A comprehensive investigation of sensitive ecosystems in South Florida with the main goal of determining the identity, spatial distribution, and sources of both organic biocides and trace elements in different environmental compartments is reported. This study presents the development and validation of a fractionation and isolation method of twelve polar acidic herbicides commonly applied in the vicinity of the study areas, including e.g. 2,4-D, MCPA, dichlorprop, mecroprop, picloram in surface water. Solid phase extraction (SPE) was used to isolate the analytes from abiotic matrices containing large amounts of dissolved organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-) in a Quadrupole Ion Trap mass spectrometer was used to perform the characterization of the herbicides of interest. The application of Laser Ablation-ICP-MS methodology in the analysis of soils and sediments is reported in this study. The analytical performance of the method was evaluated on certified standards and real soil and sediment samples. Residential soils were analyzed to evaluate feasibility of using the powerful technique as a routine and rapid method to monitor potential contaminated sites. Forty eight sediments were also collected from semi pristine areas in South Florida to conduct screening of baseline levels of bioavailable elements in support of risk evaluation. The LA-ICP-MS data were used to perform a statistical evaluation of the elemental composition as a tool for environmental forensics. A LA-ICP-MS protocol was also developed and optimized for the elemental analysis of a wide range of elements in polymeric filters containing atmospheric dust. A quantitative strategy based on internal and external standards allowed for a rapid determination of airborne trace elements in filters containing both contemporary African dust and local dust emissions. These distributions were used to qualitative and quantitative assess differences of composition and to establish provenance and fluxes to protected regional ecosystems such as coral reefs and national parks.

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

Orientadores: Francisco das Chagas Marques, Carlos Lenz César / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-29T22:06:44Z (GMT). No. of bitstreams: 1 VillegasBorrero_NelsonFabian_M.pdf: 7427305 bytes, checksum: 95d120bd4cca81a54f7e8af57dfd2ab5 (MD5) Previous issue date: 2015 / Resumo: Neste trabalho foram fabricadas nanopartículas metálicas de prata (NPsM de Ag) em soluções coloidais usando a técnica de ablação à laser. Parâmetros como o comprimento de onda do laser, energia do pulso e a taxa de repetição afetam a distribuição de tamanho das NPsM. Assim, neste trabalho estudamos a influência destes parâmetros sobre o tamanho das NPsM de Ag. Para isto foi feita uma montagem experimantal na qual um alvo de prata é imerso em um líquido e irradiado por um pulso de laser de Nd:YAG para criar soluções coloidais. Foi encontrada uma variação dos picos de absorção entre = 394nm e = 405nm. Segundo a previsão da teoria de Gustav Mie, as variações nos picos tem a ver com a variação na distribuição de tamanhos. Para comprovar estes resultados foi feita uma estimativa do tamanho médio das NPsM de Ag usando a análise de imagens tomadas com o Microscópio Eletrônico de Varredura (MEV) e a técnica de Espalhamento Dinâmico da Luz (DLS). O espectro experimental e a teoria de Gustav Mie (simulação feita usando o software mathematica) encontram-se em concordância. As NPsM produzidas foram usadas para medir o efeito de aumento no sinal Raman em superfícies (SERS) encontrando-se que o sinal do espalhamento Raman de corantes usados em diferentes pesquisas (Rodâmina B e N719) aumenta com o uso das NPsM / Abstract: In this work we fabricated silver nanoparticles (Ag NPs) in colloidal solutions with specific sizes. Parameters like laser wavelength, pulse energy and pulse repetition rate affect the distribution of NPs size. In this work we studied the influence of these parameters on the size of Ag NPs. For that purpose we mount a set-up in which a silver target was immersed in liquid and irradiated by Nd:YAG pulsed laser to create different colloids. We found that the absorption peak of these colloids lays between 394nm and 405nm. We estimated a mean size of Ag NPs from images taken by Scanning Electron Microscope (SEM) and Dynamic Ligth Scattering (DLS). The calculated absorption spectra and simulation through Gustav Mie theory (Simulated in Matthemathica software) were in good agreement. The produced NPs were used in Enhacement Raman Spectroscopy (SERS) measurements, finding that the signal of Rhodamina B and N719 Dyes increases using these NPsM / Mestrado / Física / Mestre em Física / 1247650/2013 / CAPES

