Avec la population en constante croissance, les besoins alimentaires sont de plus en plus importants. Afin de répondre à la demande des populations, ainsi que pour s’assurer d’un bon rendement agricole, les agriculteurs suivant un mode d’agriculture qualifié de conventionnel doivent palier aux limitations naturelles des cultures. C’est par exemple en utilisant des pesticides ou herbicides pour la gestion des espèces nuisibles. Ce peut être aussi en utilisant des matières résiduelles fertilisantes pour apporter dans les sols les éléments essentiels à la bonne croissance des végétaux. Ces matières peuvent être des boues récupérées en sortie de station d’épuration, ou des fumiers. Les traitements mis en œuvre pour traiter ces matières étant insuffisants, divers contaminants sont introduits en même temps que les nutriments essentiels lors de leurs épandages. Pour les boues, ce sont les produits issus des activités humaines quotidiennes (produits pharmaceutiques et de soin corporel). Il est donc possible de retrouver dans les sols de cultures conventionnelles, un mélange de pesticides, herbicides, produits pharmaceutiques et de soin corporel et autres contaminants organiques. Ces substances, présentes dans les sols sous leurs formes initiales (ingrédient actif) ou dégradées (produits de dégradation), peuvent potentiellement interagir avec les organismes biologiques des sols et causer d’éventuels effets toxiques. Les vers de terre représentent une grande partie de la biomasse animale des sols et contribuent à la régulation des processus majeurs des sols. Vivant dans les sols et s’en nourrissant, ils sont par conséquent directement exposés à tous les contaminants qui s’y trouvent. Il apparaît dans ces conditions importantes de déterminer les potentiels effets toxiques des mélanges de contaminants organiques (pesticides et produits pharmaceutiques) sur les vers de terre. Les concentrations en contaminants organiques dans les sols sont faibles, de l’ordre du ng.g-1 (poids sec), et des effets létaux sur des organismes robustes comme les vers de terre sont peu probables. D’autres effets peuvent cependant apparaître, en altérant par exemple le comportement reproducteur des vers, leur croissance, ou encore en causant des dommages à leur ADN. Ces molécules organiques peuvent aussi s’accumuler dans les tissus des vers de terre, ce qui présente des risques supplémentaires pour les maillons supérieurs du réseau trophique. Des méthodes standardisées pour évaluer ces risques existent. Cela dit, elles ont été mises en place pour estimer les limites en termes de concentrations dans les sols auxquelles les effets toxiques vont apparaître. Les molécules sont par conséquent étudiées seules et à de hautes concentrations. L’objectif principal de ces présents travaux est de mettre en place un protocole nous permettant de détecter un ensemble d’effets sublétaux des contaminants organiques sur les vers de terre de l’espèce Eisenia andrei en exposant les vers à des mélanges de pesticides et de produits pharmaceutiques à faibles concentrations (environnementales), ou bien à des produits marqueurs d’une contamination spécifique. Le protocole expérimental retenu est basé sur un test de reproduction, auquel des analyses chimiques des tissus des vers de terre et des échantillons de sol pour évaluer la bioaccumulation des contaminants sont ajoutés. Dans ce cas d’étude, la bioaccumulation fait référence à l’accumulation des contaminants organiques provenant de toutes les sources d’exposition (alimentation, contact) dans les tissus des vers de terre. L’essai comètes appliqué aux vers de terre adultes pour déterminer l’endommagement de l’ADN vient compléter les données. Ce protocole a été appliqué à plusieurs reprises, en exposant les vers de terre à des mélanges divers de contaminants organiques (pesticides et produits pharmaceutiques) ajoutés directement au sol artificiel, en concentrations environnementales (< 100 ng.g-1 , masse sèche). L’effet le plus marquant est la bioaccumulation sélective des insecticides de la famille des néonicotinoides dans les tissus des vers de terre, quelle que soit la composition de mélange de contaminants organiques ajoutés au sol. Lorsqu’exposés au triclosan à 50 ng.g-1 (dw), les vers de terre modifient leur comportement de reproduction, et accumule cette molécule. Lorsque le triclosan est ajouté par l’intermédiaire d’une boue contaminée dans ces mêmes sol artificiel et à une concentration finale équivalente, la bioaccumulation est du même ordre de grandeur que précédemment. C’est la forme dérivée du triclosan, le méthyl-triclosan, qui apparaît progressivement dans les sols et est accumulé plus fortement que le triclosan lui-même. Ce phénomène n’était pas observé lors de l’ajout du triclosan dissous dans un solvant. Bien que réalisés dans un système artificiel, les travaux présentés dans ce mémoire montrent l’importance de rechercher les effets écotoxicologiques des contaminants en conditions les plus réalistes possibles (mélanges, concentrations faibles). Le suivi de la composition chimique des sols d’exposition au cours des expériences permet de mieux comprendre l’origine des effets observés, particulièrement lorsque les produits de transformation peuvent également être analysés. Pour aller plus loin dans les études des effets sublétaux de contaminants organiques sur les vers de terre, des expériences incluant un suivi de plusieurs générations successives apporteraient de nombreuses informations sur la sensibilisation des jeunes vers et le risque pour les populations à long terme.

