The development of rubrics to measure undergraduate students' global awareness and global perspective: A validity study

Higher education institutions across the United States have developed global learning initiatives to support student achievement of global awareness and global perspective, but assessment options for these outcomes are extremely limited. A review of research for a global learning initiative at a large, Hispanic-serving, urban, public, research university in South Florida found a lack of instruments designed to measure global awareness and global perspective in the context of an authentic performance assessment. This quasi-experimental study explored the development of two rubrics for the global learning initiative and the extent to which evidence supported the rubrics' validity and reliability. One holistic rubric was developed to measure students' global awareness and the second to measure their global perspective. The study utilized a pretest/posttest nonequivalent group design. Multiple linear regression was used to ascertain the rubrics' ability to discern and compare average learning gains of undergraduate students enrolled in two global learning courses and students enrolled in two non-global learning courses. Parallel pretest/posttest forms of the performance task required students to respond to two open-ended questions, aligned with the learning outcomes, concerning a complex case narrative. Trained faculty raters read responses and used the rubrics to measure students' global awareness and perspective. Reliability was tested by calculating the rates of agreement among raters. Evidence supported the finding that the global awareness and global perspective rubrics yielded scores that were highly reliable measures of students' development of these learning outcomes. Chi-square tests of frequency found significant rates of inter-rater agreement exceeding the study's .80 minimum requirement. Evidence also supported the finding that the rubrics yielded scores that were valid measures of students' global awareness and global perspective. Regression analyses found little evidence of main effects; however, post hoc analyses revealed a significant interaction between global awareness pretest scores and the treatment, the global learning course. Significant interaction was also found between global perspective pretest scores and the treatment. These crossover interactions supported the finding that the global awareness and global perspective rubrics could be used to detect learning differences between the treatment and control groups as well as differences within the treatment group.

Microteaching Lesson Study: Mentor interaction structure and its relation to elementary preservice mathematics teacher knowledge development

This study investigated Microteaching Lesson Study (MLS) and three possible MLS mentor interaction structures during the debriefing sessions in relation to elementary preservice teacher development of knowledge for teaching. One hundred three elementary preservice teachers enrolled in five different sections of a mathematics methods course at a southern urban university were part of the study. This included 72 participants who completed MLS across three different mentor interaction structures as part of their course requirements and 31 elementary preservice teachers who did not complete MLS as part of their methods course and served as a comparison group for a portion of the study. A sequential mixed-methods research design was used to analyze the relationship between MLS mentor interaction structure and growth in preservice teachers' mathematics teacher knowledge. Data sources included pre and post assessments, group developed lesson plans and final reports, a feedback survey with Likert-type and open-ended questions, and transcripts of audio-recorded debriefing sessions. The pre and post assessments were analyzed using Analysis of Variance (ANOVA) and descriptive statistics were used to analyze the Likert-type feedback survey questions. Group MLS lesson plans, final reports, and transcripts of debriefing sessions along with the open-ended questions from the feedback survey were coded in a three-step process as described by Miles and Huberman (1994). In alignment with findings from M. Fernandez (2005, 2010), elementary preservice teachers participating in MLS grew in content knowledge related to MLS topics taught by one another. Results from the analysis of pre and post content knowledge assessments revealed that participants grew in their understanding of the mathematics topics taught during MLS irrespective of their mentor interaction structure and when compared to the participants who did not complete MLS in their methods course. Findings from the analysis of lesson plans for growth in pedagogical content knowledge revealed the most growth in this area occurred for participants assigned to the interaction structure in which the MLS mentor participated in the first two debriefing sessions. Analysis of the transcripts of the discourse during the debriefing sessions and the feedback surveys support the finding that the elementary preservice teachers assigned to the interaction structure in which the MLS mentor participated in the first and second debriefing sessions benefited more from the MLS experience when compared to elementary preservice teachers assigned to the other two interaction structures (MLS mentor participated in only the first debriefing session and MLS mentor participated in only the last debriefing session).

