Geographic Provenancing of Unprocessed Cotton Using Elemental Analysis and Stable Isotope Ratios

Cotton is the most abundant natural fiber in the world. Many countries are involved in the growing, importation, exportation and production of this commodity. Paper documentation claiming geographic origin is the current method employed at U.S. ports for identifying cotton sources and enforcing tariffs. Because customs documentation can be easily falsified, it is necessary to develop a robust method for authenticating or refuting the source of the cotton commodities. This work presents, for the first time, a comprehensive approach to the chemical characterization of unprocessed cotton in order to provide an independent tool to establish geographic origin. Elemental and stable isotope ratio analysis of unprocessed cotton provides a means to increase the ability to distinguish cotton in addition to any physical and morphological examinations that could be, and are currently performed. Elemental analysis has been conducted using LA-ICP-MS, LA-ICP-OES and LIBS in order to offer a direct comparison of the analytical performance of each technique and determine the utility of each technique for this purpose. Multivariate predictive modeling approaches are used to determine the potential of elemental and stable isotopic information to aide in the geographic provenancing of unprocessed cotton of both domestic and foreign origin. These approaches assess the stability of the profiles to temporal and spatial variation to determine the feasibility of this application. This dissertation also evaluates plasma conditions and ablation processes so as to improve the quality of analytical measurements made using atomic emission spectroscopy techniques. These interactions, in LIBS particularly, are assessed to determine any potential simplification of the instrumental design and method development phases. This is accomplished through the analysis of several matrices representing different physical substrates to determine the potential of adopting universal LIBS parameters for 532 nm and 1064 nm LIBS for some important operating parameters. A novel approach to evaluate both ablation processes and plasma conditions using a single measurement was developed and utilized to determine the “useful ablation efficiency” for different materials. The work presented here demonstrates the potential for an a priori prediction of some probable laser parameters important in analytical LIBS measurement.

Preparation of an Immunosorbent and its use in the Solid Phase Extraction of Benzodiazepines

The use of capillary electrophoresis (CE) has been restricted to applications having high sample concentrations because of its low sensitivity caused by small injection volumes and, when ultraviolet (UV) detection is used, the short optical path length. Sensitivity in CE can be improved by using more sensitive detection systems, or by preconcentration techniques which are based on chromatographic and/or electrophoretic principles. One of the promising strategies to improve sensitivity is solid phase extraction (SPE). Solid Phase Extraction utilizes high sample volumes and a variety of complex matrixes to facilitate trace detection. To increase the specificity of the SPE a selective solid phase must be chosen. Immunosorbents, which are a combination of an antibody and a solid support, have proven to be an excellent option because of high selectivity of the antibody. This thesis is an exploratory study of the application of immunosorbent-SPE combined with CE for trace concentration of benzodiazepines. This research describes the immobilization and performance evaluation of an immunosorbent prepared by immobilizing a benzodiazepine-specific antibody on aminopropyl silica. The binding capacity of the immunosorbent, measured as µg of benzodiazepine/ gram of immunosorbent, was 39 ± 10. The long term stability of the prepared immunosorbent has been improved by capping the remaining aminopropyl groups by reaction with acetic anhydride. The capped immunosorbent retained its binding capacity after several uses.

Causes of Conversion from Catholicism to Protestantism in Haiti and the role of Vodou after Conversion

The purpose of this thesis was to examine the choice patterns that lead to conversion from Catholicism to Protestantism and the role of Vodou after conversion. This study highlights disappointment with the church as the leading cause of conversion in Haiti. Other causes significant to the study were examined. In illness and healing lie the controversies of religious conversion in Haiti. The only way to cure Satanic Illness is by resorting to magic. However, conversion to Protestantism means rejection of Vodou and all of its practice. A secondary purpose is to determine the role of Vodou after conversion. A total of 100 participants between the ages of 18 to 44 were included in this study. Seven percent (7%) converted for economic reasons, 43% selected disappointment with the church, 17% community/environment encounter, 13% sickness/near death experience, 2% economic and disappointment, 7% community/environment encounter and disappointment with the church, 9% disappointment sickness and near death experience, 1% economic and sickness near death experience, 1% economic and community/environment encounter. Findings suggest that Vodou is deeply rooted in Haitian identity, though all Haitians may not practice Vodou; but there are characteristics in the Haitian society that suggest that Haitians are Vodouisant. For the conversion process to be successful in Haiti it has to deeply acknowledged Vodou, the religion practiced by the masses in Haiti.

