Organic contamination on spaceflight hardware is an ongoing concern for spaceflight safety. In addition, for the goal of analyzing for possible evidence of extra-terrestrial life, it is necessary to consider the presence of terrestrial contamination. This paper will introduce and evaluate a new method using a direct analysis real time (DART) ionization source paired with a high resolution time of flight mass spectrometer (TOFMS) for the determination of organic contamination involved in spaceflight hardware and ground support materials. This novel analytical technique has significant advantages over current methodologies. Materials analyzed in this study were historically considered as probable contaminants in spaceflight related substrates. A user determined library was generated due to the non-traditional mass spectra generated by the DART. Continual improvement of analytical methods for the detection of trace levels of contaminants in potential drinking water sources is of extreme importance to both regulatory communities and concerned citizens. This paper will evaluate a novel analytical method using stir bar sorbtive (SBSE) extraction techniques combined with analysis with a DART TOFMS. Compounds of interest will include several representative pharmaceutical contaminants of emerging concern listed in EPA method 1694. Optimal SBSE and DART experimental parameters will be investigated along with accuracy, precision, limits of detection and calibration linearity.

Extended Direct Analysis (EDA), developed at the University of Canterbury, is an advance on the AISC Direct Analysis method for the analysis of frames subjected to static forces. EDA provides a faster, simple and more rational way to properly consider the second-order effects, initial residual stresses (IRS) and the initial imperfections or steel structures under one directional loading than conventional analysis methods. This research applied the EDA method to quantify the effect of member overstrength on frame behaviour for a single storey frame. Also, the effects of IRS, which were included in the EDA static analysis, but which are not considered explicitly in non-linear seismic analysis, were evaluated in two ways. Firstly, they were considered for simple structures subject to increasing cyclic displacement in different directions. Secondly, incremental dynamic analysis with realistic ground motion was used to quantify the likely effect of IRS in earthquakes. It was found that, contrary to traditional wisdom and practice, greater member strengths can result in lower frame strengths for frames under monotonic lateral loading. The structural lateral capacity of the overstrength case was reduced by 6% compared to the case using the dependable member strengths. Also, it resulted significantly different in member demands. Therefore, it is recommended that when either plastic analysis or EDA is used, that both upper and lower bounds on the likely member strength should be considered to determine the total frame strength and the member demands. Results of push-pull analysis under displacement control showed that for IRS ratio, gamma < 0.5 and axial compressive force ratio, N*/Ns, up to 0.5, IRS did affect the structural behaviour in the first half cycle. However, the behavior in the later cycles was not significantly affected. It also showed that the effect of initial residual stresses in the frame was less significant than for the column alone when the column was subjected to similar axial compressive force. The incremental dynamic analysis results from both cantilever column and the three-storey steel frame showed that by increasing gamma = 0 to 0.5, the effect of IRS on seismic responses, based on the 50% confidence level, was less than 3% for N*/Ns, up to 0.5.

Trajectory reconstruction of shooting incidents can help investigators determine critical case information regarding the number of shooters involved, their location(s), and intent. The examination of trace amounts of intermediate target materials collected on the surface of spent bullets provides crucial information needed for trajectory reconstruction. Determining the origin of an unknown material adhered to a spent bullet allows for the identification of intermediate targets the bullet either contacted or penetrated during flight. Although significant information can be obtained from examination of these trace materials adhered to spent bullets, this aspect of trajectory reconstruction is often ignored. The ability of different bullet types to collect trace materials from intermediate targets and the ability to associate these trace materials to their origin was examined using microscopy and Direct Analysis in Real Time (DART). Full metal jacket (FMJ), jacketed hollow point (JHP), and lead round nose (LRN) bullets were fired into sheets of five different commonly used building materials (oriented strand board, sanded plywood, white melamine board, synthetic PVC board, and medium density fiberboard) to produce a total of 45 spent bullets to be examined. All spent bullets were examined and photographed using a DSLR camera paired with a stereomicroscope. The spent bullets were then examined using DART/MS to determine if any ion profiles generated from the trace materials could be associated with those of the intermediate target building materials which the bullets were fired through. The collection of trace material from all five types used was highly dependent on the type of bullet. Very minimal amounts of trace materials were observed on the majority of LRN bullets, which failed to produce an identifiable ion signature. The FMJ bullets that were fired through PVC material collected trace material that produced an ion profile, while all other building materials failed to transfer to the FMJ bullets. All JHP bullets collected significant amounts of the five building materials tested inside the hollow point cavity and along the nose of the bullet. In every spent JHP bullet sample, the trace material collected produced a unique ion profile. Additionally, MS data from four of the five building materials tested matched the MS data generated from trace material collected on JHP bullets from the respective target materials.

