The subject of this diploma thesis is the study of a sample position influence on results of an experiment in laser spectroscopy. The aim is to design an appropriate way for standardization of signal obtained at different conditions with the respect to its applicability for stand-off analysis. In the theoretical part of the diploma thesis there are the basics of LIBS method described together with the issues of stand-off experiment and both, basic and advanced approches for the processing and correction of obtained spectra. Also the experiment is designed here, which is used for the analysis of the sample inclination and distance influence on the detected signal. The choice of appropriate ways for the signal correction follows and their applicability and efficiency is then experimentally tested.

This diploma thesis deals with using laser-induced breakdown plasma spectroscopy for determining the elemental structure of unknown samples. It was necessary to design an appropriate method to qualify material by laser-induced emission spectrum. Pretreatment of data and using a variety of chemometrics methods had to be done in order to qualify the structure of elements. We achieved a required solution by projecting the data to a new PCA space, creating clusters and computing the Euclidean distance between each cluster. The experiment in the practical part was set to detect an interface of two elements. We created a data file simulating the ablation on the interface. This data set was gradually processed applying a mathematical-chemical-physical view. Several data procedures have been compiled: approximation by Lorenz, Gauss and Voigt function and also a pretreatment method such as the detection of outliers, standardization by several procedures and subsequent use of principal components analysis. A summarization of processes for input data is fully described in the thesis.

Tato diplomová práce se zabývá návrhem optomechanického modulu pro chemické mapování metodou spektroskopie laserem buzeného plazmatu (LIBS). Cílem je vyvinout modul, který bude umožňovat analýzu spektrálních čar zinku v ultrafialové (UV) oblasti. V práci jsou popsány teoretické základy metody LIBS a následně je provedena rešerše zaměřená na problematiku dálkové LIBS analýzy. V diplomové práci jsou prezentovány možné optické návrhy fokusační a sběrné optiky, z nichž jsou vybrané následně otestovány. Výsledkem práce je konstrukční návrh modulu.

This doctoral thesis investigates the application of laser-induced breakdown spectroscopy (LIBS) for detection of labeled biomolecules on nitrocellulose paper. Nitrocellulose paper is a material often used for assays involving the concentration and labeling of a target analyte, followed by label detection. Among paper-based diagnostics are lateral-flow immuno-assays (LFIAs). Research efforts have made LFIAs into accessible, portable,and low-cost tools for detecting targets such as allergens, toxins,and microbes in food and water.Gold (Au) nanoparticles are standard biomolecular labels among LFIAs, typically detected via colorimetric means.Other labels, such as quantum dots, are also often metallic, and research is ongoing to expand the number of portable instrumentations applied to their detection. A wide diversity of lanthanide-complexed polymers (LCPs) are used as immunoassay labels but have been inapt for portable paper-based assays owing to lab-bound detection instrumentation, until now. LIBS is a multi-element characterization technique which has recently developed from a bench-top to a portable/hand-held analytical tool. This is among the first studies to show that LCPs can be considered as options for biomolecule labels in paper-based assays using bench-based and hand-held LIBS as label detection modalities.<div>Chapter one reviews the importance of rapid, multiplexed detection of chemical and biological contaminants, the application of current biosensors, and the role of LIBS as an emerging biosensor. Paper-based bioassays were identified as a promising approach for contaminant detection whose capabilities could be enhanced by LIBS. The next chapter dives into LIBS system designs to address which LIBS parameters were appropriate for label detection on paper assay material. A balance of LIBS parameters was found to be important for successful analyte detection. Chaptert hree optimizes a LIBS design for sensitive detection of 17 metals and establishes limit of detection values for 7 metals. Optimal detection parameters depended on the metal being detected and were applied to the objective of the final chapter: LIBS detection of labeled antigen immobilized on a paper-based assay. Both antibody and bacteria detection assays were successfully performed and analyzed using bench top and portable LIBS,suggesting an exciting future for the use of LIBS as a biosensor.The prospect of using LIBS for multiplexed, rapid and sensitive detection of biomolecules in assays is explored, laying grounds for future work in the ever-relevant field of biological and chemical hazard detection.<br></div>