Abstract The reduction of product development cycle time is a major concern in industries to remain competitive in the marketplace. Among various manufacturing technologies, 3D printing technology or also known as additive manufacturing (AM), has shown excellent potential to reduce both the cycle time and cost of the product due to its lower consumption of energy and material usage compared to conventional manufacturing. Fused deposition modeling (FDM) is one of the most popular additive manufacturing technologies for various engineering applications which has the ability to build functional parts having complex geometrical shapes in reasonable build time and can use less expensive equipment and cheaper material. However, the quality of parts produced by FDM has some challenges such as poor surface quality.   The focus of this study is improving the surface quality produced by Fused Deposition Modeling. The investigations include 3D printing study samples with optimum parameter settings and post-processing the sample’s surfaces by laser ablation. Taguchi’s design of the experiment is employed to identify the optimum settings of laser ablation the FDM surfaces. Laser power, laser speed and pulse per inch (PPI) are the laser settings considered in the study. Characterization of the samples are done using Dino-lite USB camera images and GFM Mikro-CAD fringe projection microscope is used to measure the surface roughness of the samples. Areal surface parameters are used to characterize and compare the surfaces of as printed and laser ablated. It is observed that the effect of laser ablation varies with respect to surfaces printed at different angles and laser-ablated with different settings. The surface roughness of laser-ablated surfaces is found to be lower than as-printed FDM surfaces.

En réponse aux opérations futures d’assainissement des installations nucléaires, la décontamination par ablation laser de surfaces métalliques apparait comme une technique adaptée aux enjeux sanitaires et économiques actuels. L’objectif est d’ablater par un faisceau laser de façon préférentielle la surface oxydée contenant des radioéléments et de récupérer les éléments vaporisés pour pouvoir isoler la contamination radioactive en vue de son stockage. A la différence des techniques existantes comme le ponçage ou le traitement chimique par gel ou mousse, le traitement laser permet de ne pas produire de déchets secondaires et de pouvoir être effectué à distance en diminuant considérablement la dose reçue par les opérateurs. Le retour d’expérience a montré la nécessité d’optimiser le procédé en vue de limiter la contamination résiduelle. Les phénomènes responsables de cette limitation et identifiés dans la littérature sont la pénétration des contaminants dans le substrat métallique par effet thermiques induits par laser et le piégeage des radionucléides dans des défauts de surface micrométriques. Les travaux de thèse auront donc comme objectifs d’étudier et d’optimiser la décontamination de surfaces métalliques avec des couches d’oxydes contaminées de façon volumique avec un simulant de radionucléide (Eu) par ablation laser, en vue dans un second temps d’améliorer de l’efficacité de la technique au niveau des défauts surfaciques. Enfin, au-delà de la démarche expérimentale, cette thèse vise à contribuer à la compréhension de l’interaction laser/matière dans le cadre de notre étude via la simulation du chauffage de surface métallique par modélisation multi physique. / The preparation of future decommissioning of nuclear installations is currently facing economical and sanitary challenges. The metallic-surface decontamination by laser ablation is here studied as an appropriate and efficient technique, which involves ejection of surface contamination by subjecting the surface to high-energy laser pulses followed by subsequent trapping to avoid environmental dispersion. This process has many advantages such as the minimization of secondary waste, no production of effluents and the reduction of the exposition of workers by the automation of the process. Previous studies highlighted the need to optimize the process in order to limit the residual contamination. The identified reasons for this limitation are the contamination penetration into the metal bulk induced by the laser treatment and the entrapment of the radionuclides in surface defects like micro cracks. The aim of this work is the study and the cleaning optimization of metallic surfaces with an oxide layer implemented with a non-radioactive contamination (Eu). Secondly, the cleaning efficiency has been improved in case of damaged surfaces with defects such as cracks. Beyond an experimental study, The ablation of a metallic substrate with a submicrometric oxide layer is currently modeled using a numerical and multiphysics approach in order to determine the mechanism involved during the process.

