Thesis (M.S.)--University of North Carolina at Wilmington, 2005. / Includes bibliographical references (leaves: [30]-33)

Erosion, transportation, and deposition of sediment into receiving waters can have substantial environmental and economic impacts. Sedimentation basins are a remediation technique used to limit sediment transport from earth disturbance activities. Retention efficiency is used as a measure of a sedimentation basin's effectiveness. Several factors influence retention efficiency including the type of principal spillway used. The most common spillway is the perforated riser which dewaters the basin throughout its entire vertical profile. However, a relatively new outlet device, the skimmer, has been developed, which dewaters the basin from the water surface. A laboratory study was conducted to compare the skimmer with the perforated riser for three different soil types and determine if there were any significant differences in the trapping efficiencies of the two outlets. The test basin dewatered over a three hour period. The parameters observed were dewatering rate, effluent sediment concentration, sediment loss rate, and retention efficiency. The skimmer treatments consistently had higher values of sediment retention efficiencies. A statistical analysis performed on the retention efficiency data showed that retention efficiency was not influenced by any combination of outlet and soil type and that outlet was significant at the 5% level. Overall, the skimmer outperformed the perforated riser for all soil types tested. Additionally, retention efficiencies were predicted for shorter dewatering times. The results indicated shorter dewatering times may have smaller impacts on the retention efficiency of basins where the skimmer is utilized rather than the perforated riser. / Master of Science

Thesis (M.S.)--University of North Carolina Wilmington, 2008. / Title from PDF title page (viewed May 27, 2009) Includes bibliographical references (p. 22-24)

Each of the studies conducted herein is related to best management practices for stormwater pollutant removal. This thesis is divided into two chapters. Chapter One details the development and functionality of a novel stormwater detention pond outlet, the solid state skimmer. The device is a perforated riser having no moving parts that is capable of draining detention ponds primarily from the topmost orifices. We found that such a device is capable of reducing effluent turbidity and sediment concentrations compared to a traditional riser outlet. Chapter Two describes a water quality monitoring study performed to show that a pervious concrete detention system can remove stormwater pollutants from parking lot runoff. The stormwater flowed across asphalt paving before infiltrating into the pervious concrete and an aggregate sub-base below. We sampled the runoff before it entered the pervious and after it passed through the detention system and found significant decreases in several pollutants.

In the southeastern United States, skimmer trawls, pusher-head trawls, wing nets, and small try nets (headrope length less than 12-ft (3.66-m)) are exempt from using a turtle excluder device (TED) and instead must adhere to tow time restrictions as a mode to mitigate sea turtle bycatch. However, observer and stranding data indicate that these tow times may often be exceeded and result in mortality of sea turtles. The National Marine Fisheries Service (NMFS) published a notice of proposed rulemaking in December 2016 to extend TED requirements to other trawl types, however there has been limited development of specialized TEDs for these smaller trawls. In anticipation of a regulatory change, we developed and identified multiple versions of a top-opening TED with a minimum width of 28-in (71-cm) and height of 24-in (61-cm) as the best option for small trawl gears. Prototypes were initially equipped within small try nets and tested for gear performance and sea turtle exclusion in Panama City, Florida. The final designs were then tested for target shrimp retention, bycatch reduction, and general usability of TEDs in the commercial fisheries. A paired comparison test was conducted in 8-ft (2.44-m) and 10-ft (3.05-m) try nets aboard the NMFS R/V Caretta, three commercial skimmer trawls in vesselsFarfantepenaeus duorarum) fishery. There was a general reduction of shrimp and bycatch averaging from a minimum loss of 3.31% in the Miami wing net fishery (FV FL-01) to 22.07% in the skimmer trawl fishery (FV LA-01). This dissertation research indicates that TEDs can function properly in small trawl types, however additional studies are recommended to minimize the shrimp loss and improve the overall TED effectiveness specific to each fishery and trawl type evaluated.

