Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

Laser Thomson scattering measurements of electron temperature and density in a Hall-effect plasma

Hall-effect thrusters (HETs) are compact electric propulsion devices with high specific impulse used for a variety of space propulsion applications. HET technology is well developed but the electron properties in the discharge are not completely understood, mainly due to the difficulty involved in performing accurate measurements in the discharge. Measurements of electron temperature and density have been performed using electrostatic probes, but presence of the probes can significantly disrupt thruster operation, and thus alter the electron temperature and density. While fast-probe studies have expanded understanding of HET discharges, a non-invasive method of measuring the electron temperature and density in the plasma is highly desirable. An alternative to electrostatic probes is a non-perturbing laser diagnostic technique that measures Thomson scattering from the plasma. Thomson scattering is the process by which photons are elastically scattered from the free electrons in a plasma. Since the electrons have thermal energy their motion causes a Doppler shift in the scattered photons that is proportional to their velocity. Like electrostatic probes, laser Thomson scattering (LTS) can be used to determine the temperature and density of free electrons in the plasma. Since Thomson scattering measures the electron velocity distribution function directly no assumptions of the plasma conditions are required, allowing accurate measurements in anisotropic and non-Maxwellian plasmas. LTS requires a complicated measurement apparatus, but has the potential to provide accurate, non-perturbing measurements of electron temperature and density in HET discharges. In order to assess the feasibility of LTS diagnostics on HETs non-invasive measurements of electron temperature and density in the near-field plume of a Hall thruster were performed using a custom built laser Thomson scattering diagnostic. Laser measurements were processed using a maximum likelihood estimation method and results were compared to conventional electrostatic double probe measurements performed at the same thruster conditions. Electron temperature was found to range from approximately 1 – 40 eV and density ranged from approximately 1.0 x 1017 m-3 to 1.3 x 1018 m-3 over discharge voltages from 250 to 450 V and mass flow rates of 40 to 80 SCCM using xenon propellant.

MULTI-WAVELENGTH SPECKLE REDUCTION FOR LASER PICO-PROJECTORS USING DIFFRACTIVE OPTICS

Personal electronic devices, such as cell phones and tablets, continue to decrease in size while the number of features and add-ons keep increasing. One particular feature of great interest is an integrated projector system. Laser pico-projectors have been considered, but the technology has not been developed enough to warrant integration. With new advancements in diode technology and MEMS devices, laser-based projection is currently being advanced for pico-projectors. A primary problem encountered when using a pico-projector is coherent interference known as speckle. Laser speckle can lead to eye irritation and headaches after prolonged viewing. Diffractive optical elements known as diffusers have been examined as a means to lower speckle contrast. Diffusers are often rotated to achieve temporal averaging of the spatial phase pattern provided by diffuser surface. While diffusers are unable to completely eliminate speckle, they can be utilized to decrease the resultant contrast to provide a more visually acceptable image. This dissertation measures the reduction in speckle contrast achievable through the use of diffractive diffusers. A theoretical Fourier optics model is used to provide the diffuser’s stationary and in-motion performance in terms of the resultant contrast level. Contrast measurements of two diffractive diffusers are calculated theoretically and compared with experimental results. In addition, a novel binary diffuser design based on Hadamard matrices will be presented. Using two static in-line Hadamard diffusers eliminates the need for rotation or vibration of the diffuser for temporal averaging. Two Hadamard diffusers were fabricated and contrast values were subsequently measured, showing good agreement with theory and simulated values. Monochromatic speckle contrast values of 0.40 were achieved using the Hadamard diffusers. Finally, color laser projection devices require the use of red, green, and blue laser sources; therefore, using a monochromatic diffractive diffuser may not optimal for color speckle contrast reduction. A simulation of the Hadamard diffusers is conducted to determine the optimum spacing between the two diffusers for polychromatic speckle reduction. Experimental measured results are presented using the optimal spacing of Hadamard diffusers for RGB color speckle reduction, showing 60% reduction in contrast.