Orientador: Hung Kiang Chang / Resumo: O presente estudo explora a avaliação da distribuição de Light Non-Aqueous Phase Liquid (LNAPL) trapeado na zona saturada empregando a técnica de fluorescência induzida por laser (Laser-Induced Fluorescence – LIF). A área de estudo está localizada no município de Paulínia e tem sido investigada para contaminação por Querosene de Aviação (QAV) desde 2002. O equipamento Ultra-Violet Optical Screening Tool (UVOST®) foi utilizado por possuir a capacidade de detectar moléculas de Hidrocarbonetos Policíclicos Aromáticos (PAH) presentes no LNAPL. Foram realizados um teste piloto de bancada e 21 ensaios de perfilagem LIF em campo, incluindo monitoramento de nível d’água (NA) e nível de óleo (NO) sobrenadante em poços existentes. A perfilagem LIF foi empregada para definir com precisão a extensão lateral do LNAPL, bem como sua tipologia. Além disso, a integração de resultados de fluorescência, oscilação sazonal do NA, espessura de QAV e concentração de naftaleno conduziu para um entendimento mais claro da migração lateral e vertical do LNAPL em subsuperfície. Elevadas intensidades de fluorescência relacionadas ao QAV foram detectadas abaixo do NA na situação de descida do LNAPL em períodos de NA baixo, revelando migrações verticais pretéritas, e correspondem à presença de fase livre nesses períodos, previamente registradas em poços de monitoramento. Análises estatísticas dos quatro canais distintos (comprimentos de onda de 350 nm, 400 nm, 450 nm e 500 nm) mostraram forte correlação en... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present study explores the distribution evaluation of Light Non-Aqueous Phase Liquid (LNAPL) trapped in the saturated zone using Laser-Induced Fluorescence (LIF) technique. The study site is located in the Paulínia municipality and has been investigated for jet fuel contamination since 2002. Ultra-Violet Optical Screening Tool (UVOST®) was used for its capability in detecting Polycyclic Aromatic Hydrocarbon (PAH) molecules present in LNAPL. One pilot test and 21 LIF profiling tests were carried out in the field, including water table (WT) and floating oil level (OL) monitoring in existing wells. LIF profiling was employed to accurately define the lateral extension of weathered LNAPL, as well as its typology. In addiction, the integration of fluorescence results, seasonal fluctuation of WT, jet fuel thickness and naphthalene concentration led to a clear understanding of lateral and vertical migration of the LNAPL in the subsurface. High fluorescence intensities related to the jet fuel were detected below the WT in the situation of falling LNAPL in low WT season, revealing past vertical migration, and these correspond to the presence of free phase in periods of low WT, previously registered in monitoring wells. Statistical analysis of the four distinct channels (wavelength of 350 nm, 400 nm, 450 nm and 500 nm) showed correlation between the referred wavelengths in the presence of the contaminant, allowing differentiating with better refinement the horizons with the presence... (Complete abstract click electronic access below) / Doutor

