphorus time-series data.

The validity of load estimates from intermittent, instantaneous grab sampling is dependent on adequate spatial coverage by monitoring networks and a sampling frequency that re?ects the variability in the system under study. Catchments with a ?ashy hydrology due to surface runoff pose a particular challenge as intense short duration rainfall events may account for a signi?cant portion of the total diffuse transfer of pollution from soil to water in any hydrological year. This can also be exacerbated by the presence of strong background pollution signals from point sources during low flows. In this paper, a range of sampling methodologies and load estimation techniques are applied to phosphorus data from such a surface water dominated river system, instrumented at three sub-catchments (ranging from 3 to 5 km2 in area) with near-continuous monitoring stations. Systematic and Monte Carlo approaches were applied to simulate grab sampling using multiple strategies and to calculate an estimated load, Le based on established load estimation methods. Comparison with the actual load, Lt, revealed signi?cant average underestimation, of up to 60%, and high variability for all feasible sampling approaches. Further analysis of the time series provides an insight into these observations; revealing peak frequencies and power-law scaling in the distributions of P concentration, discharge and load associated with surface runoff and background transfers. Results indicate that only near-continuous monitoring that re?ects the rapid temporal changes in these river systems is adequate for comparative monitoring and evaluation purposes. While the implications of this analysis may be more tenable to small scale ?ashy systems, this represents an appropriate scale in terms of evaluating catchment mitigation strategies such as agri-environmental policies for managing diffuse P transfers in complex landscapes.

Approaches to the Implementation of the Water Framework Directive: Targeting Mitigation Measures at Critical Source Areas of Diffuse Phosphorus in Irish Catchments

The Water Framework Directive (WFD) has initiated a shift towards a targeted approach to implementation through its focus on river basin districts as management units and the natural ecological characteristics of waterbodies. Due to its role in eutrophication, phosphorus (P) has received considerable attention, resulting in a significant body of research, which now forms the evidence base for the programme of measures (POMs) adopted in WFD River Basin Management Plans (RBMP). Targeting POMs at critical sources areas (CSAs) of P could significantly improve environmental efficiency and cost effectiveness of proposed mitigation strategies. This paper summarises the progress made towards targeting mitigation measures at CSAs in Irish catchments. A review of current research highlights that knowledge related to P export at field scale is relatively comprehensive however; the availability of site-specific data and tools limits widespread identification of CSA at this scale. Increasing complexity of hydrological processes at larger scales limits accurate identification of CSA at catchment scale. Implementation of a tiered approach, using catchment scale tools in conjunction with field-by-field surveys could decrease uncertainty and provide a more practical and cost effective method of delineating CSA in a range of catchments. Despite scientific and practical uncertainties, development of a tiered CSA-based approach to assist in the development of supplementary measures would provide a means of developing catchment-specific and cost-effective programmes of measures for diffuse P. The paper presents a conceptual framework for such an approach, which would have particular relevance for the development of supplementary measures in High Status Waterbodies (HSW). The cost and resources necessary for implementation are justified based on HSWs’ value as undisturbed reference condition ecosystems.