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- Title
- DISCRIMINATION OF AUTOMOBILE CARPET FIBERS USING MULTIPLE ANALYTICAL TECHNIQUES AND THE SUBSEQUENT CREATION OF A SEARCHABLE DATABASE.
- Creator
-
Dorrien, Derek, Sigman, Michael, University of Central Florida
- Abstract / Description
-
Forensic fiber examination is an important part of trace evidence analysis. Fibers may be recovered from a crime scene that could link a particular suspect to the scene. Clothing fibers are most frequently encountered but automobile carpeting fibers may also be recovered. An understanding of the frequency of occurrence and the discrimination power of different analytical techniques is needed in order to better establish the evidentiary value of automobile carpet fiber evidence. Seventy-five...
Show moreForensic fiber examination is an important part of trace evidence analysis. Fibers may be recovered from a crime scene that could link a particular suspect to the scene. Clothing fibers are most frequently encountered but automobile carpeting fibers may also be recovered. An understanding of the frequency of occurrence and the discrimination power of different analytical techniques is needed in order to better establish the evidentiary value of automobile carpet fiber evidence. Seventy-five automobile carpet fiber samples were analyzed using a series of techniques ranging from nondestructive to destructive. These techniques included polarized light microscopy, fluorescence microscopy, microspectrophotometry, Fourier-transform infrared spectroscopy, microtomy (cross section analysis), dye extraction and liquid chromatography-mass spectrometry. Based on the information obtained from these techniques an overall discrimination of 98.02% was calculated. Only 55 of 2775 pairwise comparisons were indistinguishable. The information was subsequently entered into a searchable database for general public use.
Show less - Date Issued
- 2006
- Identifier
- CFE0001483, ucf:47103
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001483
- Title
- CHROMATOGRAPHIC AND MASS SPECTRAL ANALYSES OF OLIGOSACCHARIDES AND INDIGO DYE EXTRACTED FROM COTTON TEXTILES WITH MANOVA AND ANOVA STATISTICAL DATA ANALYSES.
- Creator
-
Frisch, Jessica, Sigman, Michael, University of Central Florida
- Abstract / Description
-
Research was conducted on thirteen 100% cotton denim samples using an acid wash, established by Murray, to extract oligosaccharides from the cellulosic material. The oligosaccharide ion groups (+, +, and +) for molecules with degrees of polymerization between two and seven (DP2-DP7) were analyzed using liquid chromatography coupled to mass spectrometry with an electrospray ionization interface (LC-ESI-MS). The results were compared using the least-squares means in a Multivariate ANOVA (MANOVA...
Show moreResearch was conducted on thirteen 100% cotton denim samples using an acid wash, established by Murray, to extract oligosaccharides from the cellulosic material. The oligosaccharide ion groups (+, +, and +) for molecules with degrees of polymerization between two and seven (DP2-DP7) were analyzed using liquid chromatography coupled to mass spectrometry with an electrospray ionization interface (LC-ESI-MS). The results were compared using the least-squares means in a Multivariate ANOVA (MANOVA) test followed by Univariate ANOVA and Tukey HSD tests and demonstrated that the method could correctly determine that two samples were statistically different 85.9% of the time when analyzing the amount (ng) of each of the oligosaccharide ion groups separately, and 82.0% when analyzing the total moles of monosaccharide units released. A dye extraction was performed on the denim materials and the extract analyzed using gas chromatography coupled with mass spectrometry (GC-MS). Indigo dye was present in all of the denim samples except one. When these results were combined with the two oligosaccharide statistical analyses, the discriminating power was increased to 88.5% and 85.9%, respectively. Additional cellulosic materials were also investigated including four white 100% cotton t-shirts as well as five raw cotton samples grown in Tajikistan, Uzbekistan, Egypt, Iran, and Benin West Africa. The analytical methodology gave results for the white cotton t-shirts and raw cotton samples that were inconsistent with those obtained from the denim samples.
Show less - Date Issued
- 2008
- Identifier
- CFE0002068, ucf:47583
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0002068
- Title
- ADVANCES IN FIRE DEBRIS ANALYSIS.
- Creator
-
Williams, Mary, Sigman, Michael, University of Central Florida
- Abstract / Description
-
Fire incidents are a major contributor to the number of deaths and property losses within the United States each year. Fire investigations determine the cause of the fire resulting in an assignment of responsibility. Current methods of fire debris analysis are reviewed including the preservation, extraction, detection and characterization of ignitable liquids from fire debris. Leak rates were calculated for the three most common types of fire debris evidence containers. The consequences of...
Show moreFire incidents are a major contributor to the number of deaths and property losses within the United States each year. Fire investigations determine the cause of the fire resulting in an assignment of responsibility. Current methods of fire debris analysis are reviewed including the preservation, extraction, detection and characterization of ignitable liquids from fire debris. Leak rates were calculated for the three most common types of fire debris evidence containers. The consequences of leaking containers on the recovery and characterization of ignitable liquids were demonstrated. The interactions of hydrocarbons with activated carbon during the extraction of ignitable liquids from the fire debris were studied. An estimation of available adsorption sites on the activated carbon surface area was calculated based on the number of moles of each hydrocarbon onto the activated carbon. Upon saturation of the surface area, hydrocarbons with weaker interactions with the activated carbon were displaced by more strongly interacting hydrocarbons thus resulting in distortion of the chromatographic profiles used in the interpretation of the GC/MS data. The incorporation of an additional sub-sampling step in the separation of ignitable liquids by passive headspace sampling reduces the concentration of ignitable liquid accessible for adsorption on the activated carbon thus avoiding saturation of the activated carbon. A statistical method of covariance mapping with a coincident measurement to compare GC/MS data sets of two ignitable liquids was able to distinguish ignitable liquids of different classes, sub-classes and states of evaporation. In addition, the method was able to distinguish 10 gasoline samples as having originated from different sources with a known statistical certainty. In a blind test, an unknown gasoline sample was correctly identified from the set of 10 gasoline samples without making a Type II error.