A espectrometria de emissão óptica com plasma induzido por laser (LIBS) tem se tornado uma técnica muito atrativa e bastante explorada nas análises químicas e tem ganhado destaque devido à disponibilidade de instrumentos portáteis, o qual possibilita a análise in situ. Por outro lado, a análise quantitativa tem sido considerada o \"calcanhar de Aquiles\" da técnica, face as suas dificuldades em executá-la, em especial devido à complexa interação laser-matriz. Nesse contexto, o uso de métodos de calibração apropriados é imperativo. Neste trabalho avaliou-se a possibilidade de empregar LIBS na identificação, discriminação e quantificação elementar em amostras de madeira, uma vez que essa matriz tem grande importância econômica e ambiental. O desenvolvimento de método envolveu a otimização dos parâmetros instrumentais (diâmetro de focalização de 50&#181;m, energia por pulso de 20 mJ, taxa de repetição de 10 Hz, tempo de atraso de 0,25&#181;s, padrão de análise percurso, 300 pulsos de laser, deslocamento da amostra de 0,15 mm/s e fluxo de argônio de 1,0 L/min), bem como a avaliação da influência da umidade, tamanho de partícula e homogeneidade nos resultados analíticos. Diversos métodos de calibração também foram estudados, entre eles, a calibração empregando diferentes CRMs que geraram resultados com erros relativos superiores a 30%. Calibração construída com madeira Pinus adicionada com concentrações crescentes de analito foi a que apresentou os melhores resultados (erros relativos< 20%). Outra abordagem envolveu a confecção de um branco analítico por meio da lavagem da madeira, seguida pela adição elementar o qual apresentou resultados com erros relativos de até 14%, mostrando-se bastante promissora. Apesar disso, aplicações em amostras in natura não é trivial devido à sua baixa homomogeneidade e especialmente devido ao fato de o analito naturalmente presente na amostra interagir de forma diferente ao analito artificialmente adicionado à matriz. A aplicação do LIBS na avaliação da distribuição elementar nos anéis de crescimento de árvores foi eficiente, assim como na discriminação e identificação de amostras de madeira que atingiu 100% de exatidão no índice de acerto quando aplicado KNN. / Laser-induced breakdown spectroscopy (LIBS) has become a very attractive and well-exploited technique in chemical analysis and has gained prominence due to the availability of portable instruments, which enables in situ analysis. On the other hand, quantitative analysis has been considered the \"Achilles heel\" of this technique, especially due to the strong matrix interference caused by complex laser-matrix interaction. In this context, the use of appropriate calibration methods is imperative.In this work the possibility of using LIBS in the identification, discrimination, and elemental quantification in wood samples was evaluated, since this matrix has an economic and an environmental importance. The method development involved the optimization of the instrumental parameters (50 &#181;m of spot size, 20 mJ of energy by pulse, 10 Hz of pulse repetition rate, 0.25 &#181;s of delay time, raster, 300 laser pulses, sample velocity of 0.15 mm/s and argon flow of 1.0 L/min), as well as the influence of moisture, particle size and homogeneity onto the analytical results. Several calibration methods were also studied, among them, the calibration using different CRMs which was not a good purpose since relative errors higher than 30% on the results were found. The calibration made with Pinus wood spiked with increasing concentrations of analytes showed the best results (relative errors <20%) for wood analysis. Another approach involved the preparation of an analytical blank by washing wood samples with 0.1% HNO3, followed by spiking of increasing concentration of analytes. In this case, relative errors of up to 14% were found, suggesting it is a promising approach. Despite this, applications of these proposed methods in quantitative analysis of in natura wood samples are not trivial due to their low homomogeneity and especially due to the differences on interaction between laser and naturally occurring analyte and artificially spiked analyte. The application of LIBS in the evaluation of the elemental distribution in the tree growth rings was efficient, as well as in the discrimination and identification of wood samples since 100% accuracy were reached when KNN was applied.