Test of a Smock System on CPR Primary Emergency Measures and Medical Errors During Simulated Emergencies

Rates of survival of victims of sudden cardiac arrest (SCA) using cardio pulmonary resuscitation (CPR) have shown little improvement over the past three decades. Since registered nurses (RNs) comprise the largest group of healthcare providers in U.S. hospitals, it is essential that they are competent in performing the four primary measures (compression, ventilation, medication administration, and defibrillation) of CPR in order to improve survival rates of SCA patients. The purpose of this experimental study was to test a color-coded SMOCK system on:1) time to implement emergency patient care measures 2) technical skills performance 3) number of medical errors, and 4) team performance during simulated CPR exercises. The study sample was 260 RNs (M 40 years, SD=11.6) with work experience as an RN (M 7.25 years, SD=9.42).Nurses were allocated to a control or intervention arm consisting of 20 groups of 5-8 RNs per arm for a total of 130 RNs in each arm. Nurses in each study arm were given clinical scenarios requiring emergency CPR. Nurses in the intervention group wore different color labeled aprons (smocks) indicating their role assignment (medications, ventilation, compression, defibrillation, etc) on the code team during CPR. Findings indicated that the intervention using color-labeled smocks for pre-assigned roles had a significant effect on the time nurses started compressions (t=3.03, p=0.005), ventilations (t=2.86, p=0.004) and defibrillations (t=2.00, p=.05) when compared to the controls using the standard of care. In performing technical skills, nurses in the intervention groups performed compressions and ventilations significantly better than those in the control groups. The control groups made significantly (t=-2.61, p=0.013) more total errors (7.55 SD 1.54) than the intervention group (5.60, SD 1.90). There were no significant differences in team performance measures between the groups. Study findings indicate use of colored labeled smocks during CPR emergencies resulted in: shorter times to start emergency CPR; reduced errors; more technical skills completed successfully; and no differences in team performance.

Soil Carbon Dioxide and Methane Efflux From an Everglades Tree Island and Ridge Landscape

The influence water levels have on CO2 and CH4 efflux were investigated at the Loxahatchee Impoundment Landscape Assessment (LILA) research facility, located in Boynton Beach, FL, USA. Measurements of CO2 efflux were taken for 24 h periods four times for one year from study plots. Laboratory incubations of intact soil cores were sampled for CO2, CH4, and redox potential. Additionally, soil cores from wet and dry condition were incubated for determination of enzyme activity and macronutrient limitation on decomposition of organic matter from study soils. Water levels had a significant negative influence on CO2 efflux and redox, but did not significantly influence CH4 efflux. Study plots were significantly different in CH4 efflux and redox potential. Labile carbon was more limiting to potential CO2 and CH4 production than phosphorus, with the effect significantly greater from dry conditions soils. Enzyme activity results were variable with greater macronutrient responses from dry condition soils.

Injustice Everywhere: Hemingway's Struggle with Race, Gender, and Aesthetics

The purpose of this study was to critically evaluate the aesthetic decisions and theoretical complexity of three of Ernest Hemingway’s most experimental texts: IN OUR TIME, TO HAVE AND HAVE NOT, and THE GARDEN OF EDEN, and to show that the usually maligned Hemingway was an author invested in the avant-garde and in analyzing and dissecting rigid societal rules, not championing them. Through critical analysis this study examined how Hemingway makes specific aesthetic decisions in order to more clearly examine the disparity between whites and both women and racial minorities in America. The problems that Hemingway makes clear through his art are meant to have a profound effect upon the reader and encourage re-evaluation of societal rules, their purpose, and their fairness to those who are not white, male, and typically in a position of power. The findings demonstrate that Hemingway’s entire oeuvre is open to re-interpretation on the basis of a progressive view of the author.