La connaissance du raisin et du vin est aussi vieille que l’histoire culturelle de l’humanité. Il est bien connu depuis l'ancienne civilisation l'influence du «terroir» sur le vin, c'est-à-dire un espace géographique délimité où une communauté humaine construit au cours de l’histoire un savoir collectif de production qui confère une typicité et engendrent une réputation pour un produit originaire de cet espace géographique. Les grands vins, tout comme les vins de moindre renommée, représentent une cible privilégiée des faussaires. La contrefaçon s’intensifie et se développe en grande partie en Chine. Selon la comission du vin et spiritueux du Comité National des Conseillers du Commerce Extérieur de la France, il existe au moins une bouteille de vin forgé pour chaque bouteille de vin français original. Bien que la Chine ne soit pas le seul fournisseur de vins contrefaits, la croissance rapide du marché du vin dans ce pays et l'absence de lois protégeant la propriété intellectuelle ont déclenché le marché noir. On estime que 20% des vins consommés dans le monde sont contrefaits. Selon l’Office de l’Union Européenne pour la propriété intellectuelle, l’industrie des vins et spiritueux européenne perd environ 1,3 milliard d’euros chaque année du fait de la contrefaçon sur le marché de l’UE, ce que correspond à 3,3% de ventes de ces secteurs, ce qui se traduisent en une perte directe d’environ 4800 emplois. La contrefaçon des vins peut revêtir plusieurs formes et les mesures de lutte contre la contrefaçon en vigueur ont montré leur manque d’efficacité. Ce sont des techniques invasives qui sont utilisés lors de la vérification des vins. Elles sont basées principalement sur une analyse du contenu et nécessitent donc l’ouverture de la bouteille, ce qui est dommageable lorsqu’il s’agit de vins de grande valeur. Le travail présenté ici, présente un nouvel outil de diagnostic non ambigu basé sur l'analyse ultra-trace des matériaux constituant l’emballage (verre, papier et encres, capsule) par ablation laser femtoseconde ICPMS. Cette technique non invasive est rapide (5 minutes environ), permet de détecter des traces élémentaires inférieures au ng/g et n’a pas d’équivalent en terme de performance à ce jour. Dans une première étape, nous avons designée et développé une nouvelle cellule d’ablation qui permet de réaliser l’analyse multiélémentaire direct en n’induisant aucune dégradation visible sur la bouteille. Dans une deuxième étape, la nouvelle cellule d’ablation a été apliquée a l’analyse direct de l’emballage. Pour l’analyse du papier et des encres, en raison du manque de matériaux de référence certifiés, représente un véritable challenge analytique. Nous avons mis au point une approche quantitative en développant nos propres standards par impression jet d’encre de papier à partir de solutions dopées. Finalement, un nouvel outil de diagnostic non ambigu basé sur l’espectroscopie Raman et Infrarouge a été développée pour l’analyse moleculaire qualitatif et direct du papier et des encres afin de compléter les résultats obtenus avec le fsLA-ICPMS. L’instrumentation et ces méthodes de caractérisation des emballages ont été appliquées avec succès à l’analyse d’un grand nombre de bouteilles (n>200) d’origine contrôlée et de bouteilles originaires d’autres pays. Les traitements statistiques des données basés sur une analyse multivariée (PCA, PLS, classification hiérarchique) montrent clairement la distinction entre les bouteilles d’origines et les bouteilles contrefaites en isolant et hiérarchisant les éléments traces à l’origine de cette discrimination. Il a par ailleurs été possible de différencier la signature chimique des bouteilles selon leur origine géographique et le millésime. / The knowledge of grape and wine is as old as the cultural history of humankind. It is well known since the ancient civilizations the influence of the "terroir" on wine, which is a limited geographical space where a human community constructs a collective knowledge of production, which gives wine grapes their distinctive character and generate a reputation for a product originating from this geographical area. The great wines are a prime target for counterfeiters because of their brand value, mostly originating from the Asian market. According to the National Committee of Foreign Trade Advisers of France (Comité National des Conseillers du Commerce Extérieur de la France, CNCCEF) the wine fraud is not just a matter of a few bottles but also includes an entire clandestine industry. According to the Wine and Spirits Commission of