Improved sampling, pre-concentration, and detection of hidden explosives and illicit drugs by a novel solid phase microextraction geometry coupled to ion mobility spectrometry

The 9/11 Act mandates the inspection of 100% of cargo shipments entering the U.S. by 2012 and 100% inspection of air cargo by March 2010. So far, only 5% of inbound shipping containers are inspected thoroughly while air cargo inspections have fared better at 50%. Government officials have admitted that these milestones cannot be met since the appropriate technology does not exist. This research presents a novel planar solid phase microextraction (PSPME) device with enhanced surface area and capacity for collection of the volatile chemical signatures in air that are emitted from illicit compounds for direct introduction into ion mobility spectrometers (IMS) for detection. These IMS detectors are widely used to detect particles of illicit substances and do not have to be adapted specifically to this technology. For static extractions, PDMS and sol-gel PDMS PSPME devices provide significant increases in sensitivity over conventional fiber SPME. Results show a 50–400 times increase in mass detected of piperonal and a 2–4 times increase for TNT. In a blind study of 6 cases suspected to contain varying amounts of MDMA, PSPME-IMS correctly detected 5 positive cases with no false positives or negatives. One of these cases had minimal amounts of MDMA resulting in a false negative response for fiber SPME-IMS. A La (dihed) phase chemistry has shown an increase in the extraction efficiency of TNT and 2,4-DNT and enhanced retention over time. An alternative PSPME device was also developed for the rapid (seconds) dynamic sampling and preconcentration of large volumes of air for direct thermal desorption into an IMS. This device affords high extraction efficiencies due to strong retention properties under ambient conditions resulting in ppt detection limits when 3.5 L of air are sampled over the course of 10 seconds. Dynamic PSPME was used to sample the headspace over the following: MDMA tablets (12–40 ng detected of piperonal), high explosives (Pentolite) (0.6 ng detected of TNT), and several smokeless powders (26–35 ng of 2,4-DNT and 11–74 ng DPA detected). PSPME-IMS technology is flexible to end-user needs, is low-cost, rapid, sensitive, easy to use, easy to implement, and effective. ^

Three essays on self-employment transitions, organizational capital, and firm formation

This dissertation explores how economic, organizational, and personal factors affect self-employment transitions, occupational decisions, and firm formation activities of individuals at different positions in the skill distribution. The first essay of my dissertation studies how local unemployment rates differentially affect entry into self-employment by individuals at different places in the skill distribution. The empirical results show a positive correlation between local unemployment rates and entry into self-employment for low-ability workers, but not for high-ability workers. Including employer size to eliminate possible distortions showed that the positive association between unemployment and self-employment among low-ability workers is in fact driven by the small firm effect. Controlling for firm size yields a negative association between unemployment and self-employment among high-ability workers. Effects of organizational capital, human capital and physical capital, on the firm formation activities of people at distinct skill levels depend on the type of the industry which is chosen for the new firm. Two types of industries, capital-intensive and ability-intensive, are utilized to explore this hypothesis in the second essay. A capital-intensive industry requires more physical investment, and consequently more funds, whereas, an ability-intensive industry requires more human capital. It is shown that high human capital requirements are associated with higher earnings among the most able individuals, and therefore makes them more likely to found firms in an ability-intensive industry. Wealthy people are more likely to establish both capital-intensive and ability-intensive firms, even though the amount of funds necessary for two industry types differs. Moreover, entry into both industries is predicted to happen later in life due to the removal of entry barriers constituted by required investment spending using savings when old. Empirical mixed results are observed. The third essay investigates earning differentials between future entrepreneurs and their non-entrepreneurial colleagues. Results show that high-ability firm-owners in an ability-intensive industry were earning more than those that remained in wage-work, whereas, low-ability firm-owners in a capital-intensive industry were earning less than those remaining in paid-work.

Hydrologic measurements and implications for tree island formation within Everglades National Park

Tree islands in the Shark River Slough of the Everglades National Park (ENP), in the southern state of Florida in the United States, are part of a wetland system of densely vegetated ridges interspersed within relatively open sloughs. Human alteration of this system has had dramatic negative effects on the landscape of the region and restoration efforts will require adjusting the hydrology of the region to assure the preservation of these important ecologic features. The primary objectives of this study were to document the hydrology in the vicinity of tree islands in ENP by measuring velocities in time and space and by characterizing suspended sediments. The results of such measurements were interpreted with respect to factors that may limit tree island growth. The measurements were conducted in the vicinity of three tree islands known as Black Hammock (BH), Gumbo Limbo (GL), and an unnamed island that was named for this study as Satin Leaf (SL). Acoustical Doppler Velocity (ADV) meters were used for measuring the low velocities of the Everglades water flow. Properties of suspended sediments were characterized through measurements of particle size distribution, turbidity, concentration and particle density. Mean velocities observed at each of the tree islands varied from 0.9 to 1.4 cm/s. Slightly higher mean velocities were observed during the wet season (1.2–1.6 cm/s) versus the dry season (0.8–1.3 cm/s). Maximum velocities of more than 4 cm/s were measured in areas of Cladium jamaicense die-off and at the hardwood hammock (head) of the islands. At the island’s head, water is channelized around obstructions such as tree trunks in relatively rapid flow, which may limit the lateral extent of tree island growth. Channelization is facilitated by shade from the tree canopy, which limits the growth of underwater vegetation thereby minimizing the resistance to flow and limiting sediment deposition. Suspended sediment concentrations were low (0.5–1.5 mg/L) at all study sites and were primarily of organic origin. The mean particle size of the suspended sediments was 3 μm with a distribution that was exponential. Critical velocities needed to cause re-suspension of these particles were estimated to be above the actual velocities observed. Sediment transport within the water column appears to be at a near steady state during the conditions evaluated with low rates of sediment loss balanced by presumably the release of equivalent quantities of particles of organic origin. Existing hydrologic conditions do not appear to transport sufficient suspended sediments to result in the formation of tree islands. Of interest would be to collect hydrologic and sediment transport data during extreme hydrologic events to determine if enough sediment is transported under these conditions to promote sufficient sediment accumulations.