Show less - Date Issued
- 2007
- Identifier
- CFE0001642, ucf:47242
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001642
- Title
- FORENSIC ANALYSIS OF C-4 AND COMMERCIAL BLASTING AGENTS FOR POSSIBLE DISCRIMINATION.
- Creator
-
Steele, Katie, Sigman, Michael, University of Central Florida
- Abstract / Description
-
The criminal use of explosives has increased in recent years. Political instability and the wide spread access to the internet, filled with "homemade recipes," are two conjectures for the increase. C-4 is a plastic bonded explosive (PBX) comprised of 91% of the high explosive RDX, 1.6% processing oils, 5.3% plasticizer, and 2.1% polyisobutylene (PIB). C-4 is most commonly used for military purposes, but also has found use in commercial industry as well. Current methods for the forensic...
Show moreThe criminal use of explosives has increased in recent years. Political instability and the wide spread access to the internet, filled with "homemade recipes," are two conjectures for the increase. C-4 is a plastic bonded explosive (PBX) comprised of 91% of the high explosive RDX, 1.6% processing oils, 5.3% plasticizer, and 2.1% polyisobutylene (PIB). C-4 is most commonly used for military purposes, but also has found use in commercial industry as well. Current methods for the forensic analysis of C-4 are limited to identification of the explosive; however, recent publications have suggested the plausibility of discrimination between C-4 samples based upon the processing oils and stable isotope ratios. This research focuses on the discrimination of C-4 samples based on ratios of RDX to HMX, a common impurity resulting from RDX synthesis. The relative amounts of HMX are a function of the RDX synthetic route and conditions. RDX was extracted from different C-4 samples and was analyzed by ESI-MS-SIM as the chloride adduct, EI-GC-MS-SIM, and NICI-GC-MS. Ratios (RDX/HMX) were calculated for each method. An analysis of variance (ANOVA) followed by a Tukey HSD allowed for an overall discriminating power to be assessed for each analytical method. The C-4 processing oils were also extracted, and analyzed by direct exposure probe mass spectrometry (DEP-MS) with electron ionization, a technique that requires less than two minutes for analysis. The overall discriminating power of the processing oils was calculated by conducting a series of t tests. Lastly, a set of heterogeneous commercial blasting agents were analyzed by laser induced breakdown spectroscopy (LIBS). The data was analyzed by principal components analysis (PCA), and the possibility of creating a searchable library was explored.
Show less - Date Issued
- 2007
- Identifier
- CFE0001805, ucf:47358
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001805
- Title
- DISCRIMINATION OF FORENSIC TRACE EVIDENCE USING LASER INDUCED BREAKDOWN SPECTROSCOPY.
- Creator
-
Bridge, Candice, Sigman, Michael, University of Central Florida
- Abstract / Description
-
Elemental analysis in forensic laboratories can be tedious and many trace evidence items are not analyzed to determine their elemental composition. Presently, scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDS) is the primary analytical tool for determining the elemental composition of trace evidence items. However, due to the time it takes to obtain the required vacuum and the limited number of samples that can be analyzed at any one time, SEM-EDS can be impractical...
Show moreElemental analysis in forensic laboratories can be tedious and many trace evidence items are not analyzed to determine their elemental composition. Presently, scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDS) is the primary analytical tool for determining the elemental composition of trace evidence items. However, due to the time it takes to obtain the required vacuum and the limited number of samples that can be analyzed at any one time, SEM-EDS can be impractical for a high volume of evidence items. An alternative instrument that can be used for this type of analysis is laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). While LA-ICP-MS is a very precise and quantitative analytical method that determines elemental composition based on isotopic mass measurements; however, the instrumentation is relatively expensive and therefore is budgetarily prohibitive for many forensic laboratories. It is the purpose of this research to evaluate an inexpensive instrument that can potentially provide rapid elemental analysis for many forensic laboratories. Laser induced breakdown spectroscopy (LIBS) is an analytical method that meets these requirements and offers information about the elemental composition based on ionic, atomic and diatomic molecular emissions.
Show less - Date Issued
- 2007
- Identifier
- CFE0001957, ucf:47463
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001957
- Title
- THE IDENTIFICATION OF IGNITABLE LIQUIDS IN THE PRESENCE OF PYROLYSIS PRODUCTS: GENERATION OF A PYROLYSIS PRODUCT DATABASE.
- Creator
-
Castelbuono, Joseph, Sigman, Michael, University of Central Florida
- Abstract / Description
-
The fire debris analyst is often faced with the complex problem of identifying ignitable liquid residues in the presence of products produced from pyrolysis and incomplete combustion of common building and furnishing materials. The purpose of this research is to investigate a modified destructive distillation methodology provided by the Florida Bureau of Forensic Fire and Explosive Analysis to produce interfering product chromatographic patterns similar to those observed in fire debris case...
Show moreThe fire debris analyst is often faced with the complex problem of identifying ignitable liquid residues in the presence of products produced from pyrolysis and incomplete combustion of common building and furnishing materials. The purpose of this research is to investigate a modified destructive distillation methodology provided by the Florida Bureau of Forensic Fire and Explosive Analysis to produce interfering product chromatographic patterns similar to those observed in fire debris case work. The volatile products generated during heating of substrate materials are extracted from the fire debris by passive headspace adsorption and subsequently analyzed by GC-MS. Low density polyethylene (LDPE) is utilized to optimize the modified destructive distillation method to produce the interfering products commonly seen in fire debris. The substrates examined in this research include flooring and construction materials along with a variety of materials commonly analyzed by fire debris analysts. These substrates are also burned in the presence of a variety of ignitable liquids. Comparisons of ignitable liquids, pyrolysis products, and products from pyrolysis in the presence of an ignitable liquid are performed by comparing the summed ion spectra from the GC-MS data. Pearson correlation was used to determine if substrates could be discriminated from one another. A pyrolysis products database and GC-MS database software based on comparison of summed ion spectra are shown to be useful tools for the evaluation of fire debris.