Direct Analysis in Real Time (DART) ionization/mass spectrometry allows for the high throughput analysis of a wide range of materials including but not limited to: solids, liquids, powders, tablets, and plant materials. The ability to detect cocaine was established in a reproducible manner with the use of a DART ionization source (IonSense Inc., Saugus, MA) interfaced to a modified single quadrupole mass spectrometer. Development of a methodology for the detection of cocaine within contrived street quality drug mixtures involved the optimization of the ionization source, sample introduction mechanism, ion guide, and mass analysis parameters. An analytical method was created that utilized ionized helium carrier gas heated to 300°C and an automated sample introduction apparatus consisting of a Linear Rail Enclosure that holds consumable QuickStrip^TM sample cards. Ionized molecules were then fragmented by manipulation of voltage levels within the ion guide to gain more structural information prior to detection by a single quadrupole mass spectrometer. Cocaine was detected by the modified DART/MS analytical platform and gave two peaks within the mass spectrum at m/z 304 and 182. Optimization of in-source fragmentation by manual adjustment of the skimmer focus voltage allowed for the reproducible fragmentation of cocaine and the ability to increase or decrease the amount of fragmentation seen between the two peaks detected for cocaine. With the use of fragmentation, this analytical platform can be classified as a Category A technique as defined by the Scientific Working Group for the Analysis of Seized Drugs. The robust detection of cocaine was demonstrated for reference samples at concentrations as low as 10 ng/μL (50 ng) with high signal abundance greater than ten times the signal to noise ratio. Furthermore, the detection of cocaine at 10 ng/μL was demonstrated for multi component mixtures of up to 14 additional components containing common adulterants and diluents found within street quality samples. In total, 25 common excipients were tested using the same method parameters as optimized for cocaine analysis. Of these 25 excipients tested, five were not detected in positive ion mode (one could be detected in negative ion mode). Of the twenty excipients that could be detected by mass spectrometry, two pairs of excipients (levamisole/tetramisole and creatine/creatinine) could not be differentiated from each other. There were no excipients tested that had equivalent m/z values as those of cocaine. Experimentation into the effects of various excipients at multiple concentrations on the abundance of the two cocaine peaks was performed. Regardless of excipient amount (up to 10 times more concentrated than cocaine) and the number of components (up to 15 total components) the ratio of abundance between the m/z 304 to 182 peaks did not vary greater than 22% relative standard deviation. A match criteria protocol was developed for the ability of an analyst to confirm the presence of cocaine within unknown forensic case samples that have previously tested positive for the presumptive identification of cocaine. The identification of cocaine was based on various factors such as the signal to noise ratio at m/z 304 and 182, the ratio of abundance between those two peaks as well as positive and negative controls. This match criteria protocol was utilized for 25 double blind mock forensic casework samples was performed. Determination for the presence of cocaine within these unknown samples gave an analyst error rate of 0%, with no false positives or false negatives predicted. To further aid human interpretation and identification of compounds within mixtures, the advanced chemometric software, Analyze IQ, was utilized. Development of predictive classification models using a combination of pre-processing steps, principle component analysis and machine learning techniques was achieved. Models were built using 381 unique samples for the purposes of identifying the presence of cocaine within unknown samples. Of all methods available within the Analyze IQ software, the optimization of a model using principle component analysis with support vector machine regression with a radial basis function kernel yielded an initial error rate of 0% for 72 samples tested. Furthermore, of the samples tested against the model, 20 samples were comprised of excipients that were not incorporated into the initial model development process. The inclusion of these samples (10 spiked with cocaine, 10 absent of cocaine), shows that predictive modeling based software can provide an accurate, robust, and evolving approach to the identification of cocaine within sample compositions that have not previously been tested and stored in a database of known reference samples. Predictive modeling has advantages over current mass spectral libraries, which are limited to the identification of pure compounds. To further test the abilities of predictive models, optimized machine learning models were applied to 25 double blind mock forensic casework samples. The predictive modeling error rate was identical to the human interpretation rate for the double blind mock casework samples with a 0% error rate. Using the DART/MS analytical platform, 25 mock forensic casework samples along with positive and negative controls were analyzed and identified for the presence of cocaine within 30 minutes. On the order of 15 to 30 times faster than modern GC/MS and LC/MS methods, the ability to analyze and identify samples faster would allow for an increase in samples being processed on a daily basis and allow for the reduction of case backlogs that currently plague controlled substances sections of forensic science laboratories throughout the United States.