Nitrogen dioxide (NO₂) is a pollutant of interest for study both because of its controlling role in the oxidant capacity of the atmosphere and the health risks it poses. Concerns about the health effects of NO₂ and its role in forming deleterious atmospheric species have made it desirable to have low-cost, sensitive ambient measurements of NO₂. A continuous-wave laser-diode laser-induced fluorescence (LIF) system for NO₂ was developed here which operates at ambient pressure, thereby eliminating the need for an expensive pumping system. The current prototype system has achieved sensitivity several orders of magnitude beyond previous efforts at ambient pressure (limit of detection of 2 ppb, 60 s averaging time). Ambient measurements of NO₂ were made in Portland, Oregon using both the standard NO₂ chemiluminescence method and the LIF instrument and showed good agreement (r² = 0.92). In addition, investigations into surface mediated chemistry involving oxides of nitrogen (namely, NO₂) have stimulated new inquiry into potential heterogeneous sources of NO₂ as well as challenged the stability of permanent sinks for NO₂. The possibility that surface mediated chemistry plays a significant role in NOy chemistry in urban air has for the past few decades received considerable attention. The AP-LIF NO₂ instrument is uniquely suited to measure surface chemistry under near ambient conditions. The so called 'renoxification' reaction of gaseous NO with surface bound HNO₃ yielding NO₂ (2HNO₃(surface) + NO--> 3NO₂ +H₂O(surface)) was suggested as a potentially important source of NO₂ which also degraded the stability of nitric acid as a sink of active oxides of nitrogen. Yet, there is disagreement in the literature as to the importance of this reaction. The disagreement stems from differing measurements of the rate for the renoxification reaction. Because there are differences in experimental setups no one research group has studied the renoxification reaction under ambient conditions, i.e., at moderate concentrations of NOy and in a static cell held at 1 atm. In this work, the production of NO₂ was measured using a novel AP-LIF. This setup made it possible to measure the rate of production of NO₂ due to the heterogeneous reaction of NO with HNO₃ under ambient conditions. Under these conditions it was found that renoxification due to gas-phase NO on surface HNO₃ is not a significant source of NO₂. However, this study did show the importance of water vapor in the renoxification of surface HNO₃.

Antimicrobial resistance in bacteria is a global health challenge with a projected fallout of 10 million deaths annually and cumulative costs of over 1 trillion dollars by 2050. The currently available tools exploited in the detection of bacteria or their DNA can be expensive, time inefficient, or lack multiplex capabilities among others. The research work highlighted in this dissertation advances techniques employed in the phenotypic or genotypic detection of bacteria and their DNA. In this dissertation, I present polymethyl methacrylate-pressure sensitive adhesive microfluidic platforms developed using a time-efficient, inexpensive fabrication technique. Microfluidic devices were then equipped with functionalized monoliths and utilized for sequence-specific capture and detection of picomolar concentrations of bacterial plasmid DNA harvested from cultured bacteria. I then showed multiplex detection of multiple bacteria gene targets in these devices with an improved monolith column. Finally, I demonstrated a genotypic approach to studying single bacteria growth in water-in-oil droplets with nanomolar concentrations of a fluorescence reporter, and detection via laser-induced fluorescence after convenient room temperature 2-h incubation conditions. The systems and methods described herein show potential to advance tools needed to address the surging problems and effects of drug-resistant bacteria.

Laser Induced Breakdown Spectroscopy (LIBS) is showing great potential as an atomic analytical technique. With its ability to rapidly analyze all forms of matter, with little-to-no sample preparation, LIBS has many advantages over conventional atomic emission spectroscopy techniques. With the maturation of the technologies that make LIBS possible, there has been a growing movement to implement LIBS in portable analyzers for field applications. In particular, LIBS has long been considered the front-runner in the drive for stand-off detection of trace deposits of explosives. Thus there is a need for a better understanding of the relevant processes that are responsible for the LIBS signature and their relationships to the different system parameters that are helping to improve LIBS as a sensing technology. This study explores the use of LIBS as a method to detect random trace amounts of specific organic materials deposited on organic or non-metallic surfaces. This requirement forces the limitation of single-shot signal analysis. This study is both experimental and theoretical, with a sizeable component addressing data analysis using principal components analysis to reduce the dimensionality of the data, and quadratic discriminant analysis to classify the data. In addition, the alternative approach of ‘target factor analysis’ was employed to improve detection of organic residues on organic substrates. Finally, a new method of characterizing the laser-induced plasma of organics, which should lead to improved data collection and analysis, is introduced. The comparison between modeled and experimental measurements of plasma temperatures and electronic density is discussed in order to improve the present models of low-temperature laser induced plasmas.