the CNCCEF, there is at least one bottle of forged wine for each bottle of original French wine in China. Although China is not the only supplier of counterfeited wines, the rapid growth of the wine market in this country and the absence of laws protecting intellectual property have triggered the counterfeit market. It is estimated that 20% of the wines consumed in the world are counterfeit. In fact, according to the European Union Intellectual Property Office, it is estimated that the legitimate industries losses approximately €1.3 billion of revenue annually due to the presence of counterfeit spirits (€740 million) and wine (€530 million) in the EU market, 3.3% of the sector’s sales, which results in a direct loss of about 4,800 jobs. Wine fraud may be categorized in several forms and anti-counterfeiting measures have shown lack of effectiveness. Unfortunately, invasive techniques are used for wine verification purposes, which are mainly based on liquid sampling, requiring opening the bottle that can be fateful when it comes to great value wines. This work presents a new unambiguous diagnostic tool based on the ultra-trace analysis of the wine packaging (glass, paper and inks, capsule) by femtosecond laser ablation coupled to ICPMS. This is a fast (about 5 minutes) and non-invasive technique, which allows detecting trace elements below ng/g and has no equivalent in terms of performance to date. In a first step, we have designed and developed a new ablation cell that allows direct and multi-elemental analysis of the packaging without causing any visible degradation on the bottle. In a second step, the new ablation cell has been applied to the direct analysis of the packaging components. For the analysis of paper and inks, as the lack of certified reference materials represents a real analytical challenge, we have developed a quantitative approach by developing our own standards by printing spiked solution with an inkjet printer. Finally, in order to complement the results obtained with fsLA-ICPMS, a new unambiguous diagnostic tool based on Raman spectroscopy and Infrared spectroscopy has been developed for the qualitative and direct molecular analysis of paper and inks. The instrumentation and packaging characterization methods have been applied to the analysis of a large number of bottles (n> 200) of controlled origin and bottles originating from other countries. The statistical processing of data based on multivariate analysis (PCA, PLS, hierarchical classification) clearly shows the distinction between authentic and counterfeited bottles by isolating and prioritizing the trace elements responsible for this discrimination. It was also possible to distinguish the chemical signature of the bottles according to their geographical origin and the vintage.

Der Betrieb kerntechnischer Anlagen führt zur Kontamination von Oberflächen, das heißt der Verunreinigung mit Radionukliden, innerhalb des Containments. Die Stilllegung kerntechnischer Anlagen erfordert die Dekontamination metallischer Komponenten und Baustrukturen zur Minimierung von Masse und Volumen des radioaktiven Abfalls. Stand der Technik ist die Nutzung von chemischen und mechanischen Dekontaminationsverfahren. Die Reinigung von Oberflächen mittels gescannter Laserstrahlung ermöglicht die Bearbeitung großer Flächen bei hohen Flächenraten. Gleichzeitig ist der Laserabtrag ein kontaktloses, nahezu kräftefreies Verfahren, welches zur Minimierung oben genannter Abfälle durch Einsatz für die Dekontamination beitragen kann. In der vorliegenden Arbeit werden die Ergebnisse aus der internationalen Forschung für die Auswahl eines geeigneten Lasers aufgegriffen und auf ein praxistaugliches Lasersystem übertragen. Der ns-gepulste Nd:YAG-Laser mit einer mittleren Leistung von 150 W wird für den Einsatz im kerntechnischen Umfeld durch den Einschluss der Reaktionszone angepasst und so die Rekontamination durch mobilisierte Radionuklide verhindert. Die Nutzung kurzgepulster Laser führt zum Abtrag durch Schmelzen und Verdampfen auf metallischen Oberflächen, wobei eine maximale Schmelztiefe von 1,8 μm ermittelt wird. Durch Analysen an Querschliffen mittels Auflichtmikroskopie und Rasterelektronenmikroskopie kann die Gefügeänderung der metallischen Substrate unterhalb dieser Tiefe bei Pulsfolgefrequenzen von 12 kHz ausgeschlossen werden. Der Abtrag von Dekontaminationsanstrichen erfolgt ab einer Fluenz von 1,8 J/cm² bei hohen Abtragraten um 1,1 μm/(J cm²) im Vergleich zu sehr geringen Abtragraten um 0,006 μm/(J cm²) von ferritischem Stahl. Der vollständige