The high flow rate that results as fluid decompresses through the restrictor is arguably the single greatest problem with supercritical fluid extraction techniques. As a result of these high flow rates, solvent trapping is not efficient in many cases, and the more complicated sorbent trapping technique must be used. In addition, loss of the collection solvent may occur during the process making it difficult to work with small volumes, which are desirable from the standpoint of sensitivity, cost, and environmental concerns. Similarly, these high decompressed flows have made it difficult to directly interface supercritical fluid extraction methods with separation techniques. This is unfortunate as supercritical extractions are ideal for on-line coupling in other respects, such as the fact that the fluid becomes gaseous upon depressurization and that supercritical fluids generally extract less contaminant material. In this thesis we have shown that, by elevating the post-restrictor pressure, the decompressed flow rate can be reduced, and these problems can be minimized, considerably. Off-line trapping becomes much simpler when working at elevated pressures as the need for sorbent trapping is virtually eliminated and solvent trapping may be conducted with much less difficulty. Elevated post-restrictor pressures were found to be very beneficial for on-line work as well. SFE/GC was carried out with complete transfer of the extraction effluent to a capillary GC column, which has not previously been demonstrated. Likewise the use of an open-tubular column interface, maintained at moderately elevated pressures, allowed SFE/HPLC to be conducted with quantitative analyte transfer, even in the presence of 10% modifier. In all cases - but especially for the on-line methods - more practical extraction parameters were possible, including extraction vessel volume, extraction flow rate, and dynamic extraction time. Another benefit of elevating the post-restrictor pressure is that higher extraction flow rates will generally be possible. The benefits of this were not evaluated in the research presented here, however, the effect that the extraction flow rate can have on extraction time is considered, from a theoretical standpoint, in Chapter five. / Ph. D.

Doctor of Philosophy / Department of Entomology / Thomas W. Phillips / The phase-out of methyl bromide production, the most effective fumigant for the control of the ham mite, Tyrophagus putrescentiae (Schrank) (Acari: Acaridae), on dry-cured ham has necessitated the search for other management methods. The foundation of a successful management program is an effective monitoring program that provides information on pest presence and abundance over time and space to help in making management decisions. By using the standard trap made from disposable Petri dishes and a dog food-based bait, mite activity was monitored weekly in five dry-cured ham aging rooms from three commercial processing facilities from June 2012 to September 2013. Results indicated that mite numbers in traps in facilities typically had a pattern of sharp decline after fumigation, followed by a steady increase until the next fumigation. Average trap captures varied due to trap location, indicating that traps could be used to identify locations where mite infestation of hams may be more likely to occur. Experiments were also conducted in 6 m x 3 m climate-controlled rooms to determine the effects of some physical factors on trap capture. Factors such as trap design, trap location, trap distance, duration of trapping, and light conditions had significant effects on mite capture. Mites also responded differently to light emitting diodes of different wavelengths, either as a component of the standard trap or as a stand-alone stimulus to orientation. To determine the relationship between trap capture and mite density, experiments were carried out in the climate-controlled rooms. Mite density was varied but trap number remained constant for all mite densities. There was strong positive correlation between trap capture and mite density. In simulated ham aging rooms, the distribution of mites on hams was determined and different sampling techniques such as vacuum sampling, trapping, rack sampling, ham sampling and absolute mite counts from whole hams were compared and correlated. Results showed weak or moderate correlations between sampling techniques in pairwise comparisons. Two sampling plans were developed to determine the number of samples required to estimate mite density on ham with respect to fixed precision levels or to an action threshold for making pest management decisions. Findings reported here can help in the optimization of trapping and sampling of ham mite populations to help in the development of efficient, cost-effective tools for pest management decisions incorporated with alternatives to methyl bromide.

