Dissertations / Theses on the topic 'Formation of photochemical smog'

Thesis (Ph. D.)--Earth and Atmospheric Sciences, Georgia Institute of Technology, 2005.
Russell, Armistead G., Committee Chair ; Chameides, William L., Committee Member ; Wang, Yuhang, Committee Member ; Noonan, Douglas, Committee Member ; Chang, Michael E., Committee Member. Vita. Includes bibliographical references.

Bibliography: leaves 124-131.
Photochemical smog is the name given to a complex sequence of chemical reactions that occurs in the presence of sunlight. These reactions comprise a mix of organic and inorganic compounds, including a number of toxic secondary pollutants such as ozone (O3) and peroxyacetyl nitrate. These substances are commonly referred to as oxidants and are the result of numerous reactions of primary pollutants or precursors (including nitrogen oxides (NOx) and non- methane hydrocarbons (NHHC)) emitted from vehicle exhausts and to some extent industry, O3 is the major constituent of the photochemical oxidants, and its concentration is often used to determine the severity of photochemical smog. Limited research on photochemical smog in Cape Town has been undertaken, and this study has concentrated on providing a more detailed understanding of photochemical precursor and oxidant levels in the urban atmosphere of Greater Cape Town. This was approached by the investigation and assessment of the spatial and temporal behaviour of photochemical pollutants, making use of automatic monitor data collected from 1984 to 1986, and supplemented by data collected during a spatial survey in April and Hay of 1987. Precursor levels were found to be strongly influenced by the seasonal cycle of the weather and were highest in winter when stable atmospheric conditions prevailed, particularly during morning rush hours, O3 behaviour was complex and lacked any definite relationship to season or to selected meteorological variables, although the limited data indicated high levels during the early spring months. Peak levels were generally experienced on fair weather days during the early afternoon hours at the time of maximum ultraviolet radiation, O3 levels did not exceed the USEPA 1-hour standard of 0.12ppm during 1985 and 1986. The spatial distribution of precursor and oxidant concentrations showed the NOx levels to be spatially dependent, following the major arterial roads. NHHC levels were spatially less well defined than NOx, and O3 levels were spatially relatively uniform, exhibiting depletion due to scavenging by nitric oxide (NO) in areas close to main traffic routes. High NOx levels were experienced predominantly in the city centre, while the suburbs tended to experience the higher O3 levels. Cape Town was not considered to have a photochemical smog problem of the same magnitude as Los Angeles or Sydney, ( due to a number of factors which contributed to the complex situation (such as high NO levels, relatively low NMHC levels and strong winds in summer). However in the Northern Suburbs, the absence of high NO levels together with additional NMHC emissions from nearby industry led to the recognition of this area as one of potential photochemical smog formation.

The rapid rising anthropogenic emissions driven by economic growth over China documented by satellite observations and bottom-up inventories have led to severely degraded air quality, and also have been suggested to be linked to the recent upward trends of tropospheric O₃ over the regions downwind of China. Multi-scale modeling analyses facilitated by ground-level, aircraft and satellite observations have been conducted to understand the atmospheric chemistry over China. Analyses using a 1-D photochemical model constrained by measurements at Beijing in August of 2007 suggest that reactive aromatic VOCs are the major source (~75%) of peroxy acetyl nitrate (PAN). Detailed radical budget analyses reveal the very fast ROₓ (OH + HO₂ + RO₂) production, recycling and destruction driven by VOC oxidation and heterogeneous processes. Photoenhanced aerosol surface uptake of NO₂ is found to be the predominant source of nitrous acid (HONO) during daytime (~70%). 3-D regional modeling analyses of tropospheric vertical column densities of glyoxal (CHOCHO) from SCIAMACHY show that anthropogenic emissions of aromatic VOCs are substantially underestimated (by a factor of 5 - 6, regionally varied) over China. Such an underestimation is the main cause of a large missing source of CHOCHO over the region in current global models, and could also partly explain the underestimation of organic aerosols in previous modeling studies.