In the last decade emerging contaminants research has intensified in a bid to answer questions about fate, transport, and effects as these chemicals as they get released into the environment. The chemicals of interest were the antimicrobials; triclocarban (TCC) and triclosan (TCS), and a metabolite of triclosan, methyl triclosan (MTCS). This research was designed to answer the question: what is the fate of these chemicals once they are released from the waste water treatment plant into receiving streams. Three different assessment methods; field monitoring, in-situ experiments, and laboratory studies were used to answer the overall question. TCS, TCC, and MTCS levels were measured in surface water, sediment and the Asiatic clam Corbicula fluminea. Field studies were conducted using four sites at Pecan Creek, Denton TX. Levels of all three chemicals in clams were up to fives orders of magnitude the water concentrations but an order of magnitude lower than in sediment. Highest sediment levels of chemicals were measured in samples from the mouth of Pecan Creek (highest organic matter). TCC was the most and TCS was the least accumulated chemicals. In-situ and lab studies both indicated that uptake of these chemicals into the clams was very rapid and measurable within 24hours of exposure. The after clams were transferred into clean water most of the compounds were depurated within 14 days.

Master of Science / Department of Biological and Agricultural Engineering / Naiqian Zhang / Permittivity, displayed when a dielectric material is exposed to an electric field, is a useful property for measuring impurities in a dielectric medium. These impurities often have a dipole moment different from the pure material, and the dipoles align through polarization and impede electric current. By measuring the resulting impedance in a known geometry, the permittivity can be determined. Four permittivity sensors were utilized to measure contaminants that are associated with biofuels, specifically glycerol, ethanol, and ammonia. These sensors were based around either stainless steel or aluminum plates to ensure durability and reliability. By connecting each of these sensors to a signal generating control box, the gain and phase can be measured at 609 frequencies, from 10 kHz up to 120 MHz. Data from each of the three contaminants were run through a method for detection. Measurements for ambient air and air with the contaminants were compared with a statistical analysis. Glycerol, ethanol, and ammonia each had significantly different measurements in the gain and phase data at a unique set of frequencies. Using a neural network analysis for detection resulted in a 95.8%, 93.9%, and 97.1% success rate for detecting glycerol, ethanol, and ammonia, respectively. For ethanol and ammonia, where multiple concentrations were measured, regression methods were used to relate the frequency response data to the contaminant concentration. Stepwise regression, wavelet transformation followed by stepwise regression, partial least squares regression, and neural network regression were the four methods used to establish these relationships. Several regressions over-fit the data, showing coefficient of determination (R[superscript]2) values of 1.000 for training data, yet very low R[superscript]2 values for validation data. However, the best R[superscript]2 values of all the regressions were 1.000 and 0.996 for the training and validation data, respectively, from measuring ammonia.