A espectrometria de emissão óptica com plasma induzido por laser (LIBS) tem se tornado uma técnica muito atrativa e bastante explorada nas análises químicas e tem ganhado destaque devido à disponibilidade de instrumentos portáteis, o qual possibilita a análise in situ. Por outro lado, a análise quantitativa tem sido considerada o \"calcanhar de Aquiles\" da técnica, face as suas dificuldades em executá-la, em especial devido à complexa interação laser-matriz. Nesse contexto, o uso de métodos de calibração apropriados é imperativo. Neste trabalho avaliou-se a possibilidade de empregar LIBS na identificação, discriminação e quantificação elementar em amostras de madeira, uma vez que essa matriz tem grande importância econômica e ambiental. O desenvolvimento de método envolveu a otimização dos parâmetros instrumentais (diâmetro de focalização de 50&#181;m, energia por pulso de 20 mJ, taxa de repetição de 10 Hz, tempo de atraso de 0,25&#181;s, padrão de análise percurso, 300 pulsos de laser, deslocamento da amostra de 0,15 mm/s e fluxo de argônio de 1,0 L/min), bem como a avaliação da influência da umidade, tamanho de partícula e homogeneidade nos resultados analíticos. Diversos métodos de calibração também foram estudados, entre eles, a calibração empregando diferentes CRMs que geraram resultados com erros relativos superiores a 30%. Calibração construída com madeira Pinus adicionada com concentrações crescentes de analito foi a que apresentou os melhores resultados (erros relativos< 20%). Outra abordagem envolveu a confecção de um branco analítico por meio da lavagem da madeira, seguida pela adição elementar o qual apresentou resultados com erros relativos de até 14%, mostrando-se bastante promissora. Apesar disso, aplicações em amostras in natura não é trivial devido à sua baixa homomogeneidade e especialmente devido ao fato de o analito naturalmente presente na amostra interagir de forma diferente ao analito artificialmente adicionado à matriz. A aplicação do LIBS na avaliação da distribuição elementar nos anéis de crescimento de árvores foi eficiente, assim como na discriminação e identificação de amostras de madeira que atingiu 100% de exatidão no índice de acerto quando aplicado KNN. / Laser-induced breakdown spectroscopy (LIBS) has become a very attractive and well-exploited technique in chemical analysis and has gained prominence due to the availability of portable instruments, which enables in situ analysis. On the other hand, quantitative analysis has been considered the \"Achilles heel\" of this technique, especially due to the strong matrix interference caused by complex laser-matrix interaction. In this context, the use of appropriate calibration methods is imperative.In this work the possibility of using LIBS in the identification, discrimination, and elemental quantification in wood samples was evaluated, since this matrix has an economic and an environmental importance. The method development involved the optimization of the instrumental parameters (50 &#181;m of spot size, 20 mJ of energy by pulse, 10 Hz of pulse repetition rate, 0.25 &#181;s of delay time, raster, 300 laser pulses, sample velocity of 0.15 mm/s and argon flow of 1.0 L/min), as well as the influence of moisture, particle size and homogeneity onto the analytical results. Several calibration methods were also studied, among them, the calibration using different CRMs which was not a good purpose since relative errors higher than 30% on the results were found. The calibration made with Pinus wood spiked with increasing concentrations of analytes showed the best results (relative errors <20%) for wood analysis. Another approach involved the preparation of an analytical blank by washing wood samples with 0.1% HNO3, followed by spiking of increasing concentration of analytes. In this case, relative errors of up to 14% were found, suggesting it is a promising approach. Despite this, applications of these proposed methods in quantitative analysis of in natura wood samples are not trivial due to their low homomogeneity and especially due to the differences on interaction between laser and naturally occurring analyte and artificially spiked analyte. The application of LIBS in the evaluation of the elemental distribution in the tree growth rings was efficient, as well as in the discrimination and identification of wood samples since 100% accuracy were reached when KNN was applied.