Natural Disasters and Comparative State-Formation and Nation-Building: Earthquakes in Argentina and Chile (1822-1939)

Natural disasters in Argentina and Chile played a significant role in the state-formation and nation-building process (1822-1939). This dissertation explores state and society responses to earthquakes by studying public and private relief efforts reconstruction plans, crime and disorder, religious interpretations of catastrophes, national and transnational cultures of disaster, science and technology, and popular politics. Although Argentina and Chile share a political border and geological boundary, the two countries provide contrasting examples of state formation. Most disaster relief and reconstruction efforts emanated from the centralized Chilean state in Santiago. In Argentina, provincial officials made the majority of decisions in a catastrophe’s aftermath. Patriotic citizens raised money and collected clothing for survivors that helped to weave divergent regions together into a nation. The shared experience of earthquakes in all regions of Chile created a national disaster culture. Similarly, common disaster experiences, reciprocal relief efforts, and aid commissions linked Chileans with Western Argentine societies and generated a transnational disaster culture. Political leaders viewed reconstruction as opportunities to implement their visions for the nation on the urban landscape. These rebuilding projects threatened existing social hierarchies and often failed to come to fruition. Rebuilding brought new technologies from Europe to the Southern Cone. New building materials and systems, however, had to be adapted to the South American economic and natural environment. In a catastrophe’s aftermath, newspapers projected images of disorder and the authorities feared lawlessness and social unrest. Judicial and criminal records, however, show that crime often decreased after a disaster. Finally, nineteenth-century earthquakes heightened antagonism and conflict between the Catholic Church and the state. Conservative clergy asserted that disasters were divine punishments for the state’s anti-clerical measures and later railed against scientific explanations of earthquakes.

Development and Verification of Control and Protection Strategies in Hybrid AC/DC Power Systems for Smart Grid Applications

Modern power networks incorporate communications and information technology infrastructure into the electrical power system to create a smart grid in terms of control and operation. The smart grid enables real-time communication and control between consumers and utility companies allowing suppliers to optimize energy usage based on price preference and system technical issues. The smart grid design aims to provide overall power system monitoring, create protection and control strategies to maintain system performance, stability and security. This dissertation contributed to the development of a unique and novel smart grid test-bed laboratory with integrated monitoring, protection and control systems. This test-bed was used as a platform to test the smart grid operational ideas developed here. The implementation of this system in the real-time software creates an environment for studying, implementing and verifying novel control and protection schemes developed in this dissertation. Phasor measurement techniques were developed using the available Data Acquisition (DAQ) devices in order to monitor all points in the power system in real time. This provides a practical view of system parameter changes, system abnormal conditions and its stability and security information system. These developments provide valuable measurements for technical power system operators in the energy control centers. Phasor Measurement technology is an excellent solution for improving system planning, operation and energy trading in addition to enabling advanced applications in Wide Area Monitoring, Protection and Control (WAMPAC). Moreover, a virtual protection system was developed and implemented in the smart grid laboratory with integrated functionality for wide area applications. Experiments and procedures were developed in the system in order to detect the system abnormal conditions and apply proper remedies to heal the system. A design for DC microgrid was developed to integrate it to the AC system with appropriate control capability. This system represents realistic hybrid AC/DC microgrids connectivity to the AC side to study the use of such architecture in system operation to help remedy system abnormal conditions. In addition, this dissertation explored the challenges and feasibility of the implementation of real-time system analysis features in order to monitor the system security and stability measures. These indices are measured experimentally during the operation of the developed hybrid AC/DC microgrids. Furthermore, a real-time optimal power flow system was implemented to optimally manage the power sharing between AC generators and DC side resources. A study relating to real-time energy management algorithm in hybrid microgrids was performed to evaluate the effects of using energy storage resources and their use in mitigating heavy load impacts on system stability and operational security.