In recent years, the increasing release of trace organic chemicals to the aquatic environment have been problematic to both the ecosystem and the human society. These trace organic chemicals, regarded as emerging contaminants, include different categories of chemicals, which are either deemed to be safe for human consumption or they are naturally occurring compounds. As a newly recognized class of emerging contaminant, artificial sweeteners are proven to be one of the most ubiquitous classes of emerging contaminants in environmental waters. Its transformation to different suite of TPs during water treatment processes generated more toxic influence than the parent compound is problematic. The realization of the widespread of emerging contaminants, together with their ambiguous fate and impact to the environment have led to the development of advanced oxidation processes that can effectively attenuate this wide range of contaminants. In this work, several catalytic advanced oxidation processes were studied. On one hand, it aimed to evaluate their effectiveness on the removal of the artificial sweetener - acesulfame; and on the other hand, to shed lights on the future development of catalytic advanced oxidation processes. In the first part of this thesis, the photo-Fenton treatment was evaluated on its potential to effectively remove acesulfame together with the produced transformation products, and the post-treatment toxicity screening. The photo-Fenton treatment was found to be effective in removing both the parent compound and the transformation products, without leading to an increase in toxicity, which is largely related to the effective removal of the transformation products. In attempt to reduce the reliance on UV irradiation, newly synthesized carbon and nitrogen co-doped TiO2-based photocatalyst was applied to capture the simulated sunlight for the degradation of acesulfame. The heterogenous photocatalytic treatment was found to involve several different oxidative reactive species for both degradation and transformation by using several scavengers to alter the degradation profile. Unexpected transformation product was also formed upon treatment in actual water matrix, suggesting the impact of water constituents to the transformation of emerging contaminants. Toxicity results indicated the inability to achieve detoxification, suggesting that a more effective degradation process was needed. To accelerate the degradation process, and enhance the performance at neutral pH, the use of redox mediators for Fenton/Fenton-like system was evaluated. Developed novel Fenton-like system involving copper(II) as transition metal ion, persulfate as oxidant and mercaptosuccinic acid as redox mediator led to effective removal of different contaminants. Elucidation of the proposed oxidation mechanism suggested the role of each components of the system, and the generation of different reactive species for degradation as indicated by the different acesulfame transformation profile obtained. The implementation of redox mediators to Fenton/Fenton-like system was beneficial and an effective approach. In short, this work presents several kinds of catalytic advanced oxidation process and shed lights on improving the degradation performance with directions for the future development of better and more effective water treatment processes.

Blood is a common type of medium with which patent fingerprints are deposited at crime scenes. Chemical enhancements are generally used on bloody fingerprints when some type of pattern is visible but ridge characteristics are not sufficiently defined to make the print suitable for comparison. Motor vehicles, which may be associated with crimes scenes or forensic investigations, can be exposed to a variety of contaminants from the environment, including mud, salt, pollen, dust and motor oil, as well as from the application of chemicals to protect the paint such as car wax and car polish. It is unknown if these contaminants in combination with the chemicals used to enhance bloody impressions or in combination with the blood itself, could impact the enhancement of bloody impressions found on vehicles. This study seeks to assess the effectiveness of a selection of blood enhancement methods in the presence of such contaminants. Three of the four enhancement chemicals that were tested, Amido Black, Hungarian Red, and Leucocrystal Violet, were determined to be similarly effective for the enhancement of bloody friction ridge patterns applied to the surfaces of contaminated glass and metal substrates.

"The simultaneous degradation of five organic contaminants: 1,4 dioxane, n-nitrosodimethylamine, tris-2-chloroethyl phosphate, gemfibrozil, and 17β estradiol, was investigated using a 1 L batch water-jacketed UV photoreactor utilizing titanium dioxide (TiO2) nanoparticles (Degussa P-25) as a photocatalyst. The primary objectives of this research were: (1) to experimentally assess the feasibility of heterogeneous photocatalysis as a promising alternative for the degradation of organic compounds in water; and (2) to model the chemical reactions by the application of two different approaches based on adsorption – surface reactions (Langmuir–Hinshelwood) and its simplification to a first order rate reaction. These objectives were motivated by the lack of information regarding simultaneous degradation of organic compounds in different categories as found in real aqueous matrices, and generation of specific intermediates that could eventually represent a potential risk to the environment. Contaminants were chosen based on their occurrence in water sources, their representativeness of individual sub-categories, and their importance as part of the CCL3 as potential contaminants to be regulated. Contaminant degradation was evaluated over time, and the TiO2 concentration and solution pH were varied under constant UV irradiation, oxygen delivery rate, mixing gradient, and temperature. 