[ES] La luz solar puede producir daños en el ADN por absorción directa de luz UVB, o por fotosensibilización tras la absorción de luz UVA por parte de fármacos, que pueden actuar como fotosensibilizadores (PS). La benzofenona (BP), presente en la estructura química de una amplia variedad de fármacos, tiene el potencial de fotosensibilizar daño al ADN, especialmente hacia la base de timina (Thy). Este daño puede dar lugar a dímeros de pirimidina de tipo ciclobutano (CPD) y a fotoproductos (6-4) pirimidina-pirimidona ((6-4)PPs), los cuales pueden causar mutaciones graves, melanomas o incluso la muerte celular. En algunos organismos, los (6-4)PPs pueden repararse de manera eficiente por las fotoliasas, en lo que se podría entender como una reacción Paternò-Büchi (PB) inversa a través de un intermedio de oxetano altamente inestable. Con el fin de profundizar en la fotorreactividad de los derivados BP-Thy y en la ruptura fotoinducida de oxetanos, se sintetizaron por primera vez una variedad de diadas en las que Thy y BP están covalentemente unidas por un espaciador lineal de diferente longitud y naturaleza. La fotorreactividad de los diferentes derivados se investigó por fotólisis de destello láser (LFP) y espectroscopía de absorción transitoria a escala de femtosegundo; además, se aislaron y caracterizaron los principales fotoproductos (PPs) derivados de la irradiación en estado estacionario. Los resultados mostraron un alto grado de quimioselectividad en la longitud y conformación del espaciador. En cuanto a la reactividad fotoquímica, se formaron PPs derivados de la PB y de la abstracción formal de hidrógeno; así, las diadas con el espaciador más largo dieron lugar a la formación de oxetanos y de PPs de abstracción de hidrógeno. Por el contrario, las diadas con espaciadores más cortos formaron un fotoproducto de abstracción formal de hidrógeno y/o polimerización. Por tanto, la fotorreactividad se vio influida por la longitud del espaciador, correlacionándose bien con los tiempos de 3BP*, observándose los tiempos más cortos para las diadas de espaciadores largos. En relación con la fotoapertura de oxetanos, la irradiación de los diferentes regio- y estereoisoméros condujo a la formación de la típica banda de absorción triplete-triplete de BP; por tanto, dicho proceso opera de forma adiabática. La fotólisis del oxetano que resulta de la irradiación de la diada con el espaciador más largo mostró una banda de absorción transitoria sobre 400 nm, atribuida a la formación del exciplejo triplete entre BP y Thy covalentemente unidos. Por otro lado, se investigó la reacción PB y la cicloreversión de oxetanos que surgen de la interacción entre Thy o derivados de uracilo (Ura) y BP. Así, se sintetizó una amplia gama de oxetanos Thy-BP y Ura-BP con diferentes sustituyentes en las posiciones 1 y 5 de la nucleobase, incluyéndose los regioisómeros cabeza-cabeza (HH) y cabeza-cola (HT). Los estudios espectroscópicos (absorción transitoria ultrarrápida y LFP), junto con el análisis teórico, coinciden en que la cicloreversión fotoinducida para los isómeros HH y HT implica la formación de un exciplejo en el estado excitado triplete antes de la ruptura. Generalmente, se observó que la reacción fue completamente adiabática para los regioisómeros HH. En el caso del oxetano HH que surge de la interacción entre 1,3-dimetiltimina (DMT) y BP, se observó la formación de una banda ~400 nm, que se atribuyó al exciplejo triplete 3[DMT···BP]*. Su formación fue altamente regioselectiva, siendo más rápida y eficiente para el isómero HH que para HT. Estos resultados fueron confirmados por análisis computacional. En general, se observó adiabaticidad en el proceso de fotorreversión para todos los oxetanos investigados, con un alto grado de regioselectividad y con la participación de exciplejos triplete.
[CA] La llum solar pot produir danys a l'ADN per absorció directa de llum UVB, o per fotosensibilització després de l'absorció de llum UVA per part de fàrmacs, que poden actuar com fotosensibilitzadors (PS). La benzofenona (BP), present en l'estructura química d'una àmplia varietat de fàrmacs, té el potencial de fotosensibilitzar dany a l'ADN, especialment a la base de timina (Thy). Aquest dany pot donar lloc a dímers de pirimidina de tipus ciclobutà (CPD) i a fotoproductes (6-4) pirimidina-pirimidona ((6-4)PPs), els quals poden causar mutacions greus, melanomes o fins i tot la mort cel·lular. En alguns organismes, els (6-4)PPs poden reparar-se de manera eficient per les fotoliases, en el que es podria entendre com una reacció Paternò-Büchi (PB) inversa a través d'un intermedi d'oxetà altament inestable. Amb la finalitat d'aprofundir en la fotoreactivitat dels derivats BP-Thy i en la ruptura fotoinduïda d'oxetans, es van sintetitzar per primera vegada una varietat de diades en les quals Thy i BP estan covalentment unides per un espaiador lineal de diferent longitud i naturalesa. La fotoreactivitat dels diferents derivats es va investigar per fotòlisi de centelleig làser (LFP) i espectroscopía d'absorció transitòria a escala de femtosegons; a més, es van aïllar i caracteritzar els principals fotoproductes (PPs) derivats de la irradiació en estat estacionari. Els resultats van mostrar un alt grau de quimioselectivitat en la longitud i conformació de l'espaiador. Quant a la reactivitat fotoquímica, es van formar PPs derivats de la PB i de l'abstracció formal d'hidrogen; així, les diades amb l'espaiador més llarg van donar lloc a la formació d'oxetans i de PPs d'abstracció d'hidrogen. Per contra, les diades amb espaiadors més curts van formar un fotoproducte d'abstracció formal d'hidrogen i/o polimerització. Per tant, la fotoreactivitat es va veure influïda per la longitud de l'espaiador, correlacionant-se bé amb els temps de 3BP*, observant-se els temps més curts per a les diades amb espaiadors llargs. En relació amb la fotoapertura d'oxetans, la irradiació dels diferents regi- i estereoisòmers va conduir a la formació de la típica banda d'absorció triplet-triplet de BP; per tant, aquest procés opera de manera adiabàtica. La fotòlisi de l'oxetà que resulta de la irradiació de la diada amb l'espaiador més llarg va mostrar una banda d'absorció transitòria sobre 400 nm, atribuïda a la formació de l'exciplex triplet entre BP i Thy covalentment units. D'altra banda, es va investigar la reacció PB i la cicloreversió d'oxetans que sorgeixen de la interacció entre Thy o derivats d'uracil (Ura) i BP. Així, es va sintetitzar una àmplia gamma d'oxetans Thy-BP i Ura-BP amb diferents substituents en les posicions 1 i 5 de la nucleobase, incloent-se els regioisòmers cap-cap (HH) i cap-cua (HT). Els estudis espectroscòpics (absorció transitòria ultraràpida i LFP), juntament amb l'anàlisi teòric, coincideixen en que la cicloreversió fotoinduïda per als isòmers HH i HT implica la formació d'un exciplex en l'estat excitat triplet abans de la ruptura. Generalment, es va observar que la reacció va ser completament adiabàtica per als regioisòmers HH. En el cas de l'oxetà HH que sorgeix de la interacció entre 1,3-dimetiltimina (DMT) i BP, es va observar la formació d'una banda ~400 nm, que es va atribuir a l'exciplex triplet 3[DMT···BP]*. La seua formació va ser altament regioselectiva, sent més ràpida i eficient per a l'isòmer HH que per a HT. Aquests resultats van ser confirmats per anàlisi computacional. En general, es va observar adiabaticitat en el procés de fotoreversió per a tots els oxetans investigats, amb un alt grau de regioselectivitat i amb la participació d'exciplexes triplet.
[EN] Sunlight light can produce damage to DNA through direct absorption of UVB or, more commonly, by photosensitization upon absorption of UVA light by drugs, that act as a photosensitizer (PS). Benzophenone (BP) as a building-block is present in a wide variety of drugs, and have the potential to photosensitize damage to DNA, specially towards the thymine (Thy) nucleobase. The resulting DNA damage can give rise to bulky dimers, i.e. cyclobutane pyrimidine dimers (CPDs) and pyrimidine-pyrimidone (6-4) photoproducts ((6-4)PPs), which can cause severe mutations, melanomas, or even be fatal for the cell. In some organisms, (6-4)PP can be efficiently repaired by photolyase enzymes, in what could be a reverse Paternò-Büchi (PB) reaction through an unstable oxetane intermediate. With the aim of getting deeper insight into the photoreactivity of BP-Thy derivatives and in the photoinduced cleavage of oxetanes, a variety of dyads where Thy and BP are covalently linked by a linear spacer of different lengths and nature were first synthesized. The photochemical reactivity and the photophysical properties of the different derivatives were investigated by means of laser flash photolysis (LFP) and femtosecond transient absorption spectroscopy; besides, the main photoproducts (PPs) arising from steady-state irradiation were also isolated and characterized. The results showed a high degree of chemoselectivity on the linking bridge length and conformation. Concerning the photochemical reactivity, PPs arising from the PB and from formal hydrogen abstraction were formed. In this context, the PB reaction took place for the dyads with the longest spacer with complete regio- and stereoselectivity, along with a hydrogen abstraction process. Finally, the dyads with shorter spacers gave rise to a formal hydrogen abstraction photoproduct and/or polymerization. Accordingly, the overall photoreactivity was proportional to the spacer length and was well correlated with the 3BP* lifetimes, the longer spacers giving rise to shorter lifetimes. In connection to the oxetane photocleavage, irradiation of the different regio- and stereoisomeric oxetanes led to the formation of the typical triplet-triplet absorption band of BP. Accordingly, the photoinduced cycloreversion also operates as an adiabatic process. Photolysis of the oxetane that results from irradiation of the dyad with the longest spacer showed a transient absorption at ~400 nm, which is ascribed to formation of the purported triplet exciplex between BP and Thy covalently linked. Additionally, the PB reaction and the cycloreversion of oxetanes arising from the interaction between Thy or uracil (Ura) derivatives and BP were also investigated. Thus, a wide range of Thy-BP and Ura-BP oxetanes with varying substituents at positions 1 and 5 of the nucleobase were synthesized, including both the head-to-head (HH) and head-to-tail (HT) regioisomers. Spectroscopic studies, including femtosecond transient absorption and LFP results, as well as theoretical multiconfigurational quantum chemistry analysis, agree that the photoinduced cycloreversion for the HH and HT isomers involved the formation of a triplet excited exciplex before the cleavage takes place. Generally, the photochemical reaction was fully adiabatic for the HH regioisomers. In the case of the HH-oxetane arising from the interaction between 1,3-dimethylthymine (DMT) and BP, an absorption band at ca. 400 nm was formed, and was attributed to the triplet exciplex 3[DMT···BP]*. Its formation was highly regioselective towards the HH regioisomer, being faster and more efficient than for the HT isomer. These results were confirmed by computational analysis. In general, adiabaticity was observed in the photoreversion process for all oxetanes, with a high degree of regioselectivity, which falls in line with the theory of the involvement of a triplet exciplex in the process.
Thanks to the Generalitat Valenciana for the finantial support through the Santiago Grisolía grant.
Blasco Brusola, A. (2021). Mechanistic Studies on the Photochemical Formation and Cleavage of Oxetanes Derived from Pyrimidine Bases [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/165256
TESIS

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2007.
Whetten, Robert, Committee Member ; Wang, Z.L., Committee Member ; Perry, Joe, Committee Member ; El-Sayed, Mostafa A., Committee Chair ; Orlando, Thomas, Committee Member.

Reproduction de : Thèse de doctorat : Structure et dynamique des systèmes réactifs : Lille 1 : 2005.
N° d'ordre (Lille 1) : 3618. Titre provenant de la page de titre du document numérisé. Bibliogr. à la suite de chaque chapitre.

Dans le cadre de l'étude de l'évolution du système climatique terrestre, comprendre la composition gazeuse et particulaire de l'atmosphère est un enjeu majeur dans notre compréhension de la Terre et de son atmosphère, de son passé et de son évolution à venir. Les aérosols secondaires, i.e. formés par nucléation, représentent la source la plus importante en nombre des aérosols atmosphériques mais prédire où, quand et en quelle proportion ces aérosols sont formés dans l'atmosphère demeure à ce jour un exercice peu fiable. C'est dans ce contexte que cette étude s'est attachée à compléter nos connaissances des processus conduisant à la formation et à la croissance des particules atmosphériques secondaires. Des études réalisées à partir de mesures de terrain à long terme sur différents sites d'altitude en Europe ont permis de mettre en évidence différentes spéciations verticales de la nucléation démontrant que ce phénomène semble être jusqu'à deux fois plus fréquents à la frontière avec la basse troposphère libre que dans la couche limite planétaire. D'autre part ces mêmes études ont pu mettre en évidence que les mécanismes conduisant à la nucléation de nouvelles particules se différencient avec l'altitude impliquant un rôle plus important de la voie de formation induite par les ions ainsi que des composés organiques volatils. La contribution de cette dernière famille de composés à la nucléation a été également testée durant plusieurs campagnes d'expérimentation en systèmes réactifs ainsi qu'en chambre de simulation atmosphérique. Différents comportements et paramétrisation de la nucléation selon la nature chimique du composé parent ont pu être mis en évidence. Enfin, des études numériques réalisées à partir de données de terrain et d'expérimentation ont permis d'explorer, d'infirmer, de confirmer et de proposer différentes approches numériques afin de simuler les évènements de formation des aérosols secondaires.