Effect of pH and temperature on the carbonate promoted dissolution of sodium meta-autunite

Release of uranium from Na-autunite, an artificial mineral created as a result of polyphosphate injection in the subsurface at the DOE Hanford Site, takes place during slow dissolution of the mineral structure. Stability information of the uranyl-phosphate phases is limited to conditions involving pH, temperature, and a few aqueous organic materials. The carbonate ion, which creates very strong complexes with uranium, is the predominant ion in the groundwater composition. The polyphosphate technology with the formation of autunite was identified as the most feasible remediation strategy to sequester uranium in contaminated groundwater and soil in situ. The objectives of the experimental work were (i) to quantify the effect of bicarbonate on the stability of synthetic sodium meta-autunite created as a result of uranium stabilization through polyphosphate injection, (ii) calculate the kinetic rate law parameters of the uranium release from Na-autunite during dissolution, and (iii) to compare the process parameters with those obtained for natural calcium meta-autunite. Experiments were conducted using SPTF apparatus, which consists of syringe pumps for controlling flow rate, Teflon reactors and a heating/cooling system. 0.25 grams of synthetic Na-autunite was placed in the reactor and buffer solutions with varying bicarbonate concentrations (0.0005 to 0.003 M) at different pH (6 - 11) were pumped through the reactors. Experiments were conducted at four different temperatures in the range of 5 - 60oC. It was concluded that the rate of release of uranium from synthetic Na-autunite is directly correlated to the bicarbonate concentration. The rate of release of uranium increased from 1.90 x 10-12 at pH 6 to 2.64 x 10-10 (mol m-2 s-1) at pH 11 at 23oC over the bicarbonate concentration range tested. The activation energy values were invariant with the change in the bicarbonate concentration; however, pH is shown to influence the activation energy values. Uranyl hydroxides and uranyl carbonates complexes helped accelerate the dissolution of autunite mineral.

Design Optimization of Modern Machine-drive Systems for Maximum Fault Tolerant and Optimal Operation

Modern electric machine drives, particularly three phase permanent magnet machine drive systems represent an indispensable part of high power density products. Such products include; hybrid electric vehicles, large propulsion systems, and automation products. Reliability and cost of these products are directly related to the reliability and cost of these systems. The compatibility of the electric machine and its drive system for optimal cost and operation has been a large challenge in industrial applications. The main objective of this dissertation is to find a design and control scheme for the best compromise between the reliability and optimality of the electric machine-drive system. The effort presented here is motivated by the need to find new techniques to connect the design and control of electric machines and drive systems. A highly accurate and computationally efficient modeling process was developed to monitor the magnetic, thermal, and electrical aspects of the electric machine in its operational environments. The modeling process was also utilized in the design process in form finite element based optimization process. It was also used in hardware in the loop finite element based optimization process. The modeling process was later employed in the design of a very accurate and highly efficient physics-based customized observers that are required for the fault diagnosis as well the sensorless rotor position estimation. Two test setups with different ratings and topologies were numerically and experimentally tested to verify the effectiveness of the proposed techniques. The modeling process was also employed in the real-time demagnetization control of the machine. Various real-time scenarios were successfully verified. It was shown that this process gives the potential to optimally redefine the assumptions in sizing the permanent magnets of the machine and DC bus voltage of the drive for the worst operating conditions. The mathematical development and stability criteria of the physics-based modeling of the machine, design optimization, and the physics-based fault diagnosis and the physics-based sensorless technique are described in detail. To investigate the performance of the developed design test-bed, software and hardware setups were constructed first. Several topologies of the permanent magnet machine were optimized inside the optimization test-bed. To investigate the performance of the developed sensorless control, a test-bed including a 0.25 (kW) surface mounted permanent magnet synchronous machine example was created. The verification of the proposed technique in a range from medium to very low speed, effectively show the intelligent design capability of the proposed system. Additionally, to investigate the performance of the developed fault diagnosis system, a test-bed including a 0.8 (kW) surface mounted permanent magnet synchronous machine example with trapezoidal back electromotive force was created. The results verify the use of the proposed technique under dynamic eccentricity, DC bus voltage variations, and harmonic loading condition make the system an ideal case for propulsion systems.