Show less - Date Issued
- 2008
- Identifier
- CFE0002429, ucf:47746
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0002429
- Title
- FORENSIC ANALYSIS OF AUTOMOBILE PAINTS BY ATOMIC AND MOLECULAR SPECTROSCOPIC METHODS AND STATISTICAL DATA ANALYSES.
- Creator
-
McIntee, Erin, Sigman, Michael, University of Central Florida
- Abstract / Description
-
The analysis of 110 automotive paint samples was conducted for the research presented here. Laser-induced breakdown spectroscopy (LIBS) was the central instrument utilized for analysis although scanning electron microscopy / energy dispersive x-ray spectroscopy (SEM/EDS) and Fourier transform infrared spectroscopy – attenuated total reflection (FTIR-ATR) analyses were also performed. Two separate methods of LIBS analysis of samples were used: a cross sectional analysis and a drill down...
Show moreThe analysis of 110 automotive paint samples was conducted for the research presented here. Laser-induced breakdown spectroscopy (LIBS) was the central instrument utilized for analysis although scanning electron microscopy / energy dispersive x-ray spectroscopy (SEM/EDS) and Fourier transform infrared spectroscopy – attenuated total reflection (FTIR-ATR) analyses were also performed. Two separate methods of LIBS analysis of samples were used: a cross sectional analysis and a drill down analysis. SEM/EDS analysis focused on the cross section while FTIR-ATR analysis concentrated on the clearcoat layer. Several different data/statistical analyses were evaluated including principal components analysis (PCA), two tailed t-tests based on several different metrics (Hit Quality Index (HQI), Pearson's correlation and Sorenson index), multivariate analysis of variance and receiver operating characteristic (ROC) curves. Full spectrum data analysis from LIBS spectra resulted in 99.7% discrimination between different sample comparisons and 12% between same sample comparisons based on HQI and t-tests. Peak analysis of LIBS spectra resulted in 87.5% discrimination between different sample comparisons and 5% between same sample comparisons based on MANOVA. When combining the results of the FTIR-ATR and SEM/EDS analyses, 88% of the samples could be discriminated.
Show less - Date Issued
- 2008
- Identifier
- CFE0002430, ucf:47739
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0002430
- Title
- BLACK WRITING INK ANALYSIS BY DIRECT INFUSION ELECTROSPRAY MASS SPECTROSCOPY.
- Creator
-
Moody, Christopher, Sigman, Michael, University of Central Florida
- Abstract / Description
-
An optimized method of extraction, an instrumental analysis method and data analysis was proposed for black writing inks based on direct infusion electrospray-mass spectrometry (ESI-MS). The sampling and analysis method is both minimally destructive and able to assess differences in inks from a reference collection of thirty ballpoint, gel, and rollerball inks. The methanol extracts of ink on paper samples were analyzed with three direct infusion (ESI-MS) methods. Each method varied scan...
Show moreAn optimized method of extraction, an instrumental analysis method and data analysis was proposed for black writing inks based on direct infusion electrospray-mass spectrometry (ESI-MS). The sampling and analysis method is both minimally destructive and able to assess differences in inks from a reference collection of thirty ballpoint, gel, and rollerball inks. The methanol extracts of ink on paper samples were analyzed with three direct infusion (ESI-MS) methods. Each method varied scan voltage negative and positive, ESI fragmentor applied voltage (+120V, +0V, and -120V), and mobile phase additive. Direct infusion ESI-MS analysis, followed by pair-wise comparisons of the observed ion data in binary form allowed inks to be distinguished from each other. The photobleaching of the dye Basic Violet 3 (BV3) in ink-on-paper samples was examined to determine the use of degradation products as a marker of the age of the writing sample. The extent of photobleaching of BV3 was determined using several illumination sources. Pair-wise comparison of observed ion data was able to distinguish 29 of 30 ink samples using the combined three instrumental methods. Out of 435 pair-wise comparisons 429 pairs could be discriminated from each other using the combined three methods. This is a 98.6% discrimination with the combined analysis scheme.
Show less - Date Issued
- 2010
- Identifier
- CFE0003563, ucf:48929
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003563
- Title
- STATISTICAL ANALYSIS OF VISIBLE ABSORPTION SPECTRA AND MASS SPECTRA OBTAINED FROM DYED TEXTILE FIBERS.
- Creator
-
White, Katie, Sigman, Michael, University of Central Florida
- Abstract / Description
-
The National Academy of Sciences recently published a report which calls for improvements to the field of forensic science. Their report criticized many forensic disciplines for failure to establish rigorously-tested methods of comparison, and encouraged more research in these areas to establish limitations and assess error rates. This study applies chemometric and statistical methods to current and developing analytical techniques in fiber analysis. In addition to analysis of commercially...
