Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Jingguang G. Chen, Dept. of Chemical Engineering. Includes bibliographical references.

Estimation of the transport of persistent organic pollutants via air-water exchange requires precise field concentrations from advanced experimental techniques and adequate physic-chemical parameters generated from proper methods. In this study, concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) in the ambient air and water column of Kaohsiung Harbor lagoon were measured and used to determine the air-water exchange fluxes of these compounds from December, 2003 to January, 2005. The Whitman¡¦s thin-film model was used by taking temperature and salinity corrected Henry¡¦s law constants into the model to calculate the fluxes. In addition, particulate concentrations and composition in the ambient air and water column were used to apportion PAH sources and dry particle deposition of PAHs, PCBs and HCB. Instantaneous air-water exchange fluxes of PAHs, PCBs and HCB were calculated from twenty-two pairs of air and water samples. The highest net volatile (+3560 ng m-2 day-1) and absorptive (-1230 ng m-2 day-1) PAH fluxes in this study were both obtained from the three-ring PAH, phenanthrene on April 7 and January 27 in 2004, respectively. Differences of flux magnitude and direction between dry and rain season were obvious for PAHs in this study. Most net fluxes of PCB homologues and HCB in this study are from water to air (net volatilization). The highest net volatile flux observed was +172 ng m-2 day-1 (dichlorobiphenyl) in December, 2003 due to elevated wind speed and dissolved concentration, while the only net absorptive flux observed in this study was -0.03 ng m-2 day-1 (dichlorobiphenyl) in January, 2004. Mean daily PAH diffusive fluxes were -727 ng m-2 day-1 influx in dry season but +808 ng m-2 day -1 efflux in rain season and integrated 3.6 kg and 4.0 kg of PAHs were absorbed into and emitted from harbor lagoon surface waters in dry and rain seasons, respectively. The net PCBs and HCB fluxes suggest that the annual sum of 69 PCBs and HCB measured in this study were mainly volatile (57.4 and 28.3 ¡Ñ103 ng m-2 yr-1, respectively) and integrated 1.5 kg and 0.76 kg of PCBs and HCB emitted from harbor lagoon surface waters to ambient atmosphere in the year. Sources apportionment by the isomer ratios, PAHs in the air phase were mainly from grass, wood and coal combustion and some from liquid fuel combustion. Unlike that in air phase, fluoranthene / fluoranthene + pyrene ratios of water phase suggest PAHs were from incomplete-combusted fuel particles emitted from vehicle exhaust. Principal component analysis (PCA) extracted three meaningful PCs for air and water samples, respectively. For the air samples, the three major sources suggested by three sources are vehicular emissions, volatilization to the air from contaminated soil or waters and the coal-burning emission. Among the water samples, the three major sources suggested by three sources are vehicular emissions, oil spill source and coal-burning emission. Air particulate concentrations of PAHs, PCBs and HCB were also used to calculate their dry particle deposition. Throughout our sampling campaigns, PAH dry particle fluxes were quite comparable to fluxes of air-water exchange. On the contrary, PCB and HCB dry particle deposition flux were negligible comparing to their air-water exchange fluxes. Our results suggest PAHs exhibits strong absorptive or weaker volatile fluxes in the dry season but the opposite in the rain season. However, for PCBs and HCB, Kaohsiung Harbor water is potentially an important source to ambient air.

Persistent organic pollutants (POPs) were widely distributed in the environment, and may cause hazardous effects to human health. Among these pollutants, polychlorinated biphenyls (PCBs), due to their toxicity and bioaccumulation, have been banned in the mid 1970s in most countries. They are ubiquitous and highly persistent, and therefore, PCBs are of most concern for their potential to be globally transported through air-water exchange. Previous studies such as Fang et al.¡]2008¡^ and Chen¡]2010¡^have studied the air-water exchange of PCBs in Kaohsuing Harbor. This study not only continued monitoring this area but also included Gao-Ping coastal areas and Lanyu Island in order to determine the air-water exchange fluxes of PCBs in harbor and coastal area. The aim of this study was to determine the magnitude of PCB air-water exchange fluxes and dry deposition fluxes by measuring the gas/particle phase concentrations in ambient air and dissolved/particle phase concentrations in water column, and to analyze the compositional patterns of PCB homologs. Hierarchical cluster analysis (HCA) and principal components analysis (PCA) were performed with compositional patterns of commercial products such as Aroclor mixtures to gain a better understanding of pollution topography for PCBs . The concentrations of £UPCBs in the ambient air ranged from 116 to 439 pg m-3, with an average concentration of 164 pg m-3 . The average PCB concentrations in gas and particle phase were 161 pg m-3 and 2.91 pg m-3, respectively. The concentrations of £UPCBs in water column ranged from 14.1 to 1750 pg L-1, with an average concentration of 233 pg L-1. The average PCB concentrations in dissolved and particle phase were 162 pg L-1 and 70.4 pg L-1, respectively. The highest gaseous concentration of £UPCBs was observed in GRE in November, suggesting that wind direction and Linyuan Industrial Park may be the major contributor of PCBs there. However, the highest dissolved concentration of £UPCBs was found in KHH in August, indicating that rainfall and runoff of Typhoon Morakot were evident in source. Results from HCA, PCA and compositional patterns indicate that lower chlorinated congeners (dichlorobiphenyls to tetrachlorobiphenyls) were predominant in the gas and dissolved phase of ambient air and water column. In particle phase of ambient air and water column, PCB compositions were dominated by higher chlorinated congeners (tetrachlorobiphenyls to hexachlorobiphenyls). TEQ was used to determine the level of pollution for environment and human health. The average TEQ was 0.0008 pg-TEQ m-3 in gas-phase of ambient air and was 0.0006 pg-TEQ L-1 in dissolved phase in water. PCB114 was observed to be the predominant congener in this study. The average flux of air-water exchange was ¡Ï31.5 ng m-2 day-1, and was much higher than the average flux of dry deposition (¡Ð0.54 ng m-2 day-1). The net PCB fluxes in KHH suggest that annual air-water exchange was ¡Ï40.2 mg m-2 yr-1 and estimated yearly, 0.5 kg of PCBs were emitted from water column of Kaohsiung harbor to the ambient atmosphere.