 Specific accomplishments of this study were: (1) reaction kinetics data were obtained from the UV/TiO2 experiments and showed the potential that this UV/TiO2 process has for effectively removing different types of organic compounds from water; (2) a good fit was obtained between photocatalytic reaction kinetics models and the contaminant data using pseudo first-order and Langmuir-Hinshelwood (L-H) models; (3) results of the analytical methods developed in this study were validated by measurements performed by a certified laboratory; (4) the reaction kinetic parameters obtained in this study were normalized to electrical energy per order, reactor volume and surface area of the photocatalyst in order to provide rate constants with wider applicability for scale-up to more complex systems; and (5) degradation intermediates from the oxidation process and from interaction among compounds were identified and possible pathways for their formation suggested. This research has provided a better understanding of the photocatalytic process for the removal of organic contaminants from complex aqueous matrices."

No description available.

Direct methanol fuel cells (DMFCs) are considered a clean source of electrical power for future energy demand, creating a potential to reduce our dependency on fossil fuels. Despite their advantages, including high energy density, efficiency and easy handling and distribution of fuel, the commercialization of DMFCs has suffered from some drawbacks, including methanol crossover and contamination of the system. Metal cation contaminants (such as Ni, Co, etc) introduced through the degradation of fuel cell components (bipolar plate and electro-catalyst layer) can significantly affect the Nafion-membrane properties and overall fuel cell performance. In the current study, a systematic approach is taken to characterize and identify the mechanism of the effect of metal solution contaminants on the activities of electro-catalysts of DMFCs. Cyclic voltammetry and rotating disk electrode (RDE) techniques were utilized in order to characterize the effect of various concentrations (i.e., 2x10-x M (x=1-7)) of six metal solution contaminants (i.e., Co, Ni and Zn with sulfate and nitrate as counter-anions) on the voltammetric properties and electro-catalytic activity of polycrystalline Pt during methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). The results showed a decrease in the MOR and ORR activities of Pt as the concentration of metal solution increased. The effect of counter-anion on the Pt activity was further investigated. The results showed that a combined effect of counter-anions and metal cations may be responsible for the decrease in the electro-catalytic activity of Pt. The effect of metal solution contaminants on the Nafion-ionomer of anode electro-catalysts was investigated using Nafion-coated Pt electrode. Voltammetric properties and MOR activities of Nafion-coated and bare Pt electrodes in the presence of Ni solution contaminants were characterized using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The overall results showed a significant negative effect of Ni solution contaminants on the electro-catalytic activity of bare Pt electrode as compared to the Nafion-coated Pt electrode. Based on the results, it appears that Nafion-ionomer film may interact with metal cations (through its sulfonate groups) and repel them away from the Pt active sites, partially inhibiting the negative effect of metal cations on the Pt activity of Nafion-coated Pt electrode. The effect of metal solution contaminants on the carbon-supported platinum nanoparticle (Pt/C) with various Nafion-ionomer distributions and contents (i.e., Nafion-incorporated Pt/C and Nafion-coated Pt/C electrodes) was further investigated. Cyclic voltammetry and EIS techniques were employed to characterize the effect of Ni solution contaminants on the voltammetric properties and MOR activities of Nafion-incorporated and Nafion-coated Pt/C electrodes. The overall results showed a stronger negative effect of Ni solution contaminants on the electro-catalytic activity of Nafion-incorporated Pt/C electrodes as compared to the Nafion-coated Pt/C electrodes. This further confirms previous observations showing the sulfonate groups of Nafion-ionomer film may attract the Ni metal cations, localize them away from the Pt active sites, and subsequently suppress the negative effect of cations on the activity of Nafion-coated Pt/C electrodes.