Show moreThe National Academy of Sciences recently published a report which calls for improvements to the field of forensic science. Their report criticized many forensic disciplines for failure to establish rigorously-tested methods of comparison, and encouraged more research in these areas to establish limitations and assess error rates. This study applies chemometric and statistical methods to current and developing analytical techniques in fiber analysis. In addition to analysis of commercially available dyed textile fibers, two pairs of dyes are selected for custom fabric dyeing based on the similarities of their absorbance spectra and dye molecular structures. Visible absorption spectra for all fiber samples are collected using microspectrophotometry (MSP) and mass spectra are collected using electrospray ionization (ESI) mass spectrometry. Statistical calculations are performed using commercial software packages and software written in-house. Levels of Type I and Type II error are examined for fiber discrimination based on hypothesis testing of visible absorbance spectra profiles using a nonparametric permutation method. This work also explores evaluation of known and questioned fiber populations based on an assessment of statistical p-value distributions from questioned-known fiber comparisons with those of known fiber self-comparisons. Results from the hypothesis testing are compared with principal components analysis (PCA) and discriminant analysis (DA) of visible absorption spectra, as well as PCA and DA of ESI mass spectra. The sensitivity of a statistical approach will also be discussed in terms of how instrumental parameters and sampling methods may influence error rates.
Show less - Date Issued
- 2010
- Identifier
- CFE0003454, ucf:48396
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003454
- Title
- THE FORENSIC ANALYSIS OF TRIACETONE TRIPEROXIDE (TATP) PRECURSORS AND SYNTHETIC BY-PRODUCTS.
- Creator
-
Painter, Kimberly, Sigman, Michael, University of Central Florida
- Abstract / Description
-
Triacetone Triperoxide (TATP) is a primary high explosive that can be synthesized using commercially available starting materials and has grown in use among terrorists over the past several years. Additives present in the precursors were investigated to see if they carry through the TATP synthesis and can be detected in the final product potentially aiding in the identification of the source. Additives identified in the acetones were also identified in pre-blast and in some post-blast samples...
Show moreTriacetone Triperoxide (TATP) is a primary high explosive that can be synthesized using commercially available starting materials and has grown in use among terrorists over the past several years. Additives present in the precursors were investigated to see if they carry through the TATP synthesis and can be detected in the final product potentially aiding in the identification of the source. Additives identified in the acetones were also identified in pre-blast and in some post-blast samples. However, these additives are present in trace quantities relative to the TATP, which coupled with the volatility and short lifetimes of some of the additives in TATP samples limit their detection in pre-blast and post-blast material. TATP prepared with different acids in the laboratory could generally be discriminated by observing the change in composition of the headspace of the samples upon heating and by IMS analysis of the crystals. The analysis of TATP synthesized on a larger scale was compared to the laboratory results of pre-blast material and post-blast debris. As in the laboratory samples, organic additives were also detected in the large-scale pre-blast samples and the identification of the additives in post-blast debris was consistent with the results obtained in the laboratory detonations.
Show less - Date Issued
- 2009
- Identifier
- CFE0002942, ucf:47983
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0002942
- Title
- DETERMINING THE PRESENCE OF AN IGNITABLE LIQUID RESIDUE IN FIRE DEBRIS SAMPLES UTILIZING TARGET FACTOR ANALYSIS.
- Creator
-
McHugh, Kelly, Sigman, Michael, University of Central Florida
- Abstract / Description
-
Current fire debris analysis procedure involves using the chromatographic patterns of total ion chromatograms, extracted ion chromatograms, and target compound analysis to identify an ignitable liquid according to the American Society for Testing and Materials (ASTM) E 1618 standard method. Classifying the ignitable liquid is accomplished by a visual comparison of chromatographic data obtained from any extracted ignitable liquid residue in the debris to the chromatograms of ignitable liquids...
Show moreCurrent fire debris analysis procedure involves using the chromatographic patterns of total ion chromatograms, extracted ion chromatograms, and target compound analysis to identify an ignitable liquid according to the American Society for Testing and Materials (ASTM) E 1618 standard method. Classifying the ignitable liquid is accomplished by a visual comparison of chromatographic data obtained from any extracted ignitable liquid residue in the debris to the chromatograms of ignitable liquids in a database, i.e. by visual pattern recognition. Pattern recognition proves time consuming and introduces potential for human error. One particularly difficult aspect of fire debris analysis is recognizing an ignitable liquid residue when the intensity of its chromatographic pattern is extremely low or masked by pyrolysis products. In this research, a unique approach to fire debris analysis was applied by utilizing the samplesÂÂ' total ion spectrum (TIS) to identify an ignitable liquid, if present. The TIS, created by summing the intensity of each ion across all elution times in a gas chromatography-mass spectrometry (GC-MS) dataset retains sufficient information content for the identification of complex mixtures . Computer assisted spectral comparison was then performed on the samplesÂÂ' TIS by target factor analysis (TFA). This approach allowed rapid automated searching against a library of ignitable liquid summed ion spectra. Receiver operating characteristic (ROC) curves measured how well TFA identified ignitable liquids in the database that were of the same ASTM classification as the ignitable liquid in fire debris samples, as depicted in their corresponding area under the ROC curve. This study incorporated statistical analysis to aid in classification of an ignitable liquid, therefore alleviating interpretive error inherent in visual pattern recognition. This method could allow an analyst to declare an ignitable liquid present when utilization of visual pattern recognition alone is not sufficient.
Show less - Date Issued
- 2010
- Identifier
- CFE0003042, ucf:48337
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003042
- Title
- Tandem Mass Spectrometric Analysis of Ammonium and Sodium Oligoperoxide Adducts with the Application of Two-Dimensional Correlation Spectroscopy and Computational Chemistry.
- Creator
-
Frisch, Jessica, Sigman, Michael, Fookes, Barry, Hampton, Michael, University of Central Florida
- Abstract / Description
-
Oligoperoxides, H[OO(CH3)2C]nOOH, are formed as side products in the synthesis of the primary high explosive triacetone triperoxide (TATP). Previous tandem mass spectrometry (MSn) experiments using a quadrupole ion trap reported that the open-chained oligoperoxide adducts of ammonium or sodium resulted in different product ions in the mass spectra. Dissociation mechanisms were previously proposed based on MSn experiments, where n(>)2; however, a dissociation pathway achieved by an MSn...