A comparison of the effects of classroom and Multi-User Virtual Environments on the perceived speaking anxiety of adult post-secondary English Language Learners

The population of English Language Learners (ELLs) globally has been increasing substantially every year. In the United States alone, adult ELLs are the fastest growing portion of learners in adult education programs (Yang, 2005). There is a significant need to improve the teaching of English to ELLs in the United States and other English-speaking dominant countries. However, for many ELLs, speaking, especially to Native English Speakers (NESs), causes considerable language anxiety, which in turn plays a vital role in hindering their language development and academic progress (Pichette, 2009; Woodrow, 2006). ^ Task-based Language Teaching (TBLT), such as simulation activities, has long been viewed as an effective approach for second-language development. The current advances in technology and rapid emergence of Multi-User Virtual Environments (MUVEs) have provided an opportunity for educators to consider conducting simulations online for ELLs to practice speaking English to NESs. Yet to date, empirical research on the effects of MUVEs on ELLs' language development and speaking is limited (Garcia-Ruiz, Edwards, & Aquino-Santos, 2007). ^ This study used a true experimental treatment control group repeated measures design to compare the perceived speaking anxiety levels (as measured by an anxiety scale administered per simulation activity) of 11 ELLs (5 in the control group, 6 in the experimental group) when speaking to Native English Speakers (NESs) during 10 simulation activities. Simulations in the control group were done face-to-face, while those in the experimental group were done in the MUVE of Second Life. ^ The results of the repeated measures ANOVA revealed after the Huynh-Feldt epsilon correction, demonstrated for both groups a significant decrease in anxiety levels over time from the first simulation to the tenth and final simulation. When comparing the two groups, the results revealed a statistically significant difference, with the experimental group demonstrating a greater anxiety reduction. These results suggests that language instructors should consider including face-to-face and MUVE simulations with ELLs paired with NESs as part of their language instruction. Future investigations should investigate the use of other multi-user virtual environments and/or measure other dimensions of the ELL/NES interactions.^

Interdependencies in corporate development: Relationship between strategic alliance and acquisition activities

A substantial amount of work in the field of strategic management has attempted to explain the antecedents and outcomes of organizational learning. Though multinational corporations simultaneously engage in various types of tasks, activities, and strategies on a regular basis, the transfer of organizational learning in a multi-task context has largely remained under-explored in the literature. To inform our understanding in this area, this dissertation aimed at synthesizing findings from two parallel research streams of corporate development activities: strategic alliances and acquisitions. Structured in the form of two empirical studies, this dissertation examines: 1) the strategic outcomes of alliance experience of previously allying partners in terms of subsequent acquisition attempts, and 2) the performance implications of prior alliance experience for acquisitions. The first study draws on the relational view of inter-organizational governance to explain how various deal-specific and dyadic characteristics of a partnership relate to partnering firms' post-alliance acquisition attempts. This model theorizes on a variety of relational mechanisms to build a cohesive theory of inter-organizational exchanges in a multi-task setting where strategic alliances ultimately lead to a firm's decision to commit further resources. The second study applies organizational learning theory, and specifically examines whether frequency, recency, and relatedness of different dimensions of prior alliances, beyond the dyad-level experience, relate to an acquirer's superior post-acquisition performance. The hypotheses of the studies are tested using logistic and ordinary least square regressions, respectively. Results analyzed from a sample of cross-border alliance and acquisition deals attempted (for study I) and/or completed (for study II) during the period of 1991 to 2011 generally support the theory that relational exchange determines acquiring firms' post alliance acquisition behavior and that organizational routines and learning from prior alliances influence a future acquirer's financial performance. Overall, the empirical findings support our overarching theory of interdependency, and confirm the transfer effect of learning across these alternate, yet related corporate strategies of alliance and acquisition.^

Toward A Better Understanding of the Evolution of Hotel Development: A Discussion of Product-specific Lodging Demand