This thesis describes the investigation of three aspects of the formation of secondary organic aerosol (SOA): * Aerosol formation from mixed precursors * Global modelling of SOA formation * Modelling of dynamics of SOA formation based on empirical data collected from smog chamber experiments. The formation and growth processes of secondary organic aerosol were investigated using smog chamber experimentation and modelling techniques to gain a better understanding of the application of SOA yield values in modelling both SOA mass and dynamics. Published SOA yields from a range of volatile organic compounds (VOCs) are used to model SOA mass on a local, regional or global scale, based on the assumption that the SOA yield of a mixture is the sum of the yields of the components. Experimental investigations into SOA yield from mixtures of VOC revealed potential uncertainties that would result from applying these yields to systems containing multiple VOCs. SOA formation in systems of toluene or m-xylene, compared with systems of these VOCs and propene, have shown that the introduction of propene (which has a zero SOA yield) to smog chamber photo-oxidations of toluene or m-xylene delays the formation and suppresses the overall yield of SOA from 450 to 90 µg m-3 ppm-1 for the toluene system and from 325 to 125 µg m-3 ppm-1 for the mvxylene system compared with systems of individual species without propene. The SOA partitioning yield data also indicates that partitioning of species to existing aerosol is suppressed in the mixed systems. Gas-phase modelling of these experiments showed that potential SOA species were expected to be formed sooner due to the increased system reactivity provided by propene. The observed delay in SOA nucleation, similar consumption rates of toluene and m-xylene in both the single and mixed systems and the gas-phase modelling results suggest that the addition of propene to hydrocarbon SOA systems modifies the gas-phase chemistry leading to the formation of potential SOA species from toluene and m-xylene. This result calls into question the bulk and partitioning yield values that have been published for pure substances as well as the validity of applying individual VOC yields to VOC mixture. Application of SOA yields to the global scale provides estimates of annual global SOA formation, global contributions from various VOCs and regional SOA distributions. Two SOA modules, using bulk and partitioning yield methods, were added to a global atmospheric chemical transport model, MOZART-2. The bulk yield method, representing the maximum possible global SOA burden, gave an annual production of 24.5 Tg of SOA, which is slightly lower than previous estimates (30 - 270 Tg yr-1). The partitioning method, which gives a more realistic estimate of SOA formation, produced 15.3 Tg yr-1; the biogenic fraction (13.6 Tg yr-1) compares to a previous estimate of biogenic SOA of 18.5 Tg yr-1 and 2.5 to 44 Tg yr- 1 using the partitioning method. Anthropogenic SOA contributions of 1.1 Tg yr-1 from MOZART-2 compared to recent estimates of 0.05 -2.62 Tg yr-1. SOA production was found to be dependent on oxidant availability and VOC emissions in South America and Asia. The partitioning method produced significantly less SOA due to limited availability of OC. Thepartitioning method also produced a peak SOA concentration of 10 µg m-3 over South America in September and showed that SOA is at maximum production for most of the year in Asia and Europe. The two SOA formation methods also provides data to analyse the restrictions to SOA formation in particular regions, based on the maximum amount of SOA able to form (bulk yield method) and the more realistic partitioning estimate from the same region. Limitations to SOA formation in a particular region can be attributed to deficiencies in OC availability or VOC oxidant concentrations. Comparisons to limited observational and modelled data suggest that the MOZART-2 SOA model provides a good representation of global averaged SOA. SOA mass concentrations, predicted by models such as MOZART-2, can be used in part to model the dynamics of an SOA population (e.g. size of particles, number concentrations etc.). Aerosol properties such as size and number concentration can then be used to estimate their effect on climate and health. The explicit representation of the processes that affect aerosol dynamics, such as nucleation, condensation, evaporation and coagulation can be complex and use significant computational resources. Simplification of the discrete coagulation equation and empirical coagulation coefficients for continuum and non-continuum regime diffusion kinetics provided a simplified method of coagulation capable of predicting the evolution of inert sodium chloride aerosol in chamber experiments. A variable coagulation coefficient (linked to the mean particle number concentration of each experiment) was developed. This method is an empirical surrogate for the standard coefficient corrections applied to Brownian based diffusion in the continuum regime to account for the different kinetic effects within the transition and free molecular diffusion regimes. This method removes the need for calculating individual coefficients for each particle interaction. Estimates of modeluncertainty show that within uncertainty limits the model provides a good representation of experimental data. Correlation and index of agreement (IOA) calculations revealed good statistical agreement between modelled and experimental. Some experiments showed degrees of coagulation under prediction using the variable coefficient technique. Investigations into the effect of aerosol type and size, temperature and humidity may be necessary to refine the variable coefficient calculation technique. The model showed little sensitivity to model time step and is capable of high resolution representation of the aerosol. Mass concentration is conserved within the model whereas some error due to numerical diffusion within the number concentrations results from the bin sectioning technique used. The simplicity of this sectioning method over other methods and the minimal effect of numerical diffusion establishes a simplified method of modelling relative to the high resolution of the aerosol distribution the model achieves. It is suggested that the efficiency improvements introduced by the approaches used in developing this model provide an efficient ultra-fine coagulation modelling for atmospheric models. A semi-empirical model for SOA dynamics (SPLAT) incorporating coagulation, nucleation, condensation and evaporation was developed. The aim of the model and the development process was to predict, with high resolution and minimal computational expense, the formation and growth of SOA given a SOA mass input as a function of time. The average size distribution profile from chamber experimental data was used as part of the nucleation module. This technique provided an alternative method of representing the particle distribution compared to those models that assume a single diameter of nucleated particle or a fixed log-normal mode for the entire evolution of SOA. All SPLAT simulations assume organic nucleation events within the experiments modelled, although it is stilluncertain whether they occur in the atmosphere. The modelled nucleation events have produced a single nucleation burst, a result of immediate domination of condensation as soon as nucleation occurs. This deficiency is likely to be a result of the assumption of free molecular diffusion for condensation. The rate of condensation, calculated at every time step, is based on the aerosol size distributed surface area and the particle-size-dependent saturation mass concentrations. The SPLAT coagulation module was a version of the model developed in Chapter 6. Comparisons between experimental and modelled data showed good agreement. These comparisons revealed the shortcomings in the nucleation module while a statistical analysis of the modelled and experimental data has shown SPLAT to be effective in modelling a range of SOA systems. The complexity introduced in modelling aerosol dynamics in high resolution is offset in SPLAT by efficiency improvements due to the insensitivity of the model to time step size and simplified methods of bin sectioning, nucleation, coagulation, condensation and evaporation. Published SOA yields can be applied to predict SOA mass at local, regional or global scales. Although previously unreported uncertainties in these yields have been shown to exist, the MOZART-2 global chemical transport model has shown that SOA mass concentration can be predicted with reasonable quality, considering the scale of the model and limited observational data. These global scale SOA mass predictions can be used purely for global burden and occurrence, or as the input for modelling the dynamics of an aerosol population, which is significant for estimating an aerosol population's effect on climate change and health. SOA mass concentrations from chamber experiments were used as input to a SOA dynamics model. This model (SPLAT) then predicted the evolution of particle number concentrations and size within these experiments based on this mass input. Application of the dynamics model to the output of the MOZART-2 model could then provide a comprehensive global scale SOA modelling package.