The mixing performance of multiple transverse jets has been evaluated experimentally. Measurement techniques included laser Doppler velocimetry and planar laser induced fluorescence. Basic findings are consistent with results presented in literature for single jet mixing behavior. Mixing performance has been compared to literature for the single jet case and the Holdeman parameter has been re-evaluated for effectiveness at low jet numbers. A single jet in a confined crossflow was found to have a local minimum at B(d⁄D) = 0.721. Results for two jets indicate monotonically decreasing unmixedness for the range of conditions tested, with no local optimum apparent. Data for three jets indicate a local optimum at B(d⁄D) = 0.87and relatively flat range of mixing performance in the range of 0.75 < B(d⁄D) < 1.5. Six jets indicate a minimum unmixedness near B(d⁄D) = 0.5, but exhibited poorer mixing performance than all other configurations at the highest values of B(d⁄D)tested. The most optimum configuration tested was six jets at B(d⁄D) = 0.5, resulting in an unmixedness of 0.0192. This value was 76% lower than the next lowest configuration (three jets) at the same B(d⁄D).Total momentum was found to collapse the data well, as configurations more closely matched a historical correlation for second moment of a single confined jet more closely.

This dissertation develops a computational method for simulating laser-induced cavitation and investigates the mechanism behind the formation of non-spherical bubbles induced by long-pulsed lasers. The proposed computational method accounts for the laser emission and absorption, phase transition, and the dynamics and thermodynamics of a two-phase fluid flow. In this new method, the model combines the Navier-Stokes (NS) equations for a compressible inviscid two-phase fluid flow, a new laser radiation equation, and a novel local thermodynamic model of phase transition. The Navier-Stokes equations are solved using the FInite Volume method with Exact two-phase Riemann solvers (FIVER). Following this method, numerical fluxes across phase boundaries are computed by constructing and solving one-dimensional bi-material Riemann problems. The new laser radiation equation is derived by customizing the radiative transfer equation (RTE) using the special properties of laser, including monochromaticity, directionality, high intensity, and a measurable focusing or diverging angle. An embedded boundary finite volume method is developed to solve the laser radiation equation on the same mesh created for the NS equations. The fluid mesh usually does not resolve the boundary and propagation directions of the laser beam, leading to the challenges of imposing the boundary conditions on the laser domain. To overcome this challenge, ghost nodes outside the laser domain are populated by mirroring and interpolation techniques. The existence and uniqueness of the solution are proved for the two-dimensional case, leveraging the special geometry of the laser domain. The method is up to second-order accuracy, which is also proved, and verified using numerical tests. A method of latent heat reservoir is developed to predict the onset of vaporization, which accounts for the accumulation and release of latent heat. In this work, the localized level set method is employed to track the bubble surface. Furthermore, the continuation of phase transition is possible in laser-induced cavitation problems, especially for long-pulsed lasers. A method of local correction and reinitialization is developed to account for continuous phase transitions. Several numerical tests are presented to verify the convergence of these methods. This multiphase laser-fluid coupled computational model is employed to simulate the formation and expansion of bubbles with different shapes induced by different long-pulsed lasers. The simulation results show that the computational method can capture the key phenomena in the laser-induced cavitation problems, including non-spherical bubble expansion, shock waves, and the ``Moses effect''. Additionally, the observed complex non-spherical shapes of vapor bubbles generated by long-pulsed laser reflect some characteristics (e.g., direction, width) of the laser beam. The dissertation also investigates the relation between bubble shapes and laser parameters and explores the transition between two commonly observed shapes -- namely, a rounded pear-like shape and an elongated conical shape -- using the proposed computational model. Two laboratory experiments are simulated, in which Holmium:YAG and Thulium fiber lasers are used respectively to generate bubbles of different shapes. In both cases, the predicted bubble nucleation and morphology agree reasonably well with the experimental observation. The full-field results of laser