In his essay - Toward a Better Understanding of the Evolution of Hotel Development: A Discussion of Product-Specific Lodging Demand - by John A. Carnella, Consultant, Laventhol & Horwath, cpas, New York, Carnella initially describes his piece by stating: “The diversified hotel product in the united states lodging market has Resulted in latent room-night demand, or supply-driven demand resulting from the introduction of a lodging product which caters to a specific set of hotel patrons. The subject has become significant as the lodging market has moved toward segmentation with regard to guest room offerings. The author proposes that latent demand is a tangible, measurable phenomenon best understood in light of the history of the guest room product from its infancy to its present state.” The article opens with an ephemeral depiction of hotel development in the United States, both pre’ and post World War II. To put it succinctly, the author wants you to know that the advent of the inter-state highway system changed the complexion of the hotel industry in the U.S. “Two essential ingredients were necessary for the next phase of hotel development in this country. First was the establishment of the magnificently intricate infrastructure which facilitated motor vehicle transportation in and around the then 48 states of the nation,” says Carnella. “The second event…was the introduction of affordable highway travel. Carnella goes on to say that the next – big thing – in hotel evolution was the introduction of affordable air travel. “With the airways filled with potential lodging guests, developers moved next to erect a new genre of hotel, the airport hotel,” Carnella advances his picture. Growth progressed with the arrival of the suburban hotel concept, which wasn’t fueled by developments in transportation, but by changes in people’s living habits, i.e. suburban affiliations as opposed to urban and city population aggregates. The author explores the distinctions between full-service and limited service lodging operations. “The market of interest with consideration to the extended-stay facility is one dominated by corporate office parks,” Carnella proceeds. These evolutional states speak to latent demand, and even further to segmentation of the market. “Latent demand… is a product-generated phenomenon in which the number of potential hotel guests increases as the direct result of the introduction of a new lodging facility,” Carnella brings his unique insight to the table with regard to the specialization process. The demand is already there; just waiting to be tapped. In closing, “…there must be a consideration of the unique attributes of a lodging facility relative to its ability to attract guests to a subject market, just as there must be an examination of the property's ability to draw guests from within the subject market,” Carnella proposes.

The effect of domestic credit in the economic *development process

A commonly held view is that creation of excessive domestic credit may lead to inflation problems, however, many economists uphold the possibility that, generous domestic credit under appropriate conditions will result in increases of output. This hypothesis is examined for Japan and Colombia for the period 1950-1993.^ Domestic credit theories are reviewed since the times of Thornton and Smith, until the recent times of Lewis, McKinnon, Stiglitz and of Japanese economists like K. Emi, Tachi R. and others. It is found that in Japan of the Post-War period, efficient financial markets and the decisive role of the government in orienting investment decisions seem to have influenced positively the effectiveness of domestic credit as an output-stimulating variable. On the contrary, in Colombia the absence of the above features seems to explain why domestic credit is not very effective as an output-stimulating variable.^ Multiple regression analyses show that domestic credit is a strong explanatory variable for output increases in Japan and a weak one for Colombia's case in the studied period. For Japan the correlation depicts a positive relationship between the two variables with a decreasing rate very similar to a typical production function. Moreover, the positive decreasing rate is confirmed if net domestic credit is used in the correlations. For Colombia a positive relationship is also found when accumulated domestic credit is used, but, if net domestic credit is the source of correlations, the positive decreasing rate is not obtained.^ Granger causality tests determined causality from domestic credit to output for Japan and no-causality for Colombia at the 1% significance level; the differences are explained by: (1) The low development level of the financial system in Colombia. (2) The nonexistence of consistent domestic credit policy to foster economic development. (3) The lack of an authoritative orientation in the allocation of financial resources and the nonexistence of long range industrialization programs in Colombia that could channel productively credit resources. For the system of equations relating domestic credit and exports, the Granger causality tests determined no-causality between domestic credit and exports for both Japan and Colombia also at the 1% significance level. ^

Flanerie: A post -reflexive mode of urban research inquiry

Urban ethnographic studies in social science usually proceed from within a pre-figured research framework that guides field activity and filters what is considered see-worthy and study-worthy to those phenomena which are in some way necessary for the fulfillment of specific research agendas. Reliance on formalized ethnographic research methods to explore the city, and the reflex to intellectualize that which is observed by using them, frequently leads to the neglect of much of what comprises the ethnographic richness of city-life through an overly-contemplative intellectuocentrism. ^ Flânerie, an avocational, proto-sociological ethnographic mode of urban exploration and observation originating in early-nineteenth-century Paris, is representative of an alternate approach to exploration and study of the city—one less subject to a compressed horizon of ethnographic experience. It affords insight into a broad range of phenomena taking place in interstitial urban space and time which often escape the instrumentally overly-determined gaze of professionalist research inquiry. ^ The present work addressed the fact that the concept of flânerie , though occasionally invoked in discussions of methodology in urban sociology and cultural studies, had not been subjected to a systematic attempt to relate it to the research methods of these disciplines. Though as a typological figure the flâneur is thought to have disappeared long ago, practices represented by the concept continue to be engaged in by persons inside and outside of academia who approach city life and social science with a perspective somewhat transcending the reified dichotomies of private-professional and art-and-science. This study transferred aspects of the experience of the city embodied in the flâneur to the realm of ethnographic urban studies and the building of grounded social theory, finding flânerie to be crucial to the development of a refined knowledge of urban life, and an important means by which previously overlooked social phenomena and silenced avenues of research inquiry might be exposed. ^ The conclusions reached found a “flâneuristic” approach to the city as being beneficial to research practice and the vitalization of urban ethnographic inquiry, by affording opportunities for exposure to, and immersion within, an expanded range of quotidian social phenomena that have frequently escaped the academicist gaze. ^