Bedload-trapping efficiencies for four types of pressure-difference bedload samplers – a standard Helley-Smith (intake-nozzle width and height of 76.2 mm x 76.2 mm), BLH-84 (76.2 mm x 76.2 mm), Elwha (203 mm x 102 mm) and Toutle River-2 (305 mm x 152 mm) a standard Helley-Smith, US BLH-84 (both with intake nozzle dimensions of 76.2 mm × 76.2 mm), Elwha (203 mm × 102 mm) and Toutle River-2 (TR-2; 305 mm × 152 mm) – were calculated from data collected during the StreamLab06 experiments in the St. Anthony Falls Laboratory Main Flume during January-March 2006. Sampler nozzle-flare ratios –the area of the nozzle's outlet divided by its inlet area – equaled 1.4 for all but the Helley-Smith sampler's nozzle-flare ratio of 3.22. A sampler's trapping coefficient quantifies its bedload-trapping efficiency. Technically supportable trapping coefficients are divided into raw trapping rates measured by the sampler to produce "true" bedload-transport rates equivalent to that which was inferred to have occurred in the absence of the sampler. Six combinations of sampler and bed types were tested; the BLH-84, Elwha, and Helley-Smith samplers were deployed atop a sand bed (D50 = 1.0 mm) during five steady flows ranging from 2.0-3.6 m3/s. The BLH-84, Elwha, and TR-2 samplers were deployed atop a gravel bed (D50 = 11.2 mm) at four steady flows ranging from 4.0-5.5 m3/s. Thirty-seven trials – repeated manual at-a-point deployments of a given bedload sampler for a given steady flow and bed type – took place. Trapping coefficients were calculated for each sampler and bed type in which it was deployed. Ergo, two of the samplers – the BLH-84 and Elwha – were each assigned two trapping efficiencies for sampling on a sand versus a gravel bed. These data were evaluated using four analytical methods: Ratio of Averages: This relatively simple and straight-forward method required calculating averages of bedload-transport rates derived for each of the 37 trials for a given bedload sampler and for up to nine combinations of weigh pans and time intervals. The computations were performed using untransformed data. Average of Ratios: This more complex method using real-space trapping data involved developing average transport rates from selected pan data for each bedload sample. Pan transport-averages were calculated for each interval equal to the duration of a single at-a-point bedload measurement, ranging from 15-180 seconds. Ratios (coefficients) were calculated by dividing each interval average into the single-sample trap rate. Those ratios were then averaged to produce a single trapping coefficient for the trial and then combined into a single average for each bedload-sampler/bed type/flow combination. Modified Thomas and Lewis Model (1993): The Thomas-Lewis Model was revised to operate using untransformed data in addition to cube-root transformed data (thus, the third and fourth analytical methods used, respectively), and to use nine pan-window combinations to calculate trapping coefficients. The original 3-step model required first regressing cube root-transformed sampler data on time-window averaged pan transport rates. The second step squared the regression residuals from the first step on the variance of the cube root of the interval-mean transport rate for the time window. The predicted values from the second-step regression were inverted and used as weights to re-estimate the first-step regression. Generalized trapping-coefficient calculations based on results from the four analytical methods for the bed-types in which the samplers were deployed follow: • BLH-84 Sampler: A 0.83 sand-bed trapping coefficient and 0.87 gravel-bed coefficient, which could be averaged to a single coefficient of 0.85. • Elwha Sampler: A 1.67 sand-bed trapping coefficient and 1.54 gravel-bed coefficient, which could be averaged to a single coefficient of 1.6 • Helley-Smith Sampler: The 3.11 sand-bed trapping coefficient could be applied as such or reasonably simplified to a value of 3.0, and • TR-2: The gravel-bed trapping coefficient equaled 1.70. An unadjusted bedload-trapping rate calculated from a sample collected by a given sampler can be divided by its trapping coefficient(s) to obtain the most reliable transport-rate value. / Ph.D.