Positive-ion electrospray ionisation Fourier transform ion cyclotron resonance and ion trap mass spectrometry have been used to investigate the reactions of the flavonoids 3-hydroxyflavone, 5-hydroxyflavone, 5-methoxyflavoe, quercetin, quercitrin and rutin with monovalent Li+, Na+, K+ and Cs+, divalent Cu2+, Zn2+ and Pb2+ and trivalent La3+ and Eu3+ metal cations. The effect of capillary-skimmer potential difference and the ion residence time in the hexapole ion trap of the Fourier transform ion cyclotron resonance mass spectrometer are systematically investigated for the flavonoid-alkali and divalent metal ion experiment. It is observed that these variables impact significantly on the type of ions observed in the ESI experiments and hence the mass spectra. The binding selectivity of alkali metal ions towards 3-hydroxyflavone, 5-hydroxyflavone and 5-methoxyflavone are determined using the results from FTICR mass spectrometry experiments. The selectivity order follows the order Li+>Na+>K+ for individual flavonoids. Collision-induced dissociation experiments are carried out by Fourier transform ion cyclotron resonance and ion trap mass spectrometry to compare the fragmentation behaviour of metal-flavonoid complexes. Low energy collision-induced dissociation experiments of the [2L+M]+ for 3-hydroxyflavone, 5-hydroxyflavone and 5-methoxyflavone alkali metal complexes show the loss of ligand only. When the energy is increased only the lithiated dimer [2L+Li]+ for 5-methoxyflavone shows the loss of methyl radical along with the ligand. For quercitrin the predominant dissociation pathways are the loss of rhamnose for Li+, Na+ and K+ complexes although aglycone loss is also observed for the K+ complex. The favourable dissociation pathways for rutin are the loss of disaccharide, aglycone and rhamnose for the Na+ complex and the loss of disaccharide for the K+ complex. Collision-induced dissociation data are also used to determine the threshold dissociation energies for displacement of one flavonoid ligand from alkali metal flavonoid complexes. The threshold dissociation energies for loss of one ligand from [2L+M]+ of 5-methoxyflavone and quercitrin follow the order Li+ > Na+ > K+, rutin follows the order Na+ > K+ > Li+ , and 3-hydroxyflavone and 5-hydroxyflavone follow the order Li+ > Na+. For the same metal cation experiment, 5-methoxyflavone system has the highest dissociation energy compared to the 3-hydroxyflavone and 5-hydroxyflavone experiment. Preliminary DFT calculations show that the calculated dissociation energies follow the same trend as the experimental dissociation energies for the simple flavonoid alkali metal cation experiments. For 5-methoxyflavone-divalent metal cation (Zn2+, Cu2+ and Pb2+) complexes loss of methyl radical is the common process. CO loss is also observed for the Zn2+ complex whereas CHO and H2O losses are observed for Cu2+. For 3-hydroxyflavone and 5-hydroxyflavone divalent metal cation experiments loss of ligand is the dominant process. Zn2+ and Cu2+ complexes also show CO loss. La3+ and Er3+ with the same flavonoids show the ligand as the dominant product. For quercetin-divalent metal cation experiment, ligand loss is the dominant process. For quercitrin and rutin various dissociation products are observed where the dissociation occurs via the loss of the rhamnose and/or the disaccharide moieties. Similar dissociation patterns are also observed for La3+ and Er3+ complexes for quercitrin and rutin.