Show moreOligoperoxides, H[OO(CH3)2C]nOOH, are formed as side products in the synthesis of the primary high explosive triacetone triperoxide (TATP). Previous tandem mass spectrometry (MSn) experiments using a quadrupole ion trap reported that the open-chained oligoperoxide adducts of ammonium or sodium resulted in different product ions in the mass spectra. Dissociation mechanisms were previously proposed based on MSn experiments, where n(>)2; however, a dissociation pathway achieved by an MSn experiment, where n(>)2, may not necessarily be the same pathway achieved in an MS2 experiment. For this dissertation research, the collision induced dissociation pathways were investigated for the open-chained oligoperoxides in MS2 experiments utilizing a quadrupole ion trap. Tandem mass spectral experiments were performed for the open-chained oligoperoxides ranging from the trimer to the octamer (n=3-8), including both ammonium and sodium adducts. The dissociation pathways were proposed as a result of two-dimensional correlation spectroscopy applied to the mass spectral data, which was referred to as two-dimensional correlation mass spectrometry (2D-CMS). The 2D-CMS method was first validated by analysis of simple and more complex kinetic models followed by simple and more complex molecules. To further aid in the elucidation of the dissociation mechanisms, computational chemistry was performed for the optimization of stable precursor and product ion structures and calculations of their relative energies and adduct dissociation energies.
Show less - Date Issued
- 2012
- Identifier
- CFE0004377, ucf:49371
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004377
- Title
- Development of laser spectroscopy for elemental and molecular analysis.
- Creator
-
Liu, Yuan, Richardson, Martin, Vanstryland, Eric, Bass, Michael, Sigman, Michael, University of Central Florida
- Abstract / Description
-
Laser-Induced Breakdown Spectroscopy (LIBS) and Raman spectroscopy are still growing analytical and sensing spectroscopic techniques. They significantly reduce the time and labor cost in analysis with simplified instrumentation, and lead to minimal or no sample damage. In this dissertation, fundamental studies to improve LIBS analytical performance were performed and its fusion with Raman into one single sensor was explored.On the fundamental side, Thomson scattering was reported for the...
Show moreLaser-Induced Breakdown Spectroscopy (LIBS) and Raman spectroscopy are still growing analytical and sensing spectroscopic techniques. They significantly reduce the time and labor cost in analysis with simplified instrumentation, and lead to minimal or no sample damage. In this dissertation, fundamental studies to improve LIBS analytical performance were performed and its fusion with Raman into one single sensor was explored.On the fundamental side, Thomson scattering was reported for the first time to simultaneously measure the electron density and temperature of laser plasmas from a solid aluminum target at atmospheric pressure. Comparison between electron and excitation temperatures brought insights into the verification of local thermodynamic equilibrium condition in laser plasmas.To enhance LIBS emission, Microwave-Assisted LIBS (MA-LIBS) was developed and characterized. In MA-LIBS, a microwave field extends the emission lifetime of the plasma and stronger time integrated signal is obtained. Experimental results showed sensitivity improvement (more than 20-fold) and extension of the analytical range (down to a few tens of ppm) for the detection of copper traces in soil samples. Finally, laser spectroscopy systems that can perform both LIBS and Raman analysis were developed. Such systems provide two types of complimentary information (-) elemental composition from LIBS and structural information from Raman. Two novel approaches were reported for the first time for LIBS-Raman sensor fusion: (i) an Ultra-Violet system which combines Resonant Raman signal enhancement and high ablation efficiency from UV radiation, and (ii) a Ti:Sapphire laser based NIR system which reduces the fluorescence interference in Raman and takes advantage of femtosecond ablation for LIBS.
Show less - Date Issued
- 2013
- Identifier
- CFE0005105, ucf:50729
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005105
- Title
- Qualitative and Quantitative Elemental Composition Analysis of the Surrounding Pollen Coating via ICP-MS.
- Creator
-
Voyer, Brandy, Baudelet, Matthieu, Rex, Matthew, Sigman, Michael, University of Central Florida
- Abstract / Description
-
Pollen evidence has proven to be a powerful forensic tool to trace a suspect or item to a victim or a crime scene. This is possible because it is microscopic, abundant in nature, resistant to degradation and decay; it presents dispersal patterns that can be used to generate a 'fingerprint' within specific areas, and has illustrated a unique morphology that can be used to classify species. While the pollen grain morphology has been extensively used to characterize the specific species, not...
Show morePollen evidence has proven to be a powerful forensic tool to trace a suspect or item to a victim or a crime scene. This is possible because it is microscopic, abundant in nature, resistant to degradation and decay; it presents dispersal patterns that can be used to generate a 'fingerprint' within specific areas, and has illustrated a unique morphology that can be used to classify species. While the pollen grain morphology has been extensively used to characterize the specific species, not much has been investigated as pertains to the coating that surrounds the pollen grain aside from it being categorized as waste. This Master thesis focuses on the qualitative and quantitative determination of the elemental composition of this coating surrounding pollen via Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Two methodologies for sample preparation were compared: a complete digestion and analysis of (i) the entire pollen and (ii) the surrounding pollen coating alone removed from the pollen grain by Soxhlet extraction in ethanol. The goal was to discern the elemental composition of the coating and its specific elemental composition in comparison with the whole pollen grain. The results of both F-test and T-test performed for three pollen species indicated that, of the 19 elements investigated, B, Mg, Mn, K, Ti, and Cs resulted in significant differences between the whole grain and the coating alone; while Se, V, Pb, Cr, Al, and Zn can be recognized as being characteristic of the coating surrounding the pollen grain.