In the past decades, numerous single-molecule techniques have been developed to investigate individual bio-molecules and cellular machines. While a lot is known about the structure, localization, and interaction partners of such molecules, much less is known about their mechanical properties. To investigate the weak, non-covalent interactions that give rise to the mechanics of and between proteins, an instrument capable of resolving sub-nanometer displacements and piconewton forces is necessary. One of the most prominent biophysical tool with such capabilities is an optical tweezers. Optical tweezers is a non-invasive all-optical technique in which typically a dielectric microsphere is held by a tightly focused laser beam. This microsphere acts like a microscopic, three-dimensional spring and is used as a handle to study the biological molecule of interest. By interferometric detection methods, the resolution of optical tweezers can be in the picometer range on millisecond time scales. However, on a time scale of seconds—at which many biological reactions take place—instrumental noise such as thermal drift often limits the resolution to a few nanometers. Such a resolution is insufficient to resolve, for example, the ångstrom-level, stepwise translocation of DNA-binding enzymes corresponding to distances between single basepairs of their substrate. To reduce drift and noise, differential measurements, feedback-based drift stabilization techniques, and ‘levitated’ experiments have been developed. Such methods have the drawback of complicated and expensive experimental equipment often coupled to a reduced throughput of experiments due to a complex and serial assembly of the molecular components of the experiments. We developed a high-resolution optical tweezers apparatus capable of resolving distances on the ångstrom-level over a time range of milliseconds to 10s of seconds in surface-coupled assays. Surface-coupled assays allow for a higher throughput because the molecular components are assembled in a parallel fashion on many probes. The high resolution was a collective result of a number of simple, easy-to-implement, and cost-efficient noise reduction solutions. In particular, we reduced thermal drift by implementing a temperature feedback system with millikelvin precision—a convenient solution for biological experiments since it minimizes drift in addition to enabling the control and stabilization of the experiment’s temperature. Furthermore, we found that expanding the laser beam to a size smaller than the objective’s exit pupil optimized the amount of laser power utilized in generating the trapping forces. With lower powers, biological samples are less susceptible to photo-damage or, vice versa, with the same laser power, higher trapping forces can be achieved. With motorized and automated procedures, our instrument is optimized for high-resolution, high-throughput surface-coupled experiments probing the mechanics of individual biomolecules. In the future, the combination of this setup with single-molecule fluorescence, super-resolution microscopy or torque detection will open up new possibilities for investigating the nanomechanics of biomolecules.

In the past decades, numerous single-molecule techniques have been developed to investigate individual bio-molecules and cellular machines. While a lot is known about the structure, localization, and interaction partners of such molecules, much less is known about their mechanical properties. To investigate the weak, non-covalent interactions that give rise to the mechanics of and between proteins, an instrument capable of resolving sub-nanometer displacements and piconewton forces is necessary. One of the most prominent biophysical tool with such capabilities is an optical tweezers. Optical tweezers is a non-invasive all-optical technique in which typically a dielectric microsphere is held by a tightly focused laser beam. This microsphere acts like a microscopic, three-dimensional spring and is used as a handle to study the biological molecule of interest. By interferometric detection methods, the resolution of optical tweezers can be in the picometer range on millisecond time scales. However, on a time scale of seconds—at which many biological reactions take place—instrumental noise such as thermal drift often limits the resolution to a few nanometers. Such a resolution is insufficient to resolve, for example, the ångstrom-level, stepwise translocation of DNA-binding enzymes corresponding to distances between single basepairs of their substrate. To reduce drift and noise, differential measurements, feedback-based drift stabilization techniques, and ‘levitated’ experiments have been developed. Such methods have the drawback of complicated and expensive experimental equipment often coupled to a reduced throughput of experiments due to a complex and serial assembly of the molecular components of the experiments. We developed a high-resolution optical tweezers apparatus capable of resolving distances on the ångstrom-level over a time range of milliseconds to 10s of seconds in surface-coupled assays. Surface-coupled assays allow for a higher throughput because the molecular components are assembled in a parallel fashion on many probes. The high resolution was a collective result of a number of simple, easy-to-implement, and cost-efficient noise reduction solutions. In particular, we reduced thermal drift by implementing a temperature feedback system with millikelvin precision—a convenient solution for biological experiments since it minimizes drift in addition to enabling the control and stabilization of the experiment’s temperature. Furthermore, we found that expanding the laser beam to a size smaller than the objective’s exit pupil optimized the amount of laser power utilized in generating the trapping forces. With lower powers, biological samples are less susceptible to photo-damage or, vice versa, with the same laser power, higher trapping forces can be achieved. With motorized and automated procedures, our instrument is optimized for high-resolution, high-throughput surface-coupled experiments probing the mechanics of individual biomolecules. In the future, the combination of this setup with single-molecule fluorescence, super-resolution microscopy or torque detection will open up new possibilities for investigating the nanomechanics of biomolecules.

