In-situ measurement and characterization of cloud particles using digital in-line holography

Satellite measurement validations, climate models, atmospheric radiative transfer models and cloud models, all depend on accurate measurements of cloud particle size distributions, number densities, spatial distributions, and other parameters relevant to cloud microphysical processes. And many airborne instruments designed to measure size distributions and concentrations of cloud particles have large uncertainties in measuring number densities and size distributions of small ice crystals. HOLODEC (Holographic Detector for Clouds) is a new instrument that does not have many of these uncertainties and makes possible measurements that other probes have never made. The advantages of HOLODEC are inherent to the holographic method. In this dissertation, I describe HOLODEC, its in-situ measurements of cloud particles, and the results of its test flights. I present a hologram reconstruction algorithm that has a sample spacing that does not vary with reconstruction distance. This reconstruction algorithm accurately reconstructs the field to all distances inside a typical holographic measurement volume as proven by comparison with analytical solutions to the Huygens-Fresnel diffraction integral. It is fast to compute, and has diffraction limited resolution. Further, described herein is an algorithm that can find the position along the optical axis of small particles as well as large complex-shaped particles. I explain an implementation of these algorithms that is an efficient, robust, automated program that allows us to process holograms on a computer cluster in a reasonable time. I show size distributions and number densities of cloud particles, and show that they are within the uncertainty of independent measurements made with another measurement method. The feasibility of another cloud particle instrument that has advantages over new standard instruments is proven. These advantages include a unique ability to detect shattered particles using three-dimensional positions, and a sample volume size that does not vary with particle size or airspeed. It also is able to yield two-dimensional particle profiles using the same measurements.

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.

Measuring the elastic modulus of polymers using the atomic force microscope

Testing a new method of nanoindentation using the atomic force microscope (AFM) was the purpose of this research. Nanoindentation is a useful technique to study the properties of materials on the sub-micron scale. The AFM has been used as a nanoindenter previously; however several parameters needed to obtain accurate results, including tip radius and cantilever sensitivity, can be difficult to determine. To solve this problem, a new method to determine the elastic modulus of a material using the atomic force microscope (AFM) has been proposed by Tang et al. This method models the cantilever and the sample as two springs in a series. The ratio of the cantilever spring constant (k) to diameter of the tip (2a) is treated in the model as one parameter (α=k/2a). The value of a, along with the cantilever sensitivity, are determined on two reference samples with known mechanical properties and then used to find the elastic modulus of an unknown sample. To determine the reliability and accuracy of this technique, it was tested on several polymers. Traditional depth-sensing nanoindentation was preformed for comparison. The elastic modulus values from the AFM were shown to be statistically similar to the nanoindenter results for three of the five samples tested.