Canines have been employed in matters of law enforcement because of their keen sense of smell. Presently, law enforcement officials are utilizing trained canines in routine traffic stops to assess if the vehicle contains any illicit substances. Many believe that this is an infringement on an individual’s fourth amendment rights, which has garnered the attention of both the media and the courts. Many questions have been raised with respect to canines alerting to locations where illicit substances were no longer present. Thus, the purpose of this dissertation research is to evaluate the manner in which active odorants transport and persist onto various substrates. Direct Analysis in Real Time (DART) coupled to an accurate-mass time-of-flight (AccuTOF™) mass spectrometer was used to rapidly analyze the volatile organic compounds (VOC’s) from a variety of narcotic and explosive substances. The DART ion source is a soft ionization technique used in ambient conditions to sample liquids, solids or gases in real time. Thermal desorption of the VOC’s could thus be conducted in seconds. The present study found that the VOC’s from illicit substances transport from one location to another, in a short amount of time, through a process known as advection, which may contribute to canines producing unconfirmed alerts during their training and certifications. Three of the four odorants used in this study produced positive results, with the exception being 2-ethyl-1-hexanol, as it was not detected at any time when held at distances between 0.5 and 3 meters. In addition, the amount of time needed for an active odorant to contaminate an object in its immediate vicinity was explored and the results were determined to be inconclusive. Although they were observed following longer exposure times, it was still deemed to be inconclusive since it was still possible for these odorants to be present, albeit not in detectable amounts, at lower exposure times. Controlled odor mimic permeating systems (COMPS), patented technology by IFRI were tested to determine the possibility of cross-contamination between the training aids, and the results conclude that there was not any evidence of cross-contamination observed during any of the trials.

N/A

O arroz é um dos alimentos mais consumidos no mundo, caracterizando-se como a base da alimentação para mais da metade da população mundial. De acordo com a Organização Mundial da Saúde (WHO), a ingestão de alimentos contaminados é uma das principais vias de absorção de elementos potencialmente tóxicos pelo ser humano. Por esse motivo, órgãos de fiscalização têm estabelecidos limites máximos permitidos desse tipo de elemento nos alimentos. Nesse sentido, o desenvolvimento de métodos e aplicações visando à determinação de elementos com caráter tóxico, tais como o Al, As, Cd e Pb em alimentos é de suma importância. Nesse projeto, foram desenvolvidos métodos para determinações diretas de Al, As, Cd e Pb em arroz por espectrometria de absorção atômica com forno de grafite e amostragem direta de sólidos (SS-GF AAS) que tem se mostrado uma técnica promissora especialmente devido à sua elevada sensibilidade e detectabilidade, além de dispensar morosos processos de decomposição de amostra. A adequada otimização do programa de aquecimento aliado ao uso de modificadores químicos adequados possibilitou o uso de calibração aquosa. Parâmetros importantes como o tamanho de partícula, massa de amostra e segregação de analito foram investigados. Observou-se que partículas inferiores a 100 &#181;m geravam resultados precisos. A massa mínima ideal de amostra de arroz a ser utilizada na análise foi em torno de 300 &#181;g. A massa máxima recomendada foi 500 &#181;g. Segregação de Al e Cd não foram observadas na amostra de arroz. A segunda parte do projeto envolveu a aplicação do método de análise desenvolvido em amostras de arroz comercializadas na cidade de São Paulo. Investigou-se também a influência dos processos de lavagem e cozimento dos grãos sobre a concentração de Al, As, Cd e Pb. Todas as 17 amostras de diversos tipos e marcas de arroz analisadas apresentaram concentrações de As, Cd e Pb abaixo dos limites estabelecidos por lei. Com relação ao Al, não há regulamentado o valor de limite máximo. As maiores