Show less - Date Issued
- 2018
- Identifier
- CFE0007261, ucf:52189
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007261
- Title
- The Application of Chemometrics to the Detection and Classification of Ignitable Liquids in Fire Debris Using the Total Ion Spectrum.
- Creator
-
Lewis, Jennifer, Sigman, Michael, Campiglia, Andres, Clausen, Christian, University of Central Florida
- Abstract / Description
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Current methods in ignitable liquid identification and classification from fire debris rely on pattern recognition of ignitable liquids in total ion chromatograms, extracted ion profiles, and target compound comparisons, as described in American Standards for Testing and Materials E1618-10. The total ion spectra method takes advantage of the reproducibility among sample spectra from the same American Society for Testing and Materials class. It is a method that is independent of the...
Show moreCurrent methods in ignitable liquid identification and classification from fire debris rely on pattern recognition of ignitable liquids in total ion chromatograms, extracted ion profiles, and target compound comparisons, as described in American Standards for Testing and Materials E1618-10. The total ion spectra method takes advantage of the reproducibility among sample spectra from the same American Society for Testing and Materials class. It is a method that is independent of the chromatographic conditions that affect retention times of target compounds, thus aiding in the use of computer-based library searching techniques. The total ion spectrum was obtained by summing the ion intensities across all retention times. The total ion spectrum from multiple fire debris samples were combined for target factor analysis. Principal components analysis allowed the dimensions of the data matrix to be reduced prior to target factor analysis, and the number of principal components retained was based on the determination of rank by median absolute deviation. The latent variables were rotated to find new vectors (resultant vectors) that were the best possible match to spectra in a reference library of over 450 ignitable liquid spectra (test factors). The Pearson correlation between target factors and resultant vectors were used to rank the ignitable liquids in the library. Ignitable liquids with the highest correlation represented possible contributions to the sample. Posterior probabilities for the ASTM ignitable liquid classes were calculated based on the probability distribution function of the correlation values. The ASTM ignitable liquid class present in the sample set was identified based on the class with the highest posterior probability value. Tests included computer simulations of artificially generated total ion spectra from a combination of ignitable liquid and substrate spectra, as well as large scale burns in 20'x8'x8' containers complete with furnishings and flooring. Computer simulations were performed for each ASTM ignitable liquid class across a range of parameters. Of the total number of total ion spectra in a data set, the percentage of samples containing an ignitable liquid was varied, as well as the percent of ignitable liquid contribution in a given total ion spectrum. Target factor analysis was them performed on the computer-generated sample set. The correlation values from target factor analysis were used to calculate posterior probabilities for each ASTM ignitable liquid class. Large scale burns were designed to test the detection capabilities of the chemometric approach to ignitable liquid detection under conditions similar to those of a structure fire. Burn conditions were controlled by adjusting the type and volume of ignitable liquid used, the fuel load, ventilation, and the elapsed time of the burn. Samples collected from the large scale burns were analyzed using passive headspace adsorption with activated charcoal strips and carbon disulfide desorption of volatiles for analysis using gas chromatography-mass spectrometry.
Show less - Date Issued
- 2011
- Identifier
- CFE0004477, ucf:49301
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004477
- Title
- Quantitative Assessment of the effects of Microbial Degradation of a Simple Hydrocarbon Mixture.
- Creator
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Kindell, Jessica, Sigman, Michael, Bridge, Candice, Campiglia, Andres, University of Central Florida
- Abstract / Description
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Ignitable liquids consist of either a single organic compound or a complex organic mixture. In regards to fire debris analysis, the analyst is responsible for determining if an ignitable liquid residue is present. However, when extracted from soil-containing fire debris evidence, chemical degradation from microorganisms is observed to result in the loss of compounds based on chemical structure. It can also happen when the evidence container is stored at room temperature before analysis. This...
Show moreIgnitable liquids consist of either a single organic compound or a complex organic mixture. In regards to fire debris analysis, the analyst is responsible for determining if an ignitable liquid residue is present. However, when extracted from soil-containing fire debris evidence, chemical degradation from microorganisms is observed to result in the loss of compounds based on chemical structure. It can also happen when the evidence container is stored at room temperature before analysis. This can present a challenge to the fire debris analyst when identifying and classifying the ignitable liquid residue based on the criteria established by standard test methods. The purpose of this research was to observe the microbial degradation of fourteen compounds, at room temperature over a period of time, for possible by-product formation that could coincide with compounds normally present in an ignitable liquid. Additionally, a quantitative assessment was performed to observe and record the loss rate of compounds in a representative simple mixture. Finally, the loss rate from the simple mixture was compared to commercially available ignitable liquids. Degradation studies were conducted to observe the microbial degradation of a representative compounds (individually and in a simple mixture, both weathered and unweathered) and seven ignitable liquids of different ASTM E1618 classifications. Potting soil was spiked with 20 (&)#181;L of a liquid/compound and was allowed to stand at room temperature for a period of time. The simple mixture was evaporated to 50% and 90% using a steady nitrogen gas flow to compare the degradation process to the unweathered mixture. All samples were extracted and analyzed using passive-headspace concentration and gas chromatography-mass spectrometry.The formation of by-products was not observed when degrading the compounds from the simple mixture individually as seen in other research. The simple mixture, unweathered and 50% weathered, resulted in rapid degradation of their oxygenated compounds. The straight-chained alkanes and toluene were observed to be more susceptible to microbial attack than the highly-substituted aromatics and the branched and cyclic alkanes. The 90% weathered mixture followed the same degradation trend as the unweathered and 50% weathered samples, although it only contained two compounds. The loss rates/half-lives for each simple mixture sample (unweathered, 50% weathered, and 90% weathered) were determined to be approximately 3.5, 3.5, and 0.84 days. The unweathered and 50% weathered sample half-lives were similar due to containing compounds with similar susceptibility to degradation, while the 90% weathered sample contained one compound that was more highly susceptible to degradation. When comparing the 3.5 day half-life to the seven different ASTM class liquids, the isoparaffinic product and the naphthenic-paraffinic product had similar rates of degradation while aromatic solvent and normal alkane classes had the shortest half-lives. When observing the degradation of the gasoline, medium petroleum distillate and the miscellaneous, the constituent compounds were seen to exhibit a range of degradation rates that corresponded to half-lives less than and greater than 3.5 days.