Les aérosols organiques secondaires (AOS) représentent une fraction significative de l'aérosol fin, et contribuent donc fortement à leurs impacts sur la santé, l'environnement et le climat. Connaitre les sources, l’évolution et les propriétés des AOS constitue actuellement un véritable enjeu pour la communauté scientifique. Ces AOS sont formés par condensation sur des aérosols préexistants des espèces de faible volatilité produites au cours de l’oxydation progressive de la matière organique gazeuse. L'objectif de ce travail de thèse vise à évaluer nos connaissances sur les processus de formation de l’AOS. La méthodologie mise en place consiste à (i) représenter les processus dans un modèle déterministe et explicite, (ii) confronter le modèle à des expériences de formation d’AOS effectuées dans des environnements contrôlés et (iii) examiner la sensibilité des évolutions simulées aux paramètres peu contraints. Le modèle GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) développé au LISA permet de générer des schémas chimiques explicites sur la base de principes fondamentaux et de renseigner les grandeurs cinétiques et thermodynamiques associées. Sa capacité à représenter la formation des AOS a été évaluée par comparaison avec des expériences en chambres de simulation atmosphérique (CSA). Les comparaisons modèle/mesures des rendements finaux en AOS montrent que l’outil GECKO-A restitue correctement l’influence de la structure moléculaire sur la formation d’AOS. Cependant l’analyse quantitative montre que ces rendements sont systématiquement surestimés. Ceci suggère que des processus sont manquants ou mal représentés dans le modèle, en particulier la perte de composés organiques gazeux aux parois des CSA. L’intégration de ce processus dans le modèle conduit à (i) une diminution des rendements finaux simulés pouvant atteindre un facteur 2, (ii) une modification de la composition de l’AOS avec une sensibilité importante pour les espèces de premières générations (nitrates, hydroxynitrates et carbonylesters) et (iii) une vitesse de production de l’AOS plus faible lorsque la vitesse de transfert vers les parois augmente. La dynamique de formation des AOS n'est cependant pas correctement reproduite par le modèle. Les résultats montrent que les incertitudes sur les paramètres d’accommodation à la surface des particules et de pertes gazeuses aux parois permettent d’encadrer les données expérimentales. Aucune configuration unique de ces deux paramètres ne permet, toutefois, de représenter l’ensemble des expériences
Secondary organic aerosols (SOAs) represent a large fraction of fine particle matter, and contribute therefore to their impacts on human health, environment and climate. Understanding the sources, the evolution and the properties of SOAs is a challenge for the scientific community. These SOAs are produced by condensation onto preexisting aerosols of low volatility compounds formed during the progressive oxidation of gaseous organic matter. The objective of this thesis is to assess our knowledge of SOA formation processes. The methodology aims at (i) representing the processes in a deterministic and explicit model, (ii) comparing the modeling results with SOA measurements performed in controlled environments and (iii) examining the sensitivity of simulated results to poorly constrained parameters. The GECKO-A model (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) developed at LISA generates explicit chemical schemes on the basis of fundamental principles and provides the related kinetic and thermodynamic constants. Its ability to represent SOA formation was evaluated by comparisons with experiments performed in environmental chambers. The comparisons between modeled and measured final SOA yields show that the GECKO-A tool accurately reproduces the influence of molecular structure on the SOA formation. However, quantitative analysis shows that these yields are systematically overestimated. This suggests that processes are missing or misrepresented in the model, in particular the loss of gaseous organic compounds on the chamber walls. The implementation of this process into the model leads to (i) a decrease of the simulated final yields up to a factor 2, (ii) a change on SOA composition with a high sensitivity for the first generation species (nitrates, hydroxynitrates and carbonylesters) and (iii) a decrease in the SOA production rate when the mass transfer rate to the wall is increased. The model fails however to reproduce the dynamic of SOA formation. The results show that the uncertainties on particle surface accommodation and wall losses allow to encompass the experimental data. However, no unique configuration of these two parameters can be selected for all of the experiments

Les nanotechnologies sont devenues depuis plusieurs années un axe majeur de développement dans les domaines du diagnostic, de l’imagerie, de la délivrance de médicament, du suivi thérapeutique et de l’ingénierie tissulaire. L’administration de produits non injectables sous leur forme libre ou bien possédant une toxicité élevée, peut être facilitée par l’utilisation de nanovecteurs, modifiant leur distribution. Ils permettent donc de réduire les doses administrées, limiter les effets secondaires et diriger le contenu du vecteur (agent de contraste, drogue) vers un organe cible ou une tumeur, en présentant à la surface de celui-ci des molécules de ciblage de ces zones spécifiques.Cette thèse s'inscrit dans cette thématique : nous avons exploré les possibilités de former des gels chimiques à partir des nanoparticules lipidiques qui sont constituées d'un cœur huileux pouvant encapsuler de petites molécules hydrophobes et d'une couche de surfactants permettant la stabilisation des gouttelettes en phase aqueuse.Nous avons pu synthétiser plusieurs surfactants PEGylés fonctionnalisés (thiol, maléimides, amine, oxyamines et ONB-maléimide). Les protocoles de synthèse de ces surfactants sont affinés et reproductibles.Ces surfactants ont été incorporés à la surface des nanoparticules lipidiques. Les nanoparticules fonctionnalisées ainsi obtenues ont été caractérisées et les fonctions présentes à leur surface sont mises en évidence.Différentes sortes de gels chimiques stables, résistant à la dilution, rapides à fabriquer et contrôlables ont été élaborés.Ces gels chimiques peuvent être utilisés dans l’avenir pour encapsuler des protéines ou des drogues
Nanotechnology became for several years a major development in the areas of diagnostics, imaging, drug delivery, therapeutic monitoring, and tissue engineering. The administration of non-injectable products in their free form or with high toxicity, can be facilitated by the use of nanocarriers, changing their distribution. They therefore reduce the doses administered, limit side effects and direct the contents of the vector (contrast agent, drug) to a target organ or tumor, by presenting to the surface thereof targeting molecules of these areas specific.This thesis fits into this theme : we have explored the possibilities of forming chemical gels based on lipid nanoparticles which are composed of an oily heart can encapsulate small hydrophobic molecules and a layer of surfactants allowing stabilization of the droplets in the aqueous phase.We have synthesized several PEGylated functionalized surfactants (thiol, maleimide, amine, and oxyamines ONB-maleimide). synthesis protocols of these surfactants are refined and repeatable.These surfactants were incorporated into the surface of lipid nanoparticles. The functionalized nanoparticles thus obtained have been characterized and the functions present at their surface are highlighted.Different kinds of chemical gels stable, resistant to dilution, fast and controllable manufacturing have been developed.These chemical gels can be used in the future for encapsulating proteins or drugs

La cinétique de formation de complexes électroniquement excités a été examinée dans les cas suivants : excimères intermoléculaires, exciplexes intermoléculaires et excimères intramoléculaires. Dans la première partie, le processus de formation de complexes intermoléculaires est étudié dans des milieux de viscosités différentes. Deux modèles cinétiques sont confrontés dans l'analyse des déclins de fluorescence : modèle de Birks ou les effets transitoires sont négligés et un modèle plus sophistiqué mis en place a partir d'équations de transport moléculaire brownien, de la connaissance de constantes chimiques réactionnelles et du principe de superposition. On constate que le modèle simple de Birks reste valable, dans les limites expérimentales, même dans des milieux où les effets transitoires sont importants. Dans la deuxième partie, l'étude de la cinétique de cyclisation de chaines de polystyrènes sous l'effet de la pression et de la température (dans une paraffine) par l'intermédiaire de la formation d'excimères de pyrène intramoléculaire greffé à chaque extrémité de la chaine a été abordée. Trois solvants sont utilisés : le toluène (bon solvant), le methylcyclohexane (mauvais solvant) et le cyclopentane (solvant). Cette étude permet d'élucider comment les deux facteurs : changement de la viscosité du solvant et altération des propriétés thermodynamiques du système polystyrène/solvant, induits par l'augmentation de la pression ou de la température, peuvent affecter la cyclisation de la chaine dans les différents solvants

La Pollution automobile est un sujet de plus en plus préoccupant depuis ces dernières années. Les réglementations sont de plus en plus sévères. Si certains polluants font l'objet de normes d'émissions réglementés strictes, d'autres composés sont moins surveillés bien qu'ils soient tout aussi nocifs de façon directe (pollution primaire) ou indirecte (pollution secondaire) pour l'homme, c'est le cas de certaines espèces de la famille des Composés Organiques Volatils (COV) et des Composés Carbonylés. Le présent travail associe à la fois la mesure expérimentale, l'inventaire des émissions de polluants dues aux transports et la modélisation de la qualité de l'air. Les mesures expérimentales sont réalisées, dans le cadre d'un projet Européen "Projet ARTEMIS (Assesment and Reliability of Transport Emission Models and Inventory Systems) coordonné par l'INRETS , sur un parc de 30 véhicules (Essence et Diesel) de technologies récentes. Ces véhicules sont soumis à divers cycles de conduites afin d'améliorer les bases de données concernant les émissions véhiculaires pour les véhicules particuliers. Les polluants mesurés sont principalement les COV dits "légers" (C2 à C6), les COV dits "lourds" (C7 à C15) ainsi que les composés carbonylés, l'ensemble des espèces ainsi mesurées atteint une centaines de composés, pour cette partie du projet. La détermination des facteurs d'émissions (g/km parcouru) de chacun des polluants pour chaque véhicule du parc testé a été réalisée puis ces valeurs ont été reprises dans le cadre de l'élaboration d'un cadastre des émissions véhiculaires pour la région Nord-Pas de Calais
À partir de la répartition des polluants sur la région suivant ce cadastre, les données obtenues ont servi de données d'entrées pour un modèle de simulation physicochimique de la troposphère (UAM Urban Airshed Model). Une étude précédemment menée, portant sur l'introduction de la spéciation moléculaire détaillée des COV et l'utilisation du mécanisme CBIV n'a pas donné de résultats concluants quant à l'impact de cette spéciation sur la formation d'ozone. Nous souhaitions par l'introduction d'un nouveau mécanisme avoir une prise en compte meilleure de l'ensemble de ces composés et voir ainsi leur contribution éventuelle sur la formation d'ozone sur notre domaine. Ceci nécessitait une adaptation du modèle et notamment l'installation d'un module (interface FCM = Flexible Chemical Mecanism) permettant l'introduction d'un nouveau mécanisme chimique (SAPRC 99 au lieu du CBIV) au sein même du modèle. L'ensemble des fichiers d'entrées a été adapté pour la prise en compte de la totalité des composants. L'influence de la spéciation des COV sur la formation d'ozone sur un épisode de simulation a été ensuite étudiée avec une augmentation de la concentration d'ozone calculée aux stations et un pourcentage moyen d'écart sur la formation d'ozone de l'ordre de 28% par rapport aux calculs avec le précédent mécanisme