Atmospheric transport and air-water exchange of organochlorine pesticides (OCPs) were investigated in temperate North America and the Arctic. OCPs studied were hexachlorocyclohexanes (HCHs, a-, b- and g-isomers), components of technical chlordane (trans- and cis-chlordane, trans-nonachlor), dieldrin, heptachlor exo-epoxide and toxaphene. Air and water samples were taken on cruises in the Great Lakes and Arctic to determine concentrations and gas exchange flux direction and magnitude. The Henry’s law constant, which describes the equilibrium distribution of a chemical between air and water, was determined for several OCPs as a function of temperature and used to assess the net direction of air-water exchange. Air samples were collected in Alabama to investigate southern U.S. sources of OCPs. Chemical markers (isomers, and enantiomers of chiral OCPs) were employed to infer sources and trace gas exchange. Elevated air concentrations of toxaphene and chlordanes were found in Alabama relative to the Great Lakes, indicating a southern U.S. source. Profiles of toxaphene compounds in air were similar to those in soil by being depleted in easily degraded species, suggesting that soil emissions control air concentrations. Gas exchange fluxes in the Great Lakes indicated near-equilibrium between air and water with excursions to net volatilization or deposition. Net volatilization of a-HCH from the Arctic Ocean was traced by evasion of non-racemic a-HCH into the atmosphere.

In turbulent water flows, large quantities of air bubbles are entrained at the free-surfaces. Practical applications of gas-liquid bubbly flows are found in Chemical, Civil, Environmental, Mechanical, Mining and Nuclear Engineering. Air-water flows are observed in small-scale as well as large-scale flow situations. Typical examples include thin circular jets used as mixing devices in chemical plants (Qw = 0.001 L/s, diameter = 1 mm) and spillway flows (Qw larger than 10,000 m3/s, flow thickness over 10 m). In each case, however, the interactions between the entrained air bubbles and the turbulence field are significant. The present manuscript regroups a collection of one book and 43 articles on the study of air bubble entrainment in turbulent flows. The work aims to gain a better understanding of the basic mechanisms of gas entrainment and the nteractions between entrained gas bubbles and the turbulence. It has been the purpose of the research work to assess critically the overall state of this field, to present new analysis and experimental results, to compare these with existing data, and to present new compelling conclusions regarding momentum and void fraction development of air-water gas-liquid bubbly flows. The manuscript presents a comprehensive analysis of the air entrainment processes in free-surface turbulent flows. The air-water flows are investigated as homogeneous mixtures with variable density. The variations of fluid density result from the non-uniform air bubble distributions and the turbulent diffusion process. Several types of air-water free-surface flows are studied : plunging jet flows, open channel flows, and turbulent water jets discharging into air.