Show less - Date Issued
- 2015
- Identifier
- CFE0005966, ucf:50817
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005966
- Title
- Development of Molecularly Imprinted Polymers for Forensic Applications.
- Creator
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Martinez, Sara, Sigman, Michael, Bridge, Candice, Yestrebsky, Cherie, University of Central Florida
- Abstract / Description
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In some forensic disciplines various methods of extraction are used to perform analysis. Among these methods, solid phase extraction (SPE) and solid phase microextraction (SPME) are used in fields such as toxicology and explosives analysis. To enhance extraction efficiency in SPE and SPME, molecularly imprinted polymers (MIPs), which are designer polymers, can be more selective for the binding of an analyte or group of analytes that are similarly structured. Separation of analytes from...
Show moreIn some forensic disciplines various methods of extraction are used to perform analysis. Among these methods, solid phase extraction (SPE) and solid phase microextraction (SPME) are used in fields such as toxicology and explosives analysis. To enhance extraction efficiency in SPE and SPME, molecularly imprinted polymers (MIPs), which are designer polymers, can be more selective for the binding of an analyte or group of analytes that are similarly structured. Separation of analytes from complex mixtures is possible by utilizing these polymers. This may be especially useful in forensic applications where sample sizes may be small and composition may be complex. In this work, MIP solid phase microextraction fibers (MIP-SPME) were fabricated and caffeine was selectively sampled in the presence of theophylline and theobromine. Calibration studies were performed using the MIP-SPME to quantitate the concentration of caffeine in teas and coffees. MIP-SPME fibers were also prepared with 2,4-dinitrotoluene and deuterated 2,6-dinitrotoluene. Less selectivity was obtained for extraction of 2,4-DNT and 2,6-DNT in the presence of other DNT isomers. Fabricated blank polymers extracted analytes at the same response as templated polymers for both caffeine and DNT, despite expected results. MIP-SPE columns were also fabricated using deuterated 2,6-DNT to determine if changing the extraction procedure would increase extraction selectivity. Using different solvents in the extraction procedure changed the extraction performance efficiency of the MIPs due to the change in solvent polarity. All samples were analyzed using gas chromatography mass spectrometry.
Show less - Date Issued
- 2016
- Identifier
- CFE0006477, ucf:51423
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006477
- Title
- Classification of Silicone-Based Personal and Condom Lubricants Using DART-TOFMS.
- Creator
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Harvey, Lauren, Bridge, Candice, Sigman, Michael, Campiglia, Andres, Yestrebsky, Cherie, University of Central Florida
- Abstract / Description
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Sexual lubricants are used to enable sexual encounters. There are different types of sexual lubricants such as water-based, oil-based, and silicone-based. They come pre-applied to condoms and separately in bottles as personal lubricants. Although sexual lubricants are intended for consensual use, they are also unfortunately used during the commission of sexual assaults. The analysis of sexual lubricants facilitates sexual assault investigations. With the increased usage of condoms in sexual...
Show moreSexual lubricants are used to enable sexual encounters. There are different types of sexual lubricants such as water-based, oil-based, and silicone-based. They come pre-applied to condoms and separately in bottles as personal lubricants. Although sexual lubricants are intended for consensual use, they are also unfortunately used during the commission of sexual assaults. The analysis of sexual lubricants facilitates sexual assault investigations. With the increased usage of condoms in sexual assault cases, the potential of collected DNA evidence in each case is reduced. In the absence of biological evidence, the presence of sexual lubricants after a sexual assault can provide an additional link between a suspect and the crime scene and/or victim. Having the ability to compare known and unknown sexual lubricants may be the only actionable information available for investigators. Current lubricant analysis only classifies samples into lubricant types based on the major component such as glycerol, petrolatum, and polydimethylsiloxane for water-based, oil-based, and silicone-based lubricants respectively. Differentiation within major types has not been explored. Previously, protocols have been developed to detect and categorize personal lubricants using Fourier transform infrared (FTIR) spectroscopy, gas chromatography-mass spectrometry (GC-MS), liquid chromatography mass spectrometry (LC-MS), and pyrolysis GC-MS. FTIR is routinely used as a screening tool to detect peaks of the major lubricant components and the mass spectrometry (MS) techniques are commonly used to confirm the presence of some of the major components, excluding PDMS.This thesis focused on the differentiation of silicone-based personal and condom lubricants because it is a common type of lubricant due to its ability to reduce friction for a longer period of time. Fifty-six (56) silicone personal and condom lubricants were analyzed to identify unique characteristics that can be used to determine individual sub-classes and test those sub-classes. Direct analysis in real time-time of flight mass spectrometry (DART-TOFMS) was utilized because minor and unique molecular ions that could be attributed to different sub-groups can easily be distinguished from the major sample peaks. This is primarily based on the direct mass spectrometry design of the instrumentation that can differentiate minor components from major components that might not be observed using traditional chromatographic separation. The DART source creates molecular ions for individual components in mixed samples under atmospheric conditions in either positive or negative mode. The TOF-MS, which is capable of high resolution and accurate mass analysis, allows more accurate and precise detection of molecular component ions. Additionally, no sample preparation is required to analyze neat samples, which minimizes potential contamination issues. Attenuated total reflectance-FTIR (ATR-FIR) was used to analyze the training set personal lubricants to compare previous methods of analysis to the newly developed DART-TOFMS method of analysis.Principle component analysis (PCA) and cluster analysis were used to identify potential sub-groups and subsequently a classification scheme. Linear discriminant analysis was utilized to conduct leave one out cross validation and to categorize test samples. Eight sub-groups were developed based on the presence and/or absence of PDMS and minor component peaks observed.A classification scheme was developed using the eight sub-groups identified through PCA and cluster analysis. This classification scheme was tested using LDA to classify blind samples. One group includes a scented personal lubricant. Another group includes flavored condom lubricants. The other groups were developed based on the relative intensity of PDMS peaks and minor component peaks. Variation of the intensity of PDMS peaks between and within samples of different lot numbers causes some misclassification of samples. This classification scheme also doesn't take into account real-world factors such as dilution and biodegradation. Although further research is required to create a more stable classification scheme, the identified sub-groups are a good foundation for the creation of a lubricant database and finalized classification scheme.