La combustion de bois, ou plus largement de la biomasse, est une source de pollution très importante en particules atmosphériques en hiver, particulièrement en France. Si les émissions primaires ont été étudiées depuis de nombreuses années, il existe de grandes incertitudes sur le devenir de ces émissions dans l’atmosphère. Le travail de thèse a donc porté sur l’étude du vieillissement en chambre de simulation atmosphérique de l’aérosol émis par 3 appareillages pour le chauffage au bois (conçus entre 2000 et 2010 et représentatifs de la politique de renouvellement mis en place par l’ADEME), avec un intérêt particulier pour le potentiel de formation d’aérosol organique secondaire (SOA) et la modification de l’empreinte chimique à l’échelle moléculaire au cours du transport atmosphérique. Les expériences ont montré un potentiel de formation de SOA très important. La concentration en OA peut ainsi être multipliée par 7 (1.5 – 7.1) entre l’émission et après un temps de résidence atmosphérique équivalent à 5 h. Cette étude met également en évidence l’impact de l’efficacité de combustion sur les facteurs d’émission et par conséquent le rôle crucial de l’opérateur. L’étude à l’échelle moléculaire a mis en évidence la formation de composés susceptibles de servir de marqueurs de combustion de biomasse âgée, principalement des nitrocatéchols. Enfin, cette étude démontre le rôle clé de la volatilisation du lévoglucosan, principal marqueur organique de la combustion de biomasse, au cours du processus de dilution dans l’atmosphère, et pose clairement la question de la pertinence des constantes cinétiques de dégradation préalablement calculées en chambre de simulation atmosphérique
Biomass burning is in winter a main source of air pollution by particulate matter, especially in France. While primary emissions have been characterized extensively before, few studies have addressed the aging of these emissions in the atmosphere and large uncertainties remain. Therefore, the objectives of this thesis was to study in a smog chamber the aging of the aerosol emitted by 3 different woodstoves used for residential heating (fabricated from between 2000 and 2010, and representative of the policy engaged by the French environmental agency to renew the appliances across the country), with a specific focus on the Secondary Organic Aerosol (SOA) production potential and the modification of the chemical fingerprint of the emissions at the molecular level during their transport in the atmosphere. The experiments showed the SOA production potential can be significant. The OA concentration can be increased by up to a factor of 7 (1.5 – 7.1) after being aged in the smog chamber with a time equivalent to 5 hours in the atmosphere. The study also further demonstrated the influence of the combustion efficiency on the emissions and implicitly the role of the operator. The study of the composition of the aerosol at the molecular level showed the formation of compounds, likely to serve as markers for aged biomass burning, mainly nitrocatechols. Finally, the work also illustrates the influence of the volatilization of levoglucosan, main marker of biomass burning, during the dilution process occurring in the atmosphere, and challenge the pertinence of the degradation rate constant determined previously in smog chamber

Les radicaux peroxydes RO2 (avec R = H ou CxHy) jouent un rôle important dans les cycles de photo-oxydation ayant lieu dans la troposphère. Ils sont produits principalement par l’oxydation des hydrocarbones et du monoxyde de carbone par les radicaux OH suivi de la réaction avec O2. Ils peuvent réagir avec NO pour former du NO2 qui est une source importante d’ozone troposphérique. Pour comprendre les mécanismes de génération de l’ozone troposphérique, des mesures précises et reproductibles des concentrations des radicaux peroxydes sont essentielles. A cela, des études de cinétiques, comme la mesure du temps de vie des radicaux peroxydes, sont nécessaires. Des études récentes ont montré des différences importantes entre les concentrations de radicaux peroxydes mesurées en air ambiant et celles calculées grâce aux modèles de chimie atmosphériques. Ceci peut être dû à des chemins réactionnels manquants et à l’incertitude sur les constantes de vitesses. Deux nouvelles techniques ont été développées afin d’examiner ces différences. La première technique permet la mesure sélective des radicaux HO2 et RO2 par la technique PERCA. Les radicaux HO2 sont ôtés sélectivement en utilisant un « glass denuder ». La seconde technique a pour but la mesure de la vitesse totale de disparition des radicaux HO2 dans l’atmosphère en utilisant la combinaison de la photolyse laser avec la FIL pour la détection de HO2. Les radicaux HO2 générés par photolyse laser réagissent avec les espèces réactives présentes dans l’air ambiant comme les NOx. La vitesse de disparition de HO2 est mesurée en utilisant la FIL à 308 nm après conversion chimique des HO2 grâce à l’ajout de NO
Peroxy radicals RO2 (with R = H or CxHy) play an important role in the photo-oxidation cycles of the troposphere. They are produced mainly via the atmospheric oxidation of hydrocarbons and carbon monoxide by OH radicals and subsequent reactions with O2. They can further react with NO to produce NO2, witch is an important reaction of tropospheric ozone generation. To understand the mechanism of this tropospheric ozone generation, precise and accurate measurements of ambient peroxy radical concentrations are essential. And not only atmospheric concentration measurements but also atmospheric kinetics studies such as lifetime measurements of peroxy radicals are necessary. Recent publications show big differences between measured peroxy radical concentrations and those calculated with chemical models. These could be caused by missing reaction pathways and uncertainties in reaction yields and rate constants. To investigate these missing reactions and the uncertainties in known peroxy radical reactions via ambient measurements, newly developed two instruments as described below are applied. One is a technique for the selective measurement of atmospheric peroxy radical concentrations of HO2 and RO2 using the PERCA technique. HO2 radicals are selectively removed by using a glass denuder to achieve the selective measurement. The other one is a technique for total HO2 loss rate measurement in the atmosphere by using laser-flash photolysis and LIF detection of HO2. Generated HO2 radicals by laser-flash photolysis react with ambient reactive species such as NOX in the reaction tube. HO2 loss is measured using LIF at 308 nm coupled with chemical conversion with NO

Polybrominated dibenzo-p-dioxins (PBDD) and dibenzofurans (PBDF) are a group of compounds of emerging interest as potential environmental stressors. Their structures as well as toxic responses are similar to the highly characterized toxicants polychlorinated dibenzo-p-dioxins. High levels of PBDDs have been found in algae, shellfish, and fish, also from remote areas in theBaltic Sea. This thesis presents studies on PBDD behavior in fish and offspring, and natural formation of PBDDs from naturally abundant phenolic precursors. The uptake, elimination, and maternal transfer of mono- to tetraBDD/Fs were investigated in an exposure study reported in Paper I. The effects of PBDDs in fish were examined in a dose-response study (Paper II). It was shown that fish can assimilate PBDD/Fs from their feed, although non-laterally substituted congeners were rapidly eliminated. Laterally substituted congeners were retained as was congeners without vicinal hydrogens to some extent. PBDD/Fs were transferred to eggs, and congeners that were rapidly eliminated in fish showed a higher transfer ratio to eggs. Exposure to the laterally substituted 2,3,7,8-TeBDD had significant effects on the health, gene expression and several reproduction end-points of zebrafish, even at the lowest dose applied. The geographical and temporal variations of PBDD in biota samples from the Baltic Seasuggest biogenic rather than anthropogenic origin. In Paper III, bromoperoxidase-mediated coupling of 2,4,6-tribromophenol yielded several PBDD congeners, some formed after rearrangement. The overall yield was low, but significantly higher at low temperature, and the product profile obtained was similar to congener profiles found in biota from the Swedish West Coast. In Paper IV, photo­chemi­cally induced cyclization of hydroxylated polybrominated diphenyl ethers under natural conditions produced PBDDs at percentage yield. Rearranged products were not detected, and some abundant congeners do not seem to be formed this way. However, the product profile obtained was similar to congener profiles found in biota from the Baltic Proper. Since the PBDD congeners found in biota have a high turn-over in fish, the exposure must be high and continuous to yield the PBDD levels measured in wild fish. Thus, PBDDs must presumably be formed by common precursors in general processes, such as via enzymatic oxidations, UV-initiated reactions or a combination of both. The presented pathways for formation of PBDDs are both likely sensitive to changes in climatic conditions.