Abtrag von Beschichtungen ist somit äußerst selektiv, was zur Abfallminimierung beiträgt. Der Dekontaminationseffekt wird in vergleichenden Untersuchungen zwischen stabilen und radioaktiven Isotopen geprüft. Für beide Verunreinigungen werden Präparationsroutinen zur reproduzierbaren Herstellung kontaminierter Proben entwickelt. Die Aktivität der radioaktiven Proben wird durch den Laserabtrag um mehr als 97 % reduziert, was auf die sehr gute Eignung des Laserverfahrens für die Dekontamination hinweist.:1 Einleitung 2 Kontamination in kerntechnischen Anlagen 3 Grundlagen der laserbasierten Dekontamination 4 Untersuchungen zur laserbasierten Dekontamination 5 Experimentelle Ergebnisse 6 Zusammenfassung und Ausblick / The operation of nuclear sites results in contamination of surfaces within their containment. Decommissioning of nuclear sites requires decontamination of metal surfaces and building structures to minimize the mass and volume of radioactive waste products. State of the art decontamination technologies are based on chemical and mechanical approaches, which achieve high decontamination factors, but result in the generation of chemical and secondary radioactive waste. Cleaning of surfaces by scanned laser beams renders the processing of large surfaces at high surface rates possible. Laser cleaning is simultaneously free of contact and restoring forces and could lead to the further reduction of radioactive waste from decommissioning of nuclear sites. The results of international state of science are summarized and applied for the choice of a laser, which is able to comply with the demands for application in decontamination tasks. Within this thesis a ns-pulsed Nd:YAG-laser with a mean power of 150 W is modified for the utilization in nuclear sites by enclosing the process zone around the ablation area to omit the spread of the mobilized radionuclides. Laser/substrate-interaction results in metal removal via melting and vaporization and a maximum melt depth of 1,8 μm is detected. No further changes within the grain structure of metal substrates are found by the analysis of cross-sections using microscopy and scanning electron microscopy when pulse frequencies of 12 kHz are applied. The removal of decontamination paint is achieved for fluences above 1,8 J/cm² at high removal rates of 1,1 μm/(J cm²), compared to the very low removal rate for ferritic steel of 0,006 μm/(J cm²). Complete and selective removal of the paints can thus be realized, which contributes to the waste minimization in decontamination projects. Laser-based decontamination is exercised for stable as well as radioactive isotopes in comparative experiments. For this purpose, sample preparation methods are developed to provide replicable contaminated surfaces. The activity of radioactive samples is reduced to less than 3 % of the starting value by laser-based decontamination, which is proof of the very good suitability of the process for the application in nuclear decommissioning.:1 Einleitung 2 Kontamination in kerntechnischen Anlagen 3 Grundlagen der laserbasierten Dekontamination 4 Untersuchungen zur laserbasierten Dekontamination 5 Experimentelle Ergebnisse 6 Zusammenfassung und Ausblick

En la presente Tesis Doctoral la técnica de ablación laser acoplada a ICP-OES/MS ha sido empleada para analizar muestras sólidas, como catalizadores usados en el refinado del petróleo y polímeros. Se han llevado a cabo dos tipos de análisis, un análisis global de las muestras que proporciona información general y un análisis localizado que permite obtener información acerca de la distribución espacial de los elementos de interés en las muestras. Las diferentes variables de la técnica ablación láser son estudiadas con el fin de seleccionar aquellas que conducen una señal alta y estable, así como a un menor grado de fraccionamiento. Este estudio se realiza para cada tipo de muestra, ya que los resultados dependen de la matriz estudiada. Además, en esta Tesis doctoral se desarrolla un método de calibración para llevar a cabo un análisis cuantitativo de las muestras sólidas, basado en la deposición de patrones líquidos sobre la muestra sólida. Este método es conocido como “dried droplet calibration approach” (DDCA), y permite cuantificar elementos presentes en muestras sólidas sin necesidad de usar materiales de referencia sólidos. Este nuevo método de calibración compensa el fraccionamiento elemental y los efectos de matriz, proporcionando resultados exactos y preciosos para muestras complejas tales como vidrios, catalizadores y polímeros.