radiance, temperature, velocity, and pressure are analyzed to explain bubble dynamics and energy transmission. It is found that due to the lasting energy input, the vapor bubble's dynamics is driven not only by advection, but also by the continued vaporization at its surface. Vaporization lasts less than 1 microsecond in the case of the pear-shaped bubble, compared to over 50 microseconds for the elongated bubble. It is thus hypothesized that the bubble's morphology is determined by a competition between the speed of bubble growth due to advection and continuous vaporization. When the speed of advection is higher than that of vaporization, the bubble tends to grow spherically. Otherwise, it elongates along the laser beam direction. To test this hypothesis, the two speeds are defined analytically using a model problem and then estimated for the experiments using simulation results. The results support the hypothesis and also suggest that when the laser's power is fixed, a higher laser absorption coefficient and a narrower beam facilitate bubble elongation. / Doctor of Philosophy / Laser-induced cavitation is a process where laser beams create bubbles in a liquid. This phenomenon is widely applied in research and microfluidic applications for precise control of bubble dynamics. It also naturally occurs in various laser-based processes involving liquid environments. Understanding laser-induced cavitation is important for enhancing the effectiveness and safety of related technologies. However, experimental studies encounter limitations, highlighting the development of numerical methods to advance the understanding of laser-induced cavitation. The laser-induced cavitation can be roughly described as localized boiling through thermal radiation. The detailed physics involves the absorption of laser light by a liquid, the formation of vapor bubbles due to localized heating, and the dynamics of both the bubbles and the surrounding liquid. The first part of the dissertation introduces a new computational method for modeling these phenomena. The dynamics of the two-phase flow are modeled by the Navier-Stokes equations, which are solved using the FInite Volume method with Exact two-phase Riemann solvers (FIVER). The absorption of the laser light is modeled by a new laser radiation equation, which is derived from laser energy conservation and special properties of the laser. An embedded boundary finite volume method is developed to solve this equation on the same mesh created for the NS equations. Additionally, a method of latent heat reservoir is developed to predict the onset of vaporization. In this work, the level set method is employed to track the bubble surface, and a method of local correction and reinitialization is developed to account for possible continuous phase transitions. After developing this new method, several test cases are simulated. The simulation results show that the method can capture the key phenomena in the laser-induced cavitation problems, including the absorption of laser light, non-spherical bubble expansion, and shock waves. When the laser pulse is comparable to or longer than the acoustic time scale (long-pulsed laser), vapor bubbles generated often have complex non-spherical shapes. The bubble shapes reflect some characteristics (e.g., direction, width) of the laser beam. The second part of the dissertation investigates the relation between bubble shapes and laser parameters. Two laboratory experiments are simulated, in which two different lasers are used to generate bubbles of different shapes, namely, a rounded pear-like shape and an elongated conical shape. In both cases, the simulated bubbles exhibit shapes and sizes that reasonably match the experimental results. The simulation results of temperature, pressure, and velocity fields are analyzed to explain bubble dynamics and energy transmission. The analysis shows that the expansion of bubbles induced by long-pulsed lasers is determined not only by advection but also by the continued vaporization at its surface. Vaporization lasts less than $1$ microsecond in the case of the pear-shaped bubble, compared to over $50$ microseconds for the elongated bubble. It is thus hypothesized that the bubble expansion is determined by a competition between the speed of bubble growth due to advection and continuous vaporization. When the speed of advection is higher than that of vaporization, the bubble tends to grow spherically. Otherwise, it elongates along the laser beam direction. To test this hypothesis, the two speeds are defined analytically using a model problem and then estimated for the experiments using simulation results. The results support the hypothesis and also suggest that when the laser's power is fixed, a higher laser absorption coefficient and a narrower beam facilitate bubble elongation.