L'incertitude entourant la production du pétrole et la pollution associée aux fossiles combustibles ainsi que la série d'accidents bien connus de Three Mile Island, Tchernobyl et Fukushima, en plus que le désir de diversifier les sources d'énergie sont des facteurs importants qui favorisent le développement de la technologie des cellules photovoltaïques. Certaines applications de photovoltaïques organiques sont particulièrement intéressantes à cause de la possibilité d'impréssion des circuits et la création de cellules photovoltaïques flexibles sous la forme d'un ruban adhésif. À la suite des études fondamentales de Tang, que l'on appelle hétérojonction en volume (BHJ), des cellules photovoltaïques ont été créées par une séparation de phase du polymère. Certains appareils BHJ sont déjà disponibles dans le commerce, mais leur efficacité photovoltaïque est encore faible. Afin d'améliorer cette efficacité, nous proposons de modéliser le processus critique par lequel une excitation locale ( « un exciton ») se dissocie pour former une paire électron / trou conducteur. Contrairement à la majorité des physiciens specialiste dans l'état solide impliqués dans l'étude de ce problème qui semble ignorer le caractère non-Born-Oppenheimer typique de cet événement, nous prévoyons de traiter cet événement directement par la modélisation photochimique utilisant la dynamique semiclassique (saut de suface de Tully) avec laquelle nous avons déjà une certaine expérience. Comme l'objectif est la compréhension des systèmes très complexes, nous proposons des calculs exploratoires basées sur la méthode TD-DFTB, une version semiempirique de la théorie de la fonctionnelle de densité en fonction du temps (TD-DFT) pour lequel un de nous est bien connu pour son travail pionnier. L'étude sera menée en collaboration avec le groupe ORGAVOLT des développeurs de méthodes ab initio pour la modélisation des BHJs, et avec des groupes à Singapour intéressés par les BHJs, ainsi qu'avec des groupes en Allemagne spécialisés dans la DFTB
The uncertainty surrounding petroleum production and the pollution associated with fossil fuels plus the series of well-known accidents of Three Mile Island, Chernobyl and Fukushima plus the desire to diversify energy sources are important factors favoring the development of solar cell technology. For certain applications organic photovoltaics are particularly interesting because (for example) of the possibility of printing these circuits and the creation of flexible solar cells in the form of adhesive tape. Following the seminal studies of Tang, so-called bulk heterojunction (BHJ) solarcells have been created by polymer phase separation. Some BHJ divices are already available commercially but their photovoltaic efficiency is still low. In order to aid in the improving this efficiency, we propose to model the critical process by which a local excitation (an "exciton") dissociates to form a conducting electron/hole pair. In contrast with the majority of solid-state physicists involved in studying this problem who seem to ignore the typically non-Born-Oppenheimer character of this event, we planto treat this event directly by photochemical modeling using semiclassical (Tully-type) surface-hopping dynamics with which we already have some experience. As the objective is the comprehension of highly complex systems, we propose exploratory calculations based on the TD-DFTB method, a semiemprical version of the time-dependent density-functional theory (TD-DFT) for which one of us is well-known for his pioneering work. The study will be carried out in collaboration with the ORGAVOLT group of developers of ab initio methods for modeling BHJs, and with groups in Singapore interested by BHJs, as well as with groups in Germany specializing in DFTB

Marine aerosols have attracted increasing attention over the past 15 years because of their potential significance for global climate modelling. The size distribution of these aerosols extends from super-micrometer sea salt mode particles down through 150 nm accumulation mode particles, 40 nm Aitken mode particles and nucleation mode particles which extend from 25 nm right down to clusters of a few molecules. The process by which the submicrometer modes form and grow and their composition have remained topics of debate throughout this time in large part because of the difficulties associated with determining their composition and relating it to proposed models of the formation process. The work compared the modality of marine aerosol influencing the South-east-Queensland region with that of other environmental aerosols in the region. The aerosol was found to be consistent with marine aerosols observed elsewhere with concentrations below 1000 cm-3 and frequently exhibiting the distinct bimodal structure associated with cloud processing, consisting of an Aitken mode at approximately 40 nm, an accumulation mode in the range 100-200 nm and a coarse mode attributed to sea salt between 600 and 1200 nm. This work included the development of two new techniques for aerosol research. The first technique measures aerosol density using a combination of aerosol size distribution and gravimetric mass concentration measurements. This technique was used to measure the density of a number of submicrometer aerosols including laboratory generated NaCl aerosol and ambient aerosol. The densities for the laboratory generated aerosols were found to be similar to those for the bulk materials used to produce them. The technique, extended to super-micrometer particle size range may find application in ambient aerosol research where it could be used to discriminate between periods when the aerosol is dominated by NaCl and periods when the density is more representative of crustal material or sulfates. The technique may also prove useful in laboratory or industrial settings for investigating particle density or in case where the composition is known, morphology and porosity. The second technique developed, integrates the existing physicochemical techniques of volatilisation and hygroscopic growth analysis to investigate particle composition in terms of both the volatilisation temperatures of the chemical constituents and their contribution to particle hygroscopic behaviour. The resulting volatilisation and humidification tandem differential mobility analyser or VH-TDMA, has proven to be a valuable research tool which is being used in ongoing research. Findings of investigations relating the composition of the submicrometer marine aerosol modes to candidate models for their formation are presented. Sea salt was not found in the numerically dominant particle type in coastal nucleation mode or marine Aitken and accumulation modes examined on the Southeast Queensland coast during periods where back trajectories indicated marine origin. The work suggests that all three submicrometer modes contain the same four volatile chemical species and an insoluble non-volatile residue. The volatility and hygroscopic behaviours of the particles are consistent with a composition consisting of a core composed of sulfuric acid, ammonium sulfate and an iodine oxide coated with a volatile organic compound. The volume fraction of the sulfuric acid like species in the particles shows a strong dependence on particle size.