Along with an increasing understanding of the harmful effects on the environment of a wide range of pollutants has come the need for more sensitive, faster and less expensive detection methods of identification and quantitation. Many environmental pollutants occur in low levels and often in complex matrices thus analysis can be difficult, time consuming and costly. Because of the availability and easy cultivation of the microorganisms with potentially high specificity, there is considerable interest in the use of living microorganisms as the analytical component (the biocomponent) of sensors for pollutants. While a number of biosensors using bacteria have been developed, yeast has been comparatively rarely used as the biocomponent. Yeast are attractive because they are easy to culture and they are eukaryotes which means their biochemistry is in many respects closer to that of higher organisms. This thesis describes the development of whole cell bioassays that use yeast cells as a sensing element and redox mediators to probe the intracellular redox reactions to monitor the catabolic activity of the yeast resulting from the external substrate, steady-state voltammetry is utilised as the electrochemical detection technique. The isogenic differential enzyme analysis (IDEA) concept of Lincoln Ventures Limited, lead NERF funded research consortium uses bacteria that have been cultured using specific organic pollutants as the carbon source which are the biocomponent in sensors. The use of wild type yeast Arxula adeninivorans that has the ability to use a very wide variety of substrates as sources of carbon and nitrogen was used as an alternative to bacteria to validate the “IDEA” concept. Naphthalene and di-butyl phthalate were chosen as model target contaminant molecules. The performance, detection limits and the usefulness of yeast based biosensor applications for environmental analysis are discussed. This thesis also describes the development and optimisation of a simple, cost effective in vivo estrogens bioassay for the detection of estrogens using either genetically modified or a wild type yeast Saccharomyces cerevisiae. In this study, catabolic repression by glucose was exploited to achieve specificity to estrogens in complex environmental samples that eliminates the requirement for conventional sample preparation. This is the first time that the use of wild type yeast to quantify estrogens has been reported. The attractive features of the bioassay are its use of a non-GMO organism, its speed, its high specificity and sensitivity with a detection limit of 10-15 M. The similarity of binding affinities for major estrogens to those of human estrogens receptors makes this in vivo estrogen bioassay very useful for analytical/screening procedures. The electrochemical detection method also makes it easy to interface with a variety of electronic devices.

Les réactions d'oxydoréduction de l'antimoine (V) et (III) avec la mackinawite (FeS) et du plutonium (III) et (V) avec plusieurs minéraux à fer(II) et des oxydes de fer(III) ont été étudiées dans des conditions d'anoxie. La spectroscopie d'absorption des rayons X fut utilisée pour l'analyse de l'état d'oxydation et de la structure locale du Sb et Pu associés à la phase solide. Après réaction avec la mackinawite, la chukanovite et la magnétite, PuO2, Pu(III) ou des mixtures des deux états d'oxydation ont été observé. A la surface de la magnétite un complexe tridenté du Pu(III) a pu être mis en évidence à l'aide des spectres EXAFS couplé à une simulation de Monte‐Carlo utilisant le code de calcul Feff. La quantité relative de Pu(III) est fonction de l'espèce minérale, du ratio solide/liquide, des valeurs pe et pH du système et, potentiellement, de la taille de particule et de la cristallinité de la phase solide de PuO2 en présence de laquelle le Pu(III) existe. Avec la mackinawite à pH 6,2 et à une occupation de surface de 67 nmol/m2 et avec la magnétite jusqu'à pH 8.4 et 56 nmol/m2 de Pu, uniquement du Pu(III) fut trouvé associé à la phase solide. Avec la maghémite contenant du fer(II) résiduel à pH6 Pu(III) et Pu(IV) était, probablement, présents dans des complexes de surfaces similaire à celui formé par le Pu(III) sur la magnétite. Dans les conditions expérimentales (couverture de surface ≤ 77 nmol/m2), aucune formation de PuO2 ne fut observé. Après réaction avec l'hématite et la goethite Pu(IV) était l'état d'oxydation prédominant associé à la phase solide. La sorption et la réduction du Sb(V) avec la mackinawite était fortement fonction du pH. A pH acide la sorption était rapide et Sb(V) fut complètement réduit en Sb(III), formant un complexe Sb(III)‐S3 probablement associé à la surface de la mackinawite. La réduction du Sb(V) était couplée à l'oxydation de la mackinawite et la greigite (Fe3S4) fut détectée par XRD. A pH basique, la sorption du Sb(V) est lente et la réduction vers le Sb(III) n'était complète qu'à des ratios de Sb/FeS très bas. Pour des valeurs plus élevé de Sb/FeS la sorption de Sb se faisait en partie par la réduction envers le complexe de Sb(III)‐S3 et en partie par une co‐précipitation avec le Fe(III). Il a pu être démontré que les minéraux à fer(II) peuvent effectivement contribuer à la réduction et à l'immobilisation de l'antimoine et du plutonium qui sont des contaminants environnementaux d'importance croissante.