The possible selves method in evaluating youth development interventions: The use of Integrated Qualitative /Quantitative Data Analytic Strategies (IQ -DAS)

This study investigated the feasibility of using qualitative methods to provide empirical documentation of the long-term qualitative change in the life course trajectories of “at risk” youth in a school based positive youth development program (the Changing Lives Program—CLP). This work draws from life course theory for a developmental framework and from recent advances in the use of qualitative methods in general and a grounded theory approach in particular. Grounded theory provided a methodological framework for conceptualizing the use of qualitative methods for assessing qualitative life change. The study investigated the feasibility of using the Possible Selves Questionnaire-Qualitative Extension (PSQ-QE) for evaluating the impact of the program on qualitative change in participants' life trajectory relative to a non-intervention control group. Integrated Qualitative/Quantitative Data Analytic Strategies (IQ-DAS) that we have been developing a part of our program of research provided the data analytic framework for the study. ^ Change was evaluated in 85 at risk high school students in CLP high school counseling groups over three assessment periods (pre, post, and follow-up), and a non-intervention control group of 23 students over two assessment periods (pre and post). Intervention gains and maintenance and the extent to which these patterns of change were moderated by gender and ethnicity were evaluated using a mixed design Repeated Measures Multivariate Analysis of Variance (RMANOVA) in which Time (pre, post) was the within (repeated) factor and Condition, Gender, and Ethnicity the between group factors. The trends for the direction of qualitative change were positive from pre to post and maintained at the year-end follow-up. More important, the 3-way interaction for Time x Gender x Ethnicity was significant, Roy's Θ =. 205, F(2, 37) = 3.80, p <.032, indicating that the overall pattern of positive change was significantly moderated by gender and ethnicity. Thus, the findings also provided preliminary evidence for a positive impact of the youth development program on long-term change in life course trajectory, and were suggestive with respect to the issue of amenability to treatment, i.e., the identification of subgroups of individuals in a target population who are likely to be the most amenable or responsive to a treatment. ^

The utility of an Integrated Qualitative /Quantitative Data Analytic Strategy (IQ -DAS) to evaluate the impact of youth development interventions to positive qualitative change in the life course

This study reports one of the first controlled studies to examine the impact of a school based positive youth development program (Lerner, Fisher, & Weinberg, 2000) on promoting qualitative change in life course experiences as a positive intervention outcome. The study built on a recently proposed relational developmental methodological metanarrative (Overton, 1998) and advances in use of qualitative research methods (Denzin & Lincoln, 2000). The study investigated the use the Life Course Interview (Clausen, 1998) and an integrated qualitative and quantitative data analytic strategy (IQ-DAS) to provide empirical documentation of the impact the Changing Lives Program on qualitative change in positive identity in a multicultural population of troubled youth in an alternative public high school. The psychosocial life course intervention approach used in this study draws its developmental framework from both psychosocial developmental theory (Erikson, 1968) and life course theory (Elder, 1998) and its intervention strategies from the transformative pedagogy of Freire's (1983/1970). ^ Using the 22 participants in the Intervention Condition and the 10 participants in the Control Condition, RMANOVAs found significantly more positive qualitative change in personal identity for program participants relative to the non-intervention control condition. In addition, the 2X2X2X3 mixed design RMANOVA in which Time (pre, post) was the repeated factor and Condition (Intervention versus Control), Gender, and Ethnicity the between group factors, also found significant interactions for the Time by Gender and Time by Ethnicity. ^ Moreover, the directionality of the basic pattern of change was positive for participants of both genders and all three ethnic groups. The pattern of the moderation effects also indicated a marked tendency for participants in the intervention group to characterize their sense of self as more secure and less negative at the end of the their first semester in the intervention, that was stable across both genders and all three ethnicities. The basic differential pattern of an increase in the intervention condition of a positive characterization of sense of self relative to both pre test and relative to the directionality of the movement of the non-intervention controls, was stable across both genders and all three ethnic groups. ^

