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.

The continuing need for greater energy security and energy independence has motivated researchers to develop new energy technologies for better energy resource management and efficient energy usage. The focus of this dissertation is the development of optical (spectroscopic) sensing methodologies for various fuels, and energy applications. A fiber-optic NIR sensing methodology was developed for predicting water content in bio-oil. The feasibility of using the designed near infrared (NIR) system for estimating water content in bio-oil was tested by applying multivariate analysis to NIR spectral data. The calibration results demonstrated that the spectral information can successfully predict the bio-oil water content (from 16% to 36%). The effect of ultraviolet (UV) light on the chemical stability of bio-oil was studied by employing laser-induced fluorescence (LIF) spectroscopy. To simulate the UV light exposure, a laser in the UV region (325 nm) was employed for bio-oil excitation. The LIF, as a signature of chemical change, was recorded from bio-oil. From this study, it was concluded that phenols present in the bio-oil show chemical instability, when exposed to UV light. A laser-induced breakdown spectroscopy (LIBS)-based optical sensor was designed, developed, and tested for detection of four important trace impurities in rocket fuel (hydrogen). The sensor can simultaneously measure the concentrations of nitrogen, argon, oxygen, and helium in hydrogen from storage tanks and supply lines. The sensor had estimated lower detection limits of 80 ppm for nitrogen, 97 ppm for argon, 10 ppm for oxygen, and 25 ppm for helium. A chemiluminescence-based spectroscopic diagnostics were performed to measure equivalence ratios in methane-air premixed flames. A partial least-squares regression (PLS-R)-based multivariate sensing methodology was investigated. It was found that the equivalence ratios predicted with the PLS-R-based multivariate calibration model matched with the experimentally measured equivalence ratios within 7 %. A comparative study was performed for equivalence ratios measurement in atmospheric premixed methane-air flames with ungated LIBS and chemiluminescence spectroscopy. It was reported that LIBS-based calibration, which carries spectroscopic information from a “point-like-volume,” provides better predictions of equivalence ratios compared to chemiluminescence-based calibration, which is essentially a “line-of-sight” measurement.

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.

<p dir="ltr">Examination of gaseous detonation flow-fields represents a unique experimental challenge. High-speed shock interaction within a reactive mixture manifests combustion modes across a range of spatial-temporal scales. While the kinetics along the leading front are often characterized by adiabatic compression, simultaneously strong shear induces turbulent mixing in downstream portions of the flow. This all occurs within a wave structure typically traveling near 2000 m/s. To advance fundamental understanding, high-resolution diagnostics are required to make quantitative, time-resolved measurements of the unsteady detonation propagation.</p><p dir="ltr">In this work, detonations are experimentally studied in a single-shot, narrow channel using non-intrusive optical diagnostics. The change in wave structure between mixtures fueled by methane and natural gas was characterized using 175 kHz schlieren and CH* chemiluminescence imaging. The effect of the higher order alkanes in natural gas is speed up the reaction kinetics and produce a wave structure with smaller spatial scales and in which reaction occurs closer to the leading shock front.</p><p dir="ltr">A schlieren system operating at a rate of 5 MHz is then implemented to resolve the spatial-temporal oscillation of the leading shock front. These images are used to compute the lead shock normal speed, which enables a statistical analysis of the oscillating shock velocity. The moments of distribution are compared with computed instability levels of sixteen mixtures and a positive correlation is found. Simultaneous chemiluminescence is used to create joint distribution of shock speed and chemical length scale, which are then compared with the quasi-steady reaction zone solution.</p><p dir="ltr">Experiments are performed with highly nitrogen diluted mixtures of methane and oxygen to examine specific flow features. Different regimes of transverse wave reactivity are observed, from nonreactive to detonative. The transverse detonation wave structure is modeled using oblique shock relations and good agreement is found. The chemical length scales within the configuration are compared to the relevant expansion scales to explain the observed near-steady propagation. Distinct reactive processes following transverse wave collision are also captured. In one instance an explosion immediately occurs, while in the other a reactive gas jet grows from the point of collision. An unsteady reaction zone model is applied to understand the reaction mode within the jet.</p><p dir="ltr">Lastly, 300 kHz OH PLIF is performed to study small scale and weak reaction structures within the flow. The evolution of deflagrative burning mechanisms becomes resolvable using this technique, which highlights the benefit of its use.</p>

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