Wood consists not only of cellulose, lignin and hemicellulose but also of so called extractives which includes fats and acids and these components are separated in the mill from the black liquor. These extractives are in the mill denoted as tall oil soap. Tall oil has a large field of applications like chemicals and fuel and as it is produced to the atmosphere if it can replace oil and thus reduce the oil consumption. Tall oil soap is separated from the black liquor in a skimmer and the focus of this thesis was to examine the effect of air injection and the soap layer thickness on the soap separation efficiency in a skimmer. The work was focused on in analyzing the soap content of the inlet and outlet black liquor flow of the skimmer and to detect if an enhancement has been achieved with the two mentioned methods. The reason for the pulp mill to improve the soap separation efficiency was to decrease the risk of foaming and fouling in the evaporator but also to be able to increase the production of tall oil. The air injection gave a 41% improvement of the soap separation efficiency and further improvements are probably possible to achieve. The air injection flow was about 7 l air /m3 liquor in the black liquor feed. The airflow lowers the density of soap, creating a greater difference in density between soap and black liquor and this improves the separation efficiency. A thicker soap layer could increase the likelihood for soap drops to raise and reach the soap-liquor interface, because the soap drops have the tendency to bind with each other and will be separated from the liquor instead of following with the skimmed liquor outlet (fig. i.2). However, this study shows no indication of improvement with thicknesses that exceeds 0,75- 3,5 m which also endanger the skimmer due to overflow from the skimmer or create a short circuit between the in- and the outlet black liquor flow.

Mit zeitaufgelöster Massenspektrometrie untersuchen wir die Winkelverteilung von Kohlendioxid-Monomeren bei der Streuung von Kohlendioxid-Clustern an einer Si(111)/Siliciumdioxid-Oberfläche unter Ultrahochvakuum-Bedingungen. Die präsen- tierten Studien decken eine große Breite der Clustergrößen, , 1,000 < N < 200,000 Moleküle pro Partikel, ab. Dabei liegt der Fokus auf dem Einfluss der Ausgangsentropie, die durch eine präzise Einstellung des Ausgangsdruckes und der Düsentemperatur realisiert wurde. Es zeigt sich, daß die Streuverteilung direkt den Expansionspfad widerspiegelt, wodurch eine Unterscheidung zwischen Clustern, die durch eine Expansion auf der gasförmigen oder flüssigen Seite des kritischen Punktes und der metstabilen Phase ent- stehen, ermöglicht wird. Um bei den hohen Teilchendichten eine verlässliche Aussage zu ermöglichen, wurden im Vorfeld die Eigenschaften gepulster Molekularstrahlen untersucht, insbesondere deren Abhängigkeit vom Restgasdruck und den Wechselwirkungen mit Strahlblenden. Hierzu diente die elektronische Anregung eines Helium-Strahls. Die Optimierung der Randbedingungen ermöglicht viel kältere Strahlen, so dass Helium-Cluster sogar bei einer Ausgangstemperatur von T = 410.0 K gefunden werden können. Dieses Ergebnis ist für die Cluster-Forschung, die Molekülspektroskopie und Experimente in der Quantenphysik von Bedeutung. / Employing pulsed high-pressure supersonic jet expansion and a dedicated setup for the experimental investigation of chemical processes occurring between neutral, van der Waals bound clusters and a solid surface, we report on the angular distribution observed for large carbon dioxide clusters scattered off a Si(111)/Silicon Dioxide surface under ultrahigh vacuum conditions. Scattered particles are detected using angle and time resolved mass spectrometry. The presented studies cover a broad range of cluster sizes, , 1,000 < N < 200,000 molecules per particle. The focus is on the influence of source entropy, realized by accurately setting stagnation pressure and temperature. This thesis demonstrates a dependence of the angular distribution of scattered carbon dioxide monomers on source conditions: the scattering distribution directly reflects the expansion path, allowing us to distinguish between clusters generated via expansion on the gaseous or on the liquid side of the critical point, and an intermediate regime where the expansion passes the metastable gas-liquid region. To optimize the supersonic beam, on the other hand, we reveal a substantial influence of residual gas pressure and beam–skimmer interactions on beam properties, particularly the minimum attainable translational temperature in a model system. This study contains the systematic investigation of supersonic jet expansions of helium, employing the variable distance between the Even-Lavie valve and different types of skimmers. Utilizing the ultra-high precision time-of-flight measurements of electronically tagged particles, the terminal velocities and the spread of particles allow us to correspondingly obtain much colder beams with the same source conditions. As a result, helium clusters can be found even in the jet expansion from a source temperature of T = 410.0 K. This knowledge is of particular interest to cluster science, molecular spectroscopy, and quantum physics.