Disciplining democracy: United Nations peacekeeping, international security and democratization in the post -Cold War era

After the end of the Cold War, democratization and good governance became the organizing concepts for activities of the United Nations, regional organizations and states in the fields of peace, development and security. How can this increasing interest in democratization and its connection with international security be explained? This dissertation applies the theoretical tools developed by Michel Foucault in his discussions of disciplinarity and government to the analysis of the United Nations debate on democracy in the 1990s, and of two United Nations pro-democracy peacekeeping operations and their aftermath: the United Nations interventions in Haiti and Croatia. It probes “how” certain techniques of power came into being and describes their effects, using as data the texts that elaborate the United Nations understanding of democracy and the texts that constitute peacekeeping. ^ In the face of the proliferation of unpredictable threats in the last decades of the twentieth century a new form of international power emerged. Order in the international arena increasingly was maintained through activities aimed at reducing risk and increasing predictability through the normalization of “rogue” states. The dissertation shows that in the context of these activities, which included but were not limited to UN peacekeeping, normality was identified with democracy, non-democratic regimes with international threats, and democratization with international security. “Good governance” doctrines translated the political debate on democracy into the technical language of functioning state institutions. International organizations adopted good governance as the framework that made democratization a universal task within the reach of their expertise. In Haiti, the United Nations engaged in efforts to transform punishment institutions (the judiciary, police and the prison) into disciplined and disciplinary machines. In Croatia, agreements signed in the context of peacekeeping established in detail the rules of functioning of administrations and the monitoring mechanisms for their implementation. However, in Haiti, the institutions promoted were not sustainable. And in Croatia reforms are stalled by lack of consensus. ^ This dissertation puts efforts to bring about democracy through peacekeeping in the context of a specific modality of power and suggests caution in engaging in universal normalizing endeavors. ^

The Effectiveness of an Online Workshop on Behavior Management as a Professional Development Tool for Teachers

The current study examines the effects of an online workshop pertaining to classroom behavior management on teacher self-efficacy, attitudes, motivation, knowledge, and practices. In addition, information about teacher utilization of the Internet, their opinions about professional development, and experiences with classroom management were collected. Participants included 57 1st through 5th grade special and regular education teachers. Eligible teachers were those who teach an academic subject and had at least one child in the classroom they considered as disruptive. Teachers were randomized to either a training or waitlist group. Classroom observations of teacher practices and questionnaires were utilized. Teachers in the training group participated in two assessment points, baseline and post-workshop, and received access to the online course immediately following the baseline assessment. Teachers in the waitlist group participated in three assessment points, baseline, post-workshop, and follow-up, and received access to the online course immediately following the post-workshop assessment. Findings show that all teachers had access to the Internet at home and at school and used it on a daily basis. The majority of teachers indicated having some past training on all the techniques that were presented in the online workshop. All teachers expressed satisfaction with the workshop, indicating that it should be offered again. Post-workshop, findings showed significant group differences in knowledge with a large effect for the training group scoring higher than the waitlist group on a quiz. Secondly, group differences in self-efficacy, knowledge, and attitudes with teachers’ past-training as a moderator, was examined. Past-training was not found to be a significant moderator of self-efficacy, knowledge, or attitudes. However, the main effect for training group was significant for attitudes. In addition, teacher attitudes, but not knowledge and self-efficacy, significantly predicted motivation to implement. Next, the moderating effect of barriers on motivation and classroom management skill implementation was examined. Barriers were not found to be a significant moderator. Lastly, the training group was observed to be significantly more effective at giving commands compared to the waitlist group. The current study demonstrates the potential of a low-intensity online workshop on classroom management to enhance the accessibility of teacher professional development.