Lors de la polymérisation en suspension du chlorure de vinyle, il se forme sur les parois un dépôt de polychlorure de vinyle (PVC). Ce phénomène, nommé encroûtement, génère des problèmes car il limite la production de PVC et affecte la qualité du produit final. Dans ce contexte, un projet FUI (Fond Unique Interministériel) intitulé «Ecoating», a été financé dans le cadre d’une collaboration entre plusieurs partenaires industriels et universitaires (INEOS ChlorVinyls, Mäder Research, Avenir Group, LPIM, ESPCI-ParisTech). Deux thèses ont vu le jour au LPIM, avec pour but de développer un revêtement (photo)polymère aux propriétés anti-encroûtement durables qui permettrait d’améliorer la qualité du PVC produit, d’augmenter les quantités produites et ainsi d’améliorer la compétitivité des usines de PVC. Cette thèse s’inscrit dans le développement d’un vernis photopolymère répondant au cahier des charges. Pour éviter l’encroûtement des réacteurs, il est nécessaire de stopper une étape du mécanisme d’encroûtement comme l'adsorption sur les parois du réacteur d’un copolymère nommé Acvagen Graft Copolymer (AGC). Ce copolymère est très actif dans le phénomène d’encroûtement (site de nucléation) et se trouve principalement dans la phase aqueuse du milieu réactionnel. La stratégie de recherche élaborée dans ce projet a été basée sur le développement d'un revêtement photopolymère présentant une faible affinité pour l'eau et devant adhérer à la surface des réacteurs pour éviter la formation de croûte. Les polymères à base de fluoroacrylates ont été les premiers candidats choisis dans cette étude du fait que leurs propriétés exceptionnelles (faible énergie de surface, stabilité chimique et haute hydrophobicité...) pouvaient éviter l'adsorption de l'AGC sur les parois du réacteur, et par conséquent le développement de la croûte. Une recherche bibliographique a été réalisée pour comprendre le comportement particulier de ces molécules qui migrent vers la surface du film et s’organisent en surface pour donner des surfaces hydrophobes. Des mélanges de résines fluoroacryliques modèles ont été testés pour évaluer le caractère hydrophobe du revêtement, comprendre la migration des molécules de fluor vers l’interface en fonction de la nature de substrat et aussi déterminer l’influence de l’ajout d’additifs fluorés au mélange sur les propriétés globales du film. Cette étude nous a permis de comprendre l’influence de l’additif fluoré sur les propriétés chimiques et physiques du film. À l’échelle du laboratoire des tests d’immersion de ces revêtements déposés sur l’acier inoxydable ont étés réalisés dans l’eau chaude (80°C) afin de caractériser leur caractère hydrophobe en fonction du vieillissement dans l’eau chaude ainsi que l’adhésion du film au substrat. Nous avons observé une diminution de l'hydrophobicité de la surface du film au cours du temps lors d’une immersion. [...]
Our scientific approach has explored different strategies to develop a durable UV-cured coating with antifouling properties to prevent the crust formation. Firstly, the potential of fluoroacrylate photocurable coatings was exhaustively investigated. Indeed, their outstanding properties (low surface energy, chemical stability and high hydrophobicity...) could limit the adsorption of the AGC on the reactor walls and further encrusting. A bibliographic research highlighted the behavior of fluorinated monomers on film surface and the parameters affecting the hydrophobic properties. Different fluorinated monomers were selected. At low concentration, they provide hydrophobic surfaces on 316L stainless steel, the reference substrate. However, a decrease of the films surface hydrophobicity in hot water was observed with time, and was attributed to a disorganization of the fluorinated chains on the coating surface. An optimization of the amount of fluoroacrylate monomer was performed by confocal Raman microscopy (CRM) to promote the fluorinated chains stability on the surface before and after immersion in hot water at 80°C. The beneficial effect was found maximal at a concentration ranging from 1 to 1.8 wt%. However, even after this optimization, a decrease of the film surface hydrophobicity was observed for increased immersion time in hot water. Therefore, optimized fluoroacrylate monomer concentration was combined with alternated thermal/immersion post-treatment and has conducted to more stable photocured films. This result was attributed to a rigidification of the fluorinated chains on the film surface limiting thus, the extent of their disorganization. After this study realized at a laboratory scale, we tested the photocured coating in the VCM pilot reactor. A surface cleaning, an increase of the stainless steel roughness by shot blasting and the use of alkoxysilanes as coupling agents were implemented in order to enhance the adhesion properties of the photopolymer film on stainless steel. In addition, the use of a fluorinated monomer containing a heteroatom improved the rigidification when associated with the alternated thermal/immersion post-treatment. The crust formation was limited during four successive polymerizations in the VCM pilot reactor. A durable anti-fouling UV-coating could be not obtained due to some swelling phenomena resulting from the lack of coating adhesion or some abrasion occurring from small PVC pellets during the PVC polymerization.A second part of this project was dedicated to superhydrophobic coatings. Indeed, reducing interaction with water should lead to a better protection of the substrate. A literature review on the superhydrophobic surfaces has shown that the contact with hot water generally strongly affects their antiwetting properties and induces a large contact angle decrease. [...]

碩士
國立成功大學
環境工程學系
85
ABSTRACTThe purposes of this study are to investigate the spatial and seasonal variations of pollutants in photochemical smog such as PM10、formaldehyde(HCHO) and NO2 in southern Taiwan where the pollution of photochemical smog is the most serious in Taiwan. The formation rates of nitrate and sulfate were evaluated by using the measured data with back-trajectory analysis. In addition, the potolysis rate of NO2 was measured to evaluate the ozone formation rate with photostationary state method. The measurements were conducted simutaneously for five runs in the following sites : Ping-Tung、May-Nong、Nan-Z、Hsiao- Gang、Feng-Shan、Da-Liao and Lin-Yuan from October 1995 to March 1997 and the temporal resolution was two hours.The results show that the pollution of PM10 is more serious during autumn and winter while the air quality is better in summer. The concentrations of PM10 in Ping-Tung showed significantly seasonal variations：the concentration of PM10 were 4~5 times greater in autumn and winter then those in summer. The water soluable chemical species such as Cl-、NO3-、SO42-、Na+、NH4+、 K+、Mg2+ and Ca2+ are about 20~40% of PM10. The concentrations of the most abuntant species, NO3-and SO42-, in PM10, are abuot 3~30 and 1~20ug/m3. Besides concentrations, the ratios of NO3- and SO42- in PM10 are also greater in autumn and winter then in summer.The measurements of PM2.5 and PM10 show that the ratios of PM2.5 in PM10 of the inert species , such as Na+、K+ and Mg2+, are less then 50%, but the ratios of the reactive species NO3-、SO42- and NH4+ are up to 85%. In addition, the measurements of particle size distribution also show that NO3- and SO42- have a large portion in fine particle, implying the significant contribution of secondary aerosol formed in photochemical smog.The conversion rates of NO and SO2 are about 0.04~4.28%/hr and 0.27~34%/hr, respectively. Besides gas phase reaction, a large portion of secondary aerosol comes from aqueous reaction due to the high humidity in Taiwan. Therefore, the correlation between conversion rate and O3 formation is not significant.The concentrations of two-hour average for HCHO are 0.04~86.38ppb, while the contribution of vehicles is 10~50%. Without vehicle contribution, the diurnal variation of HCHO is only obvious at Lin-Yuan site in August. The non-vehicle contributed HCHO shows strong correlation with ozone with the correlation coefficient between them of 0.78.The measured photolysis rate of NO2 at Da-Liao site was about 4*10-3sec-1 and the differences between the predicted and measured ozone formation rates were -17 to 22 ppb/hr with the median value of -5.6ppb. More study is needed in the future to modify the model for ozone formation rate, for example the loss rate ozone and the contributions of peroxides.keywords：conversion rate、ozone formation rate

Photochemical oxidation of biogenic (Isoprene) and anthropogenic (1-octene) hydrocarbons are examined. Experiments studied the individual daylight reactions of both isoprene and 1-octene, including those of OH, O3, and O([superscript 3]P). Results from both the smog chamber experiments and computer kinetic modeling were then used to develop photochemical oxidation mechanisms for each hydrocarbon. Aerosols formed by isoprene and another biogenic, beta-pinene, are characterized. The OH reaction with isoprene is studied. Methyl nitrite photolysis experiments were carried out in an outdoor smog chamber in an attempt to identify as completely as possible OH-isoprene product spectrum. Emphasis was placed on identification and quantification of oxygenated products. The design of a Tenax-based cryo-trap thermal desorber used to trap, concentrate, and dry chamber samples for identification on a GC/MS is described. Analysis of the products revealed that O([superscript 3]P) can form in reaction systems designed to study OH reactions that include high concentrations of NO, and consequently NO2, hence this reaction is also examined. The yields of methacrolein and methyl vinyl ketone are determined as 25±3 and 35.5±4%, respectively, with an additional 5.1±3% as 3-methyl furan, totaling 66±3%. These results, combined with those of previous studies-allow 80% of isoprene's products to be explicitly identified, and the general structure of the remaining products to be ascertained. The O([superscript 3]P) reaction produces 84±8% epoxides, and 8±3% species which result in production of HO2, and subsequently OH. A heretofore unidentified product of the O([superscript 3]P) reaction, 2,2 methyl butenal, is identified. The rate constant of the NO2-isoprene reaction is measured. A series of experiments have been carried out to study the ozone-isoprene reaction in a smog chamber using externally produced O3, added to the hydrocarbon in the dark. A chemical tracer, methyl cyclohexane, was added to probe the OH formation in the system. O([superscript 3]P) formation was also examined using the known distribution of products that are unique to the O([superscript 3]P)-isoprene reaction (part 1). The results provide clear evidence that both OH and O([superscript 3]P) are produced from the O3-isoprene reaction directly in large quantities; about 0.68±0.15 and 0.45±0.15 per O3 -isoprene reaction, respectively. These additional radicals severely complicate the analysis of the O3 reaction, hence computer kinetic modeling was necessary to ascertain the products of the O3 reaction itself. The product spectrum, which differs dramatically from that published previously, is: 67±9% methacrolein, 26±6% methyl vinyl ketone, and 7±3% propene, accounting for 100±10% of the reacted isoprene. Applicability of these results to the gas-phase O3 reaction with other unsaturated hydrocarbons is briefly discussed. The photooxidation chemistry of 1-octene is examined in detail. Formation of OH from the O3 reaction was examined with the use of a tracer/absorber, methyl cyclohexane. The O3 - 1-octene reaction is found to produce, apparently directly, significant quantities of OH, 0.55+0.2 on a per molecule reacted 1-octene basis. Almost 100% of the reacted 1-octene could be accounted for as 80±10% heptanal, 11±6% thermally stabilized Criegee biradical, and about 1% hexane. The OH - 1-octene reaction was found to produce only 15±5% heptanal. The remainder is assumed to result in the formation of alkyl nitrates (32%), and isomerization and eventual formation of multisubstituted products (52%). A separate experiment examining the O([superscript 3]P)-1-octene reaction, showed that 1-octyl oxide accounted for about 80% of the reacted 1-octene. A photochemical model was developed for 1-octene oxidation, and is compared with smog chamber results from NO/NO2-octene experiments. The most crucial factor in the performance of the model is the quantity of assumed alkyl nitrate formation. A mechanism for the oxidation of isoprene is developed and includes the recent developments on each of isoprene's atmospherically important reactions: O3, OH, O([superscript 3]P), and NO3. The mechanism is tested against chamber data that includes a range of mixtures of these reactions. While it performs reasonably well under conditions where the OH and O([superscript 3]P) reactions dominate, it tends to over predict O3 formation, as well as the speed of development of O3 under conditions where the O3 and NO3 reactions are important. The NO3 reaction is the most uncertain aspect of the isoprene mechanism, and may be responsible for a large part of this discrepancy. The discrepancy may also arise from the difficulty in extrapolating the results of O3 experimental results, necessarily carried out in the absence of NOx, to conditions that include significant concentrations of NOx. An extensive set of outdoor smog chamber experiments was carried out to study aerosol formation by two representative biogenic hydrocarbons: isoprene and beta-pinene. The hydrocarbons, at concentrations ranging from a few ppb to a few ppm, were photooxidized in the presence of NOx. Isoprene was found to produce negligible aerosol at ambient conditions, whereas beta-pinene aerosol carbon yields were as high as 8%, depending strongly on the hydrocarbon to NOx ratio. Aerosol samples subjected to infrared absorption spectroscopy revealed that the dominant aerosol products for both isoprene and beta-pinene are organic nitrates, organic acids, as well as other carbonyls and hydroxy compounds. GCMS of the neutral fraction of the beta-pinene aerosol revealed nopinone and several other compounds with molecular weights ranging from 138-200 amu, indicating mainly mono- and dioxygenated products. The average vapor pressure of the 13-pinene aerosol was estimated to be 37 ± 24 ppt at 31 C. Scanning electron micrographs showed that the particles consist of both liquid droplets and agglomerates of small (40-60 nm) solid particles.