Mechanisms of Chloroperoxidase-catalyzed Enantioselective Reactions as Probed by Site-directed Mutagenesis and Isotopic Labeling

Chloroperoxidase (CPO) is a heme-containing glycoprotein secreted by the marine fungus Caldariomyces fumago. Chloroperoxidase contains one ferriprotoporphyrin IX prosthetic group per molecule and catalyzes a variety of reactions, such as halogenation, peroxidation and epoxidation. The versatile catalytic activities of CPO coupled with the increasing demands for chiral synthesis have attracted an escalating interest in understanding the mechanistic and structural properties of this enzyme. In order to better understand the mechanisms of CPO-catalyzed enantioselective reactions and to fine-tune the catalytic properties of chloroperoxidase, asparagine 74 (N74) located in the narrow substrate access channel of CPO was replaced by a bulky, nonpolar valine and a polar glutamine using site-directed mutagenesis. The CPO N74 mutants displayed significantly enhanced activity toward nonpolar substrates compared to wild-type CPO as a result of changes in space and polarity of the heme distal environment. More interestingly, N74 mutants showed dramatically decreased chlorination and catalase activity but significantly enhanced epoxidation activity as a consequence of improved kinetic perfection introduced by the mutation as reflected by the favorable changes in kcat and kcat/KM of these reactions. It is also noted that the N74V mutant is capable of decomposing cyanide, the most notorious poison for many hemoproteins, as judged by the unique binding behavior of N74V with potassium cyanide. Histidine 105 (H105) was replaced by a nonpolar amino acid alanine using site-directed mutagenesis. The CPO H105 mutant (H105A) displayed dramatically decreased chlorination and catalase activity possibly because of the decreased polarity in the heme distal environment and loss of the hydrogen bonds between histidine 105 and glutamic acid 183. However, significantly increased enantioselectivity was observed for the epoxidation of bulky styrene derivatives. Furthermore, my study provides strong evidence for the proposed histidine/cysteine ligand switch in chloroperoxidase, providing experimental support for the structure of the 420-nm absorption maximum for a number of carbon monoxide complexes of heme-thiolate proteins. For the NMR study, [dCPO(heme)] was produced using 90% deuterated growth medium with excess heme precursors and [dCPO(Phe)] was grown in the same highly deuterated medium that had been supplemented with excess natural phenylalanine. To make complete heme proton assignments, NMR spectroscopy has been performed for high-resolution structural characterization of [dCPO(heme)] and [dCPO(Phe)] to achieve unambiguous and complete heme proton assignments, which also allows important amino acids close to the heme active center to be determined.

Measuring the Impact of Melaleuca quinquenervia Biochar Application on Soil Quality, Plant Growth, and Microbial Gas Flux

Biochar has been heralded a mechanism for carbon sequestration and an ideal amendment for improving soil quality. Melaleuca quinquenervia is an aggressive and wide-spread invasive species in Florida. The purpose of this research was to convert M. quinquenervia biomass into biochar and measure how application at two rates (2% or 5% wt/wt) impacts soil quality, plant growth, and microbial gas flux in a greenhouse experiment using Phaseolus vulgaris L. and local soil. Plant growth was measured using height, biomass weight, specific leaf area, and root-shoot ratio. Soil quality was evaluated according to nutrient content and water holding capacity. Microbial respiration, as carbon dioxide (CO2), was measured using gas chromatography. Biochar addition at 5% significantly reduced available soil nutrients, while 2% biochar application increased almost all nutrients. Plant biomass was highest in the control group, p2 flux decreased significantly in both biochar groups, but reductions were not long term.