Hispanic orientalism: The literary development of a cultural paradigm, from medieval Spain to modern Latin America

This dissertation offers a novel approach to Hispanic Orientalism, developing a dynamic paradigm from its origins in medieval and Renaissance Iberia during the process of the Christian Reconquest, to its transatlantic migration and establishment in the early years of the Colony, from where it changed in late colonial and post-Independence Latin America, and onto modernity. ^ The study argues that Hispanic Orientalism does not necessarily imply a negative depiction of the Other, a quality associated with the traditional critique of Saidian Orientalism. Neither, does it entirely comply with the positivist approach suggested in the theoretical research of Said’s opponents, like Julia Kushigian. This dissertation also argues that sociopolitical changes and the shift in the discourse of powers, from imperial to non-imperial, had a significant impact of the development of Hispanic Orientalism, shaping the relationship with the Other. The methodology involves close reading of representative texts depicting the interactions of the dominant and dominated societies from each of the four historic periods that coincided with significant sociopolitical transformations in Hispanic society. Through an intercultural approach to literary studies, social history, and religious studies, this project develops an original paradigm of Hispanic Orientalism, derived from the image of the reinvented Semitic Other portrayed in the literary works depicting the relationship between the hegemonic and the subaltern cultures during the Reconquest period in Spain. Then, it traces the turn of the original paradigm towards reinterpretation during its transatlantic migration to Latin America through the analysis of the chronicles and travelogs of the first colonizers and explorers. During the transitional late colonial and early Independence periods Latin America sees a significant change in the discourse of powers, and Hispanic Orientalism reflects this oscillation between the past and the present therough the works of the Latin American authors from the seventeenth to the nineteenth centuries. Finally, once the non-imperial discourse of power established itself in the former Colony, a new modern stage in the development of Hispanic Orientalist paradigm takes place. It is marked by the desire to differentiate itself from the O(o)thers, as manifested in the works of the representatives of Modernism and the Boom.^

In Vivo Characterization of Myocardial Tissue Post Myocardial Infarction Using Combined Fluorescence and Diffuse Reflectance Spectroscopy

Accurately assessing the extent of myocardial tissue injury induced by Myocardial infarction (MI) is critical to the planning and optimization of MI patient management. With this in mind, this study investigated the feasibility of using combined fluorescence and diffuse reflectance spectroscopy to characterize a myocardial infarct at the different stages of its development. An animal study was conducted using twenty male Sprague-Dawley rats with MI. In vivo fluorescence spectra at 337 nm excitation and diffuse reflectance between 400 nm and 900 nm were measured from the heart using a portable fiber-optic spectroscopic system. Spectral acquisition was performed on - (1) the normal heart region; (2) the region immediately surrounding the infarct; and (3) the infarcted region - one, two, three and four weeks into MI development. The spectral data were divided into six subgroups according to the histopathological features associated with various degrees / severities of myocardial tissue injury as well as various stages of myocardial tissue remodeling, post infarction. Various data processing and analysis techniques were employed to recognize the representative spectral features corresponding to various histopathological features associated with myocardial infarction. The identified spectral features were utilized in discriminant analysis to further evaluate their effectiveness in classifying tissue injuries induced by MI. In this study, it was observed that MI induced significant alterations (p < 0.05) in the diffuse reflectance spectra, especially between 450 nm and 600 nm, from myocardial tissue within the infarcted and surrounding regions. In addition, MI induced a significant elevation in fluorescence intensities at 400 and 460 nm from the myocardial tissue from the same regions. The extent of these spectral alterations was related to the duration of the infarction. Using the spectral features identified, an effective tissue injury classification algorithm was developed which produced a satisfactory overall classification result (87.8%). The findings of this research support the concept that optical spectroscopy represents a useful tool to non-invasively determine the in vivo pathophysiological features of a myocardial infarct and its surrounding tissue, thereby providing valuable real-time feedback to surgeons during various surgical interventions for MI.

The Development of High Performance Liquid Chromatography Systems for the Analysis of Improvised Explosives

Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.

Headspace Analysis of Smokeless Powders: Development of Mass Calibration Methods using Microdrop Printing for Chromatographic and Ion Mobility Spectrometric Detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03 - 0.8 ng for the GC-MS and between 0.03 - 2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.