Show less - Date Issued
- 2016
- Identifier
- CFE0006459, ucf:51415
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006459
- Title
- Characterization of Post-Fire Priming Cup Residue Using Scanning Electron Microscopy Coupled With Energy Dispersive X-Ray Spectrometry.
- Creator
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Terry, Molly, Bridge, Candice, Sigman, Michael, Campiglia, Andres, University of Central Florida
- Abstract / Description
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Ammunition is most often comprised of a lead-based priming mixture which contributes to the traditional characteristics of gunshot residue (GSR). Due to the health risks often associated with lead, lead-free primer alternatives are becoming increasingly more popular. Thus, it is becoming more difficult to determine the presence of GSR based on traditional means, i.e. the presence of lead (Pb), barium (Ba), and antimony (Sb). Eight different ammunitions were purchased which consisted of one...
Show moreAmmunition is most often comprised of a lead-based priming mixture which contributes to the traditional characteristics of gunshot residue (GSR). Due to the health risks often associated with lead, lead-free primer alternatives are becoming increasingly more popular. Thus, it is becoming more difficult to determine the presence of GSR based on traditional means, i.e. the presence of lead (Pb), barium (Ba), and antimony (Sb). Eight different ammunitions were purchased which consisted of one lead-based and one lead-free from four different manufacturers, including Winchester, Federal, Liberty, and Sellier (&) Bellot. Half of the rounds from each manufacturer and chemical composition (i.e. lead-based or lead-free) were disassembled, e.g. the projectile and smokeless powder were removed, leaving the priming cup in place (i.e. primed only). The remaining cartridges were left intact (i.e. full cartridge). Both the full cartridges and the primed only cartridges for each ammunition were fired using a 9mm Glock and the cartridges were collected post-fire, and subsequently deprimed. Five cups and five anvils from each type of ammunition were adhered to aluminum stubs via colloidal graphite. The GSR remaining on the anvils and in the cups was then analyzed using scanning electron microscopy coupled with energy dispersive x-ray spectrometry (SEM-EDX). Three spectra were collected for each anvil and each cup resulting in 30 total spectra per type of ammunition. The primary element peaks were then selected and four different dataset matrices were created for the full cartridge anvils, full cartridge cups, primed only anvils, and primed only cups. The data was processed using unit vector normalization and was then analyzed using principal component analysis (PCA) and linear discriminant analysis (LDA) to determine the characterization between lead-free and lead-based ammunition. The anvils provided better separation and characterization based on the ability to better collect x-rays, and therefore demonstrated the capability of the ammunition to cluster by both primer mixture composition and manufacturer. The lead-based and lead-free primers showed consistencies across samples, such as the presence or absence of K, which allowed for characterization based on primer composition.
Show less - Date Issued
- 2016
- Identifier
- CFE0006509, ucf:51377
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006509
- Title
- LASER FILAMENT INTERACTION WITH AEROSOLS AND CLOUDS.
- Creator
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Jeon, Cheonha, Richardson, Martin, Vanstryland, Eric, Baudelet, Matthieu, Sigman, Michael, University of Central Florida
- Abstract / Description
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A high powered ultrashort laser pulse can propagate as a diffraction-free self-channeled structure called a filament, created by a combination of nonlinear processes. With its ability to convey extremely high intensity beams to distant targets, many applications such as remote sensing, cloud seeding, and discharge guiding are potentially possible. However, one of the main challenges of outdoor field applications is the laser propagation through the atmosphere where pressure fluctuations and...
Show moreA high powered ultrashort laser pulse can propagate as a diffraction-free self-channeled structure called a filament, created by a combination of nonlinear processes. With its ability to convey extremely high intensity beams to distant targets, many applications such as remote sensing, cloud seeding, and discharge guiding are potentially possible. However, one of the main challenges of outdoor field applications is the laser propagation through the atmosphere where pressure fluctuations and concentrations of aerosols may be present. The rationale behind the work presented in this dissertation is to evaluate the robustness of the filamentation, measure the interaction losses as well as understanding the modifications to (i) filament length (ii) supercontinuum generation, and (iii) the beam profile along propagation through perturbed media.Detailed studies of the interaction of a single filament with a single water droplet are presented. In addition, preliminary results on filament propagation through a cloud of aerosols are discussed. The effect of pressure on the beam profile along propagation and on the supercontinuum generated by the filament is studied. This document provides valuable insight into the complex nonlinear processes affecting the formation, propagation and post propagation of filaments under adverse atmospheric conditions.
Show less - Date Issued
- 2016
- Identifier
- CFE0006530, ucf:51368
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006530