Predictors of Adolescent Sexual Intentions and Behavior: Attitudes, Parenting, and Neighborhood Risk

The current study was a cross-sectional examination of data collected during an HIV risk reduction intervention in south Florida. The purpose of the study was to explore the relationships between neighborhood stress, parenting, attitudes, and adolescent sexual intentions and behavior. The Theory of Planned Behavior was used as a model to guide variable selection and propose an interaction pathway between predictors and outcomes. Potential predictor variables measured for adolescents ages 13-18 (n=196) included communication about sex, parent-family connectedness, parental presence, parent-adolescent activity participation, attitudes about sex and condom use, neighborhood disorder, and exposure to violence. Outcomes were behavioral intentions and sexual behavior for the previous eight months. Neighborhood data was supplemented with ZIP Code level data from regional sources and included median household income, percentage of minority and Hispanic residents, and number of foreclosures. Statistical tests included t-tests, Pearson’s correlations, and hierarchical linear regressions. Results showed that males and older adolescents reported less positive behavioral intentions than females and adolescents younger than 16. Intentions were associated with condom attitudes, sexual attitudes, and parental presence; unprotected sexual behavior was associated with parental presence. The best fit model for intentions included gender, sexual attitudes, condom attitudes, parental presence, and neighborhood disorder. The unsafe sexual behavior model included whether the participant lived with both natural parents in the previous year, and the percent of Hispanic residents in the neighborhood. Study findings indicate that more research on adolescent sexual behavior is warranted, specifically examining the differentials between variables that affect intentions and those that affect behavior. A focus on gender and age differences during intervention development may allow for better targeting and more efficacious interventions. Adding peer and media influences to the framework of attitudes, parenting, and neighborhood may offer more insight into patterns of adolescent sexual behavior risk.

Not Getting By: Poverty Management and Homelessness in Miami

Urban inequality has emerged as one of the dominant themes of modern life and globalization. More than three million people experienced homelessness in the United States last year; in Miami-Dade, more than 15,000 individuals were homeless. Surviving extreme poverty, and exiting or avoiding homelessness, involves negotiating a complex mix of public and private assistance. However, a range of factors influence what types of help are available and how they can be accessed. Frequently, larger social structures determine which resource are available, leaving many choices entirely out of the individual’s control. For single men, who are ineligible for many benefits, homelessness can be difficult to avoid and even harder to exit. My study seeks to better understand how adult, minority men living in extreme poverty in Miami-Dade negotiate their daily survival. Specific research questions address: Do black and Hispanic men who are homeless or at risk of homelessness have different personal characteristics and different experiences in avoiding or exiting homelessness? How does Miami’s response to extreme poverty/homelessness, including availability of public benefits and public and private service organizations, either maximize or constrain the choices available to this population? And, what is the actual experience of single, adult men who are homeless or at risk of homelessness, in negotiating their daily survival? A mixed methods approach combines quantitative survey data from 7,605 homeless men, with qualitative data from 54 semi-structured interviews incorporating the visual ethnography techniques of Photo Elicitation Interviewing. Results show the differences experienced by black and Hispanic men who are poor and homeless in Miami. Findings also highlight how the community’s official and unofficial responses to homelessness intersect with the actual experiences of the persons targeted by the policies and programs, challenging preconceived notions regarding the lives of persons living in extreme poverty. It adds to the existing body of literature by focusing on the urban Miami context, emphasizing disparities amongst racial and ethnic groups. Findings are intended to provide an empirically grounded thesis that humanizes the subjects and illuminates their personal experiences, helping to inform public policy around the needs of extremely poor populations.

Taking Issue with History: Empathy and the Ethical Imperatives of Creative Interventions

The purpose of this thesis was to contribute to a dialogue that considers the relationship between history, literature, and empathy as a literary affect. Specifically, I explored sites of literature’s transformative potential as it relates to cultural studies and the ethics of deconstruction. Via a deconstructive, post-colonial reading of Toni Morrison’s Beloved and Junot Díaz’s The Brief Wondrous Life of Oscar Wao, I considered how subjects in our current socio-political moment can feel history. Emerging from a post-structurally mediated engagement with history, signification, and feeling, I argued that empathy, as it is contentiously presented in the context of deconstruction, is not necessarily a reductive or essentialist approach towards relating or “being-with” an-other. Instead, I proposed that the act of reading historiographical novels that take constructions of the Atlantic Slave Trade to task might generate an affective empathy, which could in turn engender a more empathetic relationality and way of being-in-the-world.