abstract: Geochronology and thermochronology are valuable tools for investigating the synergy between the deformational and erosional processes that shape mountainous terrains. Though numerous techniques have been developed to probe the rate and timing of events within these settings, the research presented here explores how scientists can use fewer samples to produce richer data products with broader contextual importance. The beginning of this compilation focuses on establishing laboratory techniques to facilitate this goal. I developed a novel laser ablation ‘double dating’ (LADD) technique that rapidly yields paired U/Pb and (U-Th)/He dates for the accessory minerals zircon, titanite, and apatite. The technique obviates the need for geometric corrections typically applied during (U-Th)/He data reduction, enables the analysis of a broader spectrum of detrital crystals, and provides the opportunity for additional mapping and isotopic analyses that are traditionally challenging to procure and/or fraught with assumptions. Despite the technique’s promise, I also found it essential to weigh several considerations of relevance when attempting to date young (≤ Miocene) accessory minerals with low concentrations of U + Th. Consequently, I discuss the impact that such variables have on the magnitude of analytical imprecision and the data’s flexibility for geologic interpretation. Beyond the lab, I collected a suite of bedrock and detrital samples from small catchments draining the southeastern Sierra Nevada mountains of California. Using the techniques described above as well as conventional methods for (U-Th)/He zircon dating, I compared the utility of both bedrock and detrital approaches for extrapolating local exhumation histories. I additionally tested the ability to employ detrital datasets to extrapolate cooling histories that span from mineral crystallization to rock exhumation through the upper crust. Employing principal mode dates from a combination of zircon and apatite LADD dates and detrital hornblende 40Ar/39Ar dates, I was able to derive thermal models that demonstrate the existence of significant variability in the cooling histories of various intrusive units along the eastern Sierra Nevada. While these results only scratch the surface of what’s possible within the realm of detrital-based research, this contribution demonstrates the utility of expanding the temporal and spatial scope of traditional detrital methodologies. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2019

Adhesive tapes are a common type of evidence involved in violent crimes and national security threats. This research evaluated the utility of LA-ICP-MS and LIBS for the characterization of the trace elemental signature in adhesive tapes for forensic comparisons. LA-ICP-MS and LIBS methods were developed, for the first time, for the qualitative and quantitative analysis of adhesive tapes. The backings of 90 black electrical tapes, previously characterized by conventional techniques (physical examination, IR, Py-GC-MS, and SEM-EDS), were analyzed by LA-ICP-MS to evaluate the ability of the technique to discriminate samples originating from different sources and to associate pieces of tapes originating from the same roll. The discrimination for the LA-ICP-MS analysis of the 90 samples was found to be 93.9%, greater than the discrimination found using SEM-EDS (87.3%). Moreover, 100% correct association resulted for the control samples evaluated in this study. The analysis of tapes by LIBS allowed to separate pairs of tapes that were not previously distinguished by LA-ICP-MS by detecting differences in lithium, calcium, and potassium. The potential of normalization strategies was evaluated for LIBS spectral and statistical comparisons. Two quantitative analysis methods were developed for the analysis of tapes and other polymers. These quantitative methods can help in creating and populating databases that can lead to the use of likelihood ratios and the development of standard methods of analysis and interpretation for tape evidence. Two interlaboratory trials including 7 operational and research laboratories were completed as part of this study. SEM-EDS resulted in 16.7% and 12.5% false positive rates for interlaboratory tests #1 and #2, respectively. Up to 7 and 8 elements were detected by SEM-EDS for interlaboratory test #1 and #2, respectively. LIBS and LA-ICP-MS resulted in no false positives or false negatives. In addition, increased characterization of the samples was obtained by detecting up to 17 elements by LIBS and 32 elements by LA-ICP-MS. The increased sensitivity and selectivity of LIBS and LA-ICP-MS methods has been shown to distinguish tapes originating from different sources, and to correctly associate tapes belonging to the same rolls in different laboratories and by different analysts.