Stepped chutes have been used as hydraulic structures for more than 3.5 millennia for different purposes: For example, to dissipate energy, to enhance aeration rate in the flow and to comply with aesthetical functions. They can be found acting as spillways in dams and weirs, as energy dissipators in artificial channels, gutters and rivers, and as aeration enhancers in water treatment plants and fountains. Spillways are used to prevent dam overtopping caused by floodwaters. Their design has changed through the centuries. In ancient times, some civilizations used steps to dissipate energy in open channels and dam over-falls in a similar fashion as natural cascades. However, in the first half of the twentieth century, the use of concrete became popular and the hydraulic jump was introduced as an efficient energy dissipator. In turn, the use of a stepped geometry became obsolete and was replaced with smooth chutes followed by hydraulic jump stilling basins. In recent years, new construction techniques and materials (Roller Compacted Concrete RCC, rip-rap gabions, wire-meshed gabions, etc.) together with the development of new applications (e.g. re-aeration cascades, fish ladders and embankment overtopping protection or secondary spillways) have allowed cheaper construction of stepped chutes, increasing the interest in stepped chute design. During the last three decades, research in the hydraulics of stepped spillways has been very active. However, studies prior to 1993 neglected the effect of free-surface aeration. A number of studies since this time have focused on air-water flows in steep chutes (θ ≈ 50o). But experimental data is still scarce, and the hydraulic performance of stepped cascades with moderate slope is not yet understood. This study details an experimental investigation of physical air-water flow characteristics down a stepped spillway conducted in two laboratory models with moderate slopes: the first model was a 3.15 m long stepped chute with a 15.9o slope comprising two interchangeable-height steps (h = 0.1 m and h = 0.05 m); the second model was a 2.5 m long, stepped channel with a 21.8o slope comprising 10 steps (h = 0.1 m). Different arrangements of turbulence manipulators (vanes) were also placed throughout the chute in the second model. A broad range of discharges within transition and skimming flow regimes was investigated to obtain a reliable representation of the air-water flow properties. Measurements were conducted using single and double tip conductivity probes at multiple span wise locations and at streamwise distances along the cavity between step edges to obtain a complete three-dimensional representation of the flow. Although the present study was conducted for two moderate slope chutes (θ = 15.9º & 21.8o), it is believed that the outcomes are valid for a wider range of chute geometry and flow conditions. The purpose of this study is to improve the understanding of turbulent air-water flows cascading down moderate slope stepped chutes, and gain new understandings of the interactions between aeration rate, flow turbulence and energy dissipation; scale effects are also investigated. The study provides new, original insights into air-water turbulent flows cascading down moderate slope stepped spillways not foreseen in prior studies, thus contributing to improve criterion designs. It also presents an extensive experimental database (available in a CD-ROM attached at the end of this thesis) and a new design criterion that can be used by designers and researchers to improve the operation of stepped chutes with moderate slopes. The present thesis work included a twofold approach. Firstly, the study provided a detailed investigation of the energy dissipative properties of a stepped channel, based upon detailed airwater flow characteristics measurements conducted with sub-millimetric conductivity probes. Secondly, the study focused on the microscopic scale properties of the airwater flow, using the experimental data to quantify the microscopic scale physical processes (e.g. momentum transfer, shear layer development, vertical mixing, airbubbles/ water-droplets break-up and coalescence etc.) that are believed to increase the flow resistance in stepped canals. The study highlighted the tridimensionality of skimming flows and hinted new means of enhancing flow resistance by manipulating turbulence in the stepped chute. Basic dimensional analysis results emphasized that physical modelling of stepped chutes is more sensitive to scale effects than classical smooth-invert chute studies and thus suggested that the extrapolation of results obtained from heavily scaled experimental models should be avoided. The present study also demonstrated that alterations of flow recirculation and fluid exchanges between free-stream and cavity flow affects drastically form losses and in turn the rate of energy dissipation. The introduction of vanes demonstrated simple turbulence manipulation and form drag modification that could lead to more efficient designs in terms of energy rate dissipation without significant structural load on the stepped chute.

Thesis (PhD.(Chemistry)--University of Pretoria, 2008. / On title page: Submitted in partial fulfilment of the requirements for the degree Doctor of Philosophy in Chemistry in the faculty of Natural and Agricultural Sciences of the University of Pretoria. Includes bibliographical references.

No description available.

The rise of soft robots poses a promising revolution across a variety of fields, such as invasive surgical procedures or aquatic animal monitoring and sampling, by providing a softer solution to delicate problems. However, with their youth comes a need for growth, particularly in regard to increasing mobility in aquatic environments seeing as motion is often slow and belabored. Additionally, exit strategies in breaking the air-water interface are not thoroughly explored to date. To address these challenges, this study looks to bioinspiration for the answer in the form of Emperor Penguins. By utilizing microbubbles in their plumage to decrease drag forces on their bodies, Emperor Penguins are able to propel themselves out of the water to heights not theoretically achievable through buoyancy alone. Not only is the strategy highly effective, it lends well to the soft robotic field as pneumatic actuation is a commonly used mechanism of locomotion. To explore this behavior and simulate its effects, this study tests a hollow silicone ellipsoid with hole punctures applied to its surface for microbubble release. Bubble characteristics such as separation point, bubble diameter, and downstream bubble expansion were monitored when subjected to a fluid flow to determine ideal air pressure through the ellipsoid body. Drag reduction is tested by measuring the robot’s leap height out of the water.

No description available.