This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. Part I describes an experimental and modeling effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where our understanding is not complete. The outdoor experimental facility, which was built to provide the second set of experimental data, consists of a 65 cubic meter teflon smog chamber together with full instrumentation capable of measuring ozone, nitrogen dioxide, nitric oxide, peroxyacetyl nitrate (PAN), carbon monoxide, relative humidity, temperature, aerosol size distributions, and of course toluene and its photooxidation products.

In Part II, we present a theoretical analysis of lumped chemical reaction mechanisms for photochemical smog. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. When applied to mechanisms for photochemical smog, this analysis is shown capable of providing answers to previously inaccessible questions such as the relative contributions of individual organics to photochemical ozone formation. The counter species analysis is applied to six existing mechanisms for photochemical smog to determine why they predict substantially different degrees of emission controls to achieve the same desired air quality under identical conditions. For each mechanism critical areas are identified that when altered bring the predictions of the various mechanisms into much closer agreement. Finally, a new lumped mechanism for photochemical smog is developed and tested against experimental data from two smog chamber facilities. Advantages of this mechanism relative to the existing lumped mechanisms are discussed.

The main goal of this dissertation thesis is to quantify the environmental burden associated with household consumption in the Czech Republic. Emissions of three groups of gases were selected to express the burden on the environment, namely emissions causing climate change, acidification and the formation of photosmog. These emissions arise from the consumption of fuels in households, and they are usually referred to as direct household emissions. Or they arise in the production and distribution of goods and services, and they are usually referred to as indirect household emissions. Although indirect emissions come from combustion in energy production and other industrial processes and agricultural activities, not from households, they are a consequence of household demand for final products. Therefore, such emissions are considered to be a consequence of household consumption. The resulting emission values are given for the average household and households divided into expenditure deciles. Emissions increase with expenditure per household member in total consumption and in individual consumption groups across all deciles. In the case of climate change-related emissions, more than half come from heating (41%) and electricity (21%). For acidification, heating (31%) and food (24%) are the dominant...

The development of effective ozone control strategies requires the use of atmospheric models. There is general agreement within the scientific community that several aspects of the chemistry within these models has yet to be fully elucidated, and is influential in their predictions. The work in this thesis is aimed at trying to determine some of the unknown aspects of the mechanisms of important atmospheric species. Specifically, the gas-phase reactions of two large alkanes, 2,2,4-trimethylpentane and 2,2,5-trimethylhexane are investigated. These two alkanes are present in urban air, and are potential aerosol precursors. The chemistry of several aromatic hydrocarbons are also studied using both theoretical and experimental techniques. The effects of NO2 on the photooxidation of toluene, m-xylene, and p-xylene are examined, and mechanisms of each of these organics are thouroughly evaluated through closely coordinated laboratory work and computer modeling. In addition, product studies of the photooxidation of 1,2,4-trimethylbenzene and m-ethyltoluene are conducted. These studies provide the first identification of ring-retained products from 1,2,4-trimethylbenzene, and ring-retained and fragmented products from m-ethyltoluene. A new indoor experimental reactor was designed to investigate gas-phase reaction kinetics and mechanisms. This new system has served to launch the atmospheric chemistry program at Caltech into a wide variety of new research topics.

碩士
國立雲林科技大學
環境與安全工程技術研究所
88
Abstract This paper presents a study of flow characteristic and photochemical reactivity of ozone precursors using a pilot-scale smog chamber. The interior wall material of chamber is made of Teflon film with the size of 1-m3. The chamber is irradiated by 40 sets of 30-W UV light sources and aluminum external reflectors surrounding the chamber are used to enhance the light intensity evenly. Primarily, the fresh air contained in the smog chamber in the dark (without UV light) was conducted to evaluate the chamber decay and wall effects. Secondly, tracer is used to describe the flow characteristic. Thirdly, the irradiation of compounds with UV light source was performed to assess ozone formation potential of isoprene. Pollutants include NO, NO2, CO, VOCs and carbonyl were monitored in-suit by means of analyzer, GC-MS and HPLC. The decay for NO, NO2 and CO are not significantly. The loss rate of O3 and NMHC are 8 10-5 min-1 and 4 10-4 min-1, respectively. In batch flow characteristic, THC, methane and NMHC are saturated in ninety percents. In continuous flow characteristic, the decay constants (k) of THC, methane and NMHC in min-1 are 457-540, 198-234 and 260-306, respectively. The relationship between isoprene and oxidation production (Methacrolein and Methyl vinyl ketone) at radiation intensity of 12.4 W / cm2 are studied. The yields of Methacrolein (MACR) and Methyl vinyl ketone (MVK) are 2.2: 1 and their OH radicals yield ranges are 0.8-1.6 when NO initial concentrations are 50 ppb. The yields of MACR and MVK are 6-7.8: 1 and their OH radicals yield ranges are 0.7-1.5 when NO initial concentrations are 100 ppb. This study can provide us with a better means for evaluation of photochemical reactions. Furthermore, smog chamber can study the reactivities of different volatile organic compounds (VOCs) from a variety of oxygenated fuel and emission sources.

Thesis (Ph.D.)--York University, 2005. Graduate Programme in Chemistry.
Typescript. Includes bibliographical references (leaves 199-210). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pNR11608

碩士
國立中央大學
環境工程研究所
82
This study utilized the continuous stirred tank reactor (CSTR) with the artificial sunlight to investigate the formation of ammonium sulfate aerosols and the influences imposed by varying the environmental factors chosen as temperature, relative humidity (RH), and light intensity. It isfocused on the aerosol size distribution and productivity through the process of homogeneous heteromolecular nucleation or heterogeneous hetero molecular nucleation. The results showed that the types of aerosols produced were mainly sulfate particles with fewer nitrate species to make the ratios between nitrate and sulfate from 1:2 to 1:8. It was found that the aerosols were accumulated in the size range less than 150nm in the process of homogeneous heteromolecular nucleation and the geometric standard deviations (GSD) were inbetween 1.4 to 1.6 for the initial 15 minutes when the aerosols were generated. The GSD was then increased with time and reached the equalibrium state finally. Under various control conditions (temperatures were at 15, 25 , and 35,degree C RH were at 30, 40, 60,80, and 90%, light intensity at 0.14, 0.18,0.24, and 0.35 mV ), the volume medium diameters of the aerosols produced were from 0.22 to 0.26ug which were similar to what was generated in the gas-to- particle conversion of the flue gas from power plants. In the aerosol formation stage of this work, the principal reaction was firstly proceeded with the homogeneous heteromolecular nucleation and later was followed by the heterogeneous heteromolecular nucleation when the number of particles reached a certain level to be limited by the generation rate. The effects on the two generation mechanisms from the environmental factors showed that high RH and light intensity were generally beneficial to the generation of aerosol particles, whereas the temperature effect was