The role of recharge and evapotranspiration as hydraulic drivers of ion concentrations in shallow groundwater on Everglades tree islands, Florida (USA)

Recently, evapotranspiration has been hypothesized to promote the secondary formation of calcium carbonate year-round on tree islands in the Everglades by influencing groundwater ions concentrations. However, the role of recharge and evapotranspiration as drivers of shallow groundwater ion accumulation has not been investigated. The goal of this study is to develop a hydrologic model that predicts the chloride concentrations of shallow tree island groundwater and to determine the influence of overlying biomass and underlying geologic material on these concentrations. Groundwater and surface water levels and chloride concentrations were monitored on eight constructed tree islands at the Loxahatchee Impoundment Landscape Assessment (LILA) from 2007 to 2010. The tree islands at LILA were constructed predominately of peat, or of peat and limestone, and were planted with saplings of native tree species in 2006 and 2007. The model predicted low shallow groundwater chloride concentrations when inputs of regional groundwater and evapotranspiration-to-recharge rates were elevated, while low evapotranspiration-to-recharge rates resulted in a substantial increase of the chloride concentrations of the shallow groundwater. Modeling results indicated that evapotranspiration typically exceeded recharge on the older tree islands and those with a limestone lithology, which resulted in greater inputs of regional groundwater. A sensitivity analysis indicated the shallow groundwater chloride concentrations were most sensitive to alterations in specific yield during the wet season and hydraulic conductivity in the dry season. In conclusion, the inputs of rainfall, underlying hydrologic properties of tree islands sediments and forest structure may explain the variation in ion concentration seen across Everglades tree islands.

The utilization of chiral ion mobility spectrometry for the detection of enantiomeric mixtures and thermally labile compounds

This dissertation utilized electrospray ion mobility mass spectrometry (ESI-IMS-MS) to develop methods necessary for the separation of chiral compounds of forensic interest. The compounds separated included ephedrines and pseudoephedrines, that occur as impurities in confiscated amphetamine type substances (ATS) in an effort to determine the origin of these substances. The ESI-IMS-MS technique proved to be faster and more cost effective than traditional chromatographic methods currently used to conduct chiral separations such as gas and liquid chromatography. Both mass spectrometric and computational analysis revealed the separation mechanism of these chiral interactions allowing for further development to separate other chiral compounds by IMS. Successful separation of chiral compounds was achieved utilizing a variety of modifiers injected into the IMS drift tube. It was found that the modifiers themselves did not need to be chiral in nature and that achiral modifiers were sufficient in performing the required separations. The ESI-IMS-MS technique was also used to detect thermally labile compounds which are commonly found in explosive substances. The methods developed provided mass spectrometric identification of the type of ionic species being detected from explosive analytes as well as the appropriate solvent that enhances detection of these analytes in either the negative or positive ion mode. An application of the developed technique was applied to the analysis of a variety of low explosive smokeless powder samples. It was found that the developed ESI-IMS-MS technique not only detected the components of the smokeless powders, but also provided data that allowed the classification of the analyzed smokeless powders by manufacturer or make. ^

The Role of Recharge and Evapotranspiration as Hydraulic Drivers of Ion Concentrations in Shallow Groundwater on Everglades Tree Islands, Florida (USA)

Recently, evapotranspiration has been hypothesized to promote the secondary formation of calcium carbonate year-round on tree islands in the Everglades by influencing groundwater ions concentrations. However, the role of recharge and evapotranspiration as drivers of shallow groundwater ion accumulation has not been investigated. The goal of this study is to develop a hydrologic model that predicts the chloride concentrations of shallow tree island groundwater and to determine the influence of overlying biomass and underlying geologic material on these concentrations. Groundwater and surface water levels and chloride concentrations were monitored on eight constructed tree islands at the Loxahatchee Impoundment Landscape Assessment (LILA) from 2007 to 2010. The tree islands at LILA were constructed predominately of peat, or of peat and limestone, and were planted with saplings of native tree species in 2006 and 2007. The model predicted low shallow groundwater chloride concentrations when inputs of regional groundwater and evapotranspiration-to-recharge rates were elevated, while low evapotranspiration-to-recharge rates resulted in a substantial increase of the chloride concentrations of the shallow groundwater. Modeling results indicated that evapotranspiration typically exceeded recharge on the older tree islands and those with a limestone lithology, which resulted in greater inputs of regional groundwater. A sensitivity analysis indicated the shallow groundwater chloride concentrations were most sensitive to alterations in specific yield during the wet season and hydraulic conductivity in the dry season. In conclusion, the inputs of rainfall, underlying hydrologic properties of tree islands sediments and forest structure may explain the variation in ion concentration seen across Everglades tree islands.