concentrações desse elemento foram observadas nos grãos de arroz integral. O processo de lavagem removeu significativamente a concentração de Al e Pb na maioria das amostras, entretanto, o mesmo não foi observado para o Cd. O processo de cozimento diminuiu a concentração de Cd e Pb em parte das amostras, e um pequeno aumento na concentração do Al foi observado, o qual pode ser atribuído à contaminação pelo ambiente. O cozimento do arroz em frascos de vidro ou panelas a base de alumínio não alterou a concentração desse elemento no arroz, nem mesmo quando a panela de alumínio foi polida com palha de aço / Rice is a staple food for more than 40% of the world\'s population. Considering that the main reason of contamination by potentially toxic element occurs by food ingestion, World Health Organization (WHO) has been controlling the levels of some contaminants. In this context, development of methods and applications associated to determination of potentially toxic elements such as Al, As, Cd and Pb in food are important. In this work, methods for direct determination of Al, As, Cd and Pb in rice by solid sampling graphite furnace atomic absorption spectrometry (SS-GF AAS) were developed. Solid sampling-GF AAS has shown as a promising technique especially due to its high sensitivity and detectability and the possibility to practice direct analysis of solid samples, dismissing tedious and error prone sample preparation step. The adequate heating program optimization associated to the use of chemical modifier allowed direct rice analysis against aqueous calibration. The influence of some parameters, such as particle size, sample mass size and analyte segregation on the analytical results were investigated. Results showed that particle size smaller than 100 &#181;m generated accurate results. The minimum sample mass size recommended for analysis was around 300 &#181;g and the maximum sample mass size was around 500 &#181;g. Segregation of Cd and Al was not observed in the rice sample. The second part of the work involved the analysis of 17 rice samples commercially available in São Paulo city. Influence of rice washing and cooking procedure on the Al, As, Cd and Pb concentrations was also investigated. Concentration of all analytes were lower than the maximum allowed by WHO in all samples. The highest concentrations of Al were found in coarse rice. The washing process reduced significantly the concentrations of Al and Pb in most samples, however, the same was not observed for Cd. Cooking process reduced the concentration of Cd and Pb for most samples, probably by volatilization. On the other hand, an increase in Al concentration was observed. This fact could be attributed to the sample contamination during cooking process. Rice cooked in glass or aluminum container presented the same concentration of Al, even when polished aluminum container was used. These results indicated that there is no translocation of Al from container to food

For steel structures, stability is a very important concept since many steel structures are governed by stability limit states. Therefore, stability of a structure should be assessed carefully considering all parameters that affect the stability of the structure. The most important of these parameters can be listed as geometric imperfections, member inelasticity and connection rigidity. Geometric imperfections and member inelasticity are taken into account with the stability method used in the design. At this point, the stability methods gain importance. The Direct Analysis Method, the default stability method in 2010 AISC Specification, is a new, more transparent and more straightforward method, which captures the real structure behavior better than Effective Length Method. In this thesis, a study has been conducted on the semi-rigid steel frames to compare Direct Analysis Method and Effective Length Method and to investigate the effect of flexible connections to stability. Four frames are designed for different connection rigidities with stability methods existing in the 2010 AISC Specification: Direct Analysis Method and Effective Length Method. At the end,conclusions are drawn about the comparison of these two stability methods and the effect of semi-rigid connections to stability.