This dissertation is a collection of works that investigates issues related to environmental chemistry. The first portion of this research explores the role of water vapor on the kinetics of important atmospheric reactions. Work is presented on the self-reaction of β-hydroxyethyl peroxy radical (β-HEP) and the catalytic increase in reaction rate by water vapor. β-HEP serves as a model system for investigating the possible role of water vapor in perturbing the kinetics and product branching ratio of atmospheric reactions of other alkyl peroxy radicals. The self-reaction rate coefficient of β-HEP was investigated between 276-296 K with 1.0 × 10^15 to 2.5 × 10^17 molecules cm^-3 of water vapor at 200 Torr total pressure by slow-flow laser flash photolysis coupled with UV time-resolved spectroscopy and long-path, wavelength-modulated, diode-laser spectroscopy. The overall disproportionation rate constant is expressed as the product of temperature-dependent and water vapor-dependent terms giving k(T,H2O) = 7.8 × 10^-14 (e^8.2 ^(±2.5) ^kJ/RT)(1 + 1.4 × 10^-34 × e^92 ^(±11) ^kJ/RT[H2O]). The results suggest that formation of a β--HEP-H2O complex is responsible for the observed water vapor enhancement of the self-reaction rate coefficient. Complex formation is supported with computational results identifying three local energy minima for the β--HEP-H2O complex. Both the temperature range and water vapor concentrations used were chosen because of their significance to conditions in the troposphere. As the troposphere continues to get warmer and wetter, more complexes with water will form, which in turn may perturb the kinetics and product branching ratios of atmospheric reactions. Future studies are proposed for the reaction of β-HEP + NO leading to NO2 formation. A laser-induced fluorescence cell was designed, built, and tested in preparation for studies of NO2 formation. Additionally Harriott-cell optics were manufactured and tested to detect HO2 using two-tone frequency-modulated diode-laser spectroscopy. In a related work, the breakdown of the environmental contaminants polychlorinated biphenyls (PCB's) was investigated using a new method. A new method for analyzing anaerobic digestion is also presented. The degradation rate and efficiency of digestion processes are typically measured by introducing a substrate or pollutant into a digester and then monitoring the effluents for the pollutant or substrate, a costly and slow process. A new method for rapid measurement of the rates and efficiencies of anaerobic degradation of pollutants and lignocellulose substrates from various pretreatments is described. The method uses micro-reactors (10-30 mL) containing a mixed culture of anaerobic bacteria obtained from a working anaerobic digester. The rates of degradation and metabolism of pollutants are measured in parallel sets of micro-reactors. Measurements of metabolic rate and pollutant degradation simultaneously is an effective means of rapidly examining pollutant degradation on a micro-scale. Calorimetric measurements alone allow rapid, relative evaluation of various substrate pretreatment methods. Finally calorimetric and electrophoretic methods were used to further knowledge in analytical techniques applied to important problems. In the last section of this dissertation the thermal and photolytic breakdown of promethazine hydrochloride is reported. Promethazine hydrochloride is a mediation that is commonly used as an antihistamine, a sedative, and an antiemetic, and to treat motion sickness. Perivascular extravasation, unintentional intra-arterial injection and intraneuronal or perineuronal infiltration may lead to irreversible tissue damage if the drug is not properly diluted or is administered too quickly. Data on the stability of promethazine hydrochloride diluted in sodium chloride 0.9% are lacking. This study evaluates the thermal and photolytic degradation of promethazine hydrochloride concentrations of 250 µg/mL and 125 µg/mL diluted in sodium chloride 0.9% over a period of 9 days. Degradation rates of promethazine hydrochloride were determined under UV-light, fluorescent light, and no light at various temperatures and concentrations to determine medication stability. The shelf-life (<10% degradation) at 25°C under normal fluorescent lights is 4.9 days, at 25°C protected from light, 6.6 days, and at 7°C in the dark, 8.1 days. These results may increase patient safety by improving current protocols for intravenous promethazine administration

Dans le domaine des cellules photovoltaïques à base de couches minces, l'alliage de Cu(In1-x,Gax)Se2 (CIGSe) constitue l'une des filières les plus avancées. Le passage à l'échelle industrielle soulève cependant de nouvelles problématiques. En effet, si le procédé standard de co-évaporation permet d'atteindre des rendements records supérieurs à 20 %, il reste relativement couteux à mettre en place. C'est ainsi que dans un contexte toujours plus compétitif, l'électrodépôt apparait comme une alternative de choix pour diminuer les coûts de production tout en garantissant des rendements compétitifs sur de grandes surfaces. Néamoins, de nombreuses propriétés spécifiques à ce mode de dépôt restent méconnues. En particulier les propriétés optiques à l'origine du photo-courant. Le premier objectif de cette thèse est donc de déterminer les constantes optiques de chaque couche du dispositif par ellipsométrie. Une attention particulière est donnée à la couche absorbante de CIGSe électrodéposée pour laquelle un protocole spécifique est employé. Une seconde partie de la thèse est dédiée à la réalisation d'un outil de caractérisation sans contact : la photoréflectance (PR). La PR va permettre de mesurer avec précision les énergies de transition interbandes d'un semi-conducteur, dont l'énergie de gap. Nous décrivons dans le détail le dispositif expérimental. Une implémentation originale utilisant une double modulation des sources a été développée et permet de réduire le bruit de mesure induit par la rugosité et la diffusion. L'étude de 14 échantillons de CIGS permet finalement de corréler des paramètres opto-électriques issus des caractéristiques courant-tension aux spectres PR. / Regarding, thin film photovoltaic market, Cu(In1-x,Gax)Se2 (CIGSe) based material is one of the most advanced technologies. Its high absorption coefficient allows it to absorb an important part of the solar spectrum with only two micron thickness. But while moving from fundamental research to the development of batch flow production, issues still remain. If the standard co-evaporation process lead to the best efficiency up to 20 %, high energy consumption is needed. In an increasingly competitive market, electroplating allows to reduce operating cost related to vacuum processes while guaranteeing competitive efficiencies on large scale modules. Nevertheless, due to the specificities of electroplating, new issues occur and some properties may differ from vacuum routes. In particular, optical properties which are responsible for photo-current generation. The first part of this thesis is thus devoted to obtain the optical constants for each layer of the device by spectroscopic ellipsometry. We pay special attention to the electrodeposited CIGSe absorber layer for which a specific method have been used in order to perform measurements on the back side. The second part of this thesis is dedicated to the development of an caracterisation tool : the photoreflectance (PR). The experimental setup is precisely described. An special implementation, using dual modulation technique, increases accuracy by removing luminescence and scattering perturbations. The study of 14 CIGS samples allows finally to correlate opto-electrical parameters from I(V) curves with PR spectra.