<div>A growing global population and improved standard of living in developing countries have resulted in an unprecedented increase in energy demand over the past several decades. While renewable energy sources are increasing, a huge portion of energy is still converted into useful work using heat engines. The combustion process in diesel and petrol engines releases carbon dioxide and other greenhouse gases as an unwanted side-effect of the energy conversion process. By improving the efficiency of internal combustion engines, more chemical energy stored in petroleum resources can be realized as useful work and, therefore, reduce global emissions of greenhouse gases. This research focused on improving the thermal efficiency of opposed-piston engines, which, unlike traditional reciprocating engines, do not use a cylinder head. The cylinder head is a major source of heat loss in reciprocating engines. Therefore, the opposed-piston engine has the potential to improve overall engine efficiency relative to inline or V-configuration engines.</div><div><br></div>The objective of this research project was to further improve the design of opposed-piston engines by using computational fluid dynamics (CFD) modeling to optimize the engine geometry. The CFD method investigated the effect of intake port geometry and exhaust piston lead angle on the scavenging process and in-cylinder turbulence. After the CFD data was analyzed, scavenging efficiency was found insensitive to transfer port geometry and exhaust piston lead angle with a maximum change of 0.61%. Trapping efficiency was altered exclusively by exhaust piston lead angle and changed from 18% to 26% as the lead angle was increased. The in-cylinder turbulence parameters of the engine (normalized swirl circulation, normalized tumble circulation, and normalized TKE) experienced more complex relationships. All turbulence parameters were sensitive to changing transfer port geometry and exhaust piston lead angle. Some examples of trends seen during the analysis include: an increase in normalized swirl circulation from 0.01 to 4.45 due to changes in swirl angle, a change in normalized tumble circulation from -28.52 to 21.11 as swirl angle increased, and an increase in normalized tumble circulation from 14.20 to 33.68 as exhaust piston lead angle was increased. Based on the present work, an optimum configuration was identified for a swirl angle of 15°, a tilt angle of 10°, and an exhaust piston lead angle of 20°. Future work includes expanding the numerical model’s domain to support a complete cylinder-port configuration, adding combustion products to the diffusivity equation in the UDF, and running additional test cases to describe the entire input space for the sensitivity analysis.<br>

Capillary trapping plays a central role in the geological storage of CO2, oil recovery, and water soil infiltration. The key aim of this study is to investigate the impact of surface properties (wettability, roughness, heterogeneous mineral composition) on the dynamics of quasi-static fluid displacement process and capillary trapping efficiency in porous medium. We concluded that for homogeneous wet smooth glass beads surfaces, a transition in fluid displacement pattern occurs from a compact (for θ < 90°; imbibition process) to a fractal front-pattern (for θ > 90°; drainage process) leading to a crossover in capillary trapping efficiency from zero to maximum. The impact of surface roughness on capillary trapping efficiency was also studied, and an opposite trends in terms of wettability dependency was observed. Rough natural sands surfaces depicts a non-monotonous wettability dependency, i.e. a transition from maximal trapping (for θ < 90°) to no-trapping occurs (at θ = 90°), followed by an increase to medium trapping (for θ > 90°). For a fractional-wet media, the percolating cluster of hydrophobic sediments (connected hydrophobic pathways) characterize the fluid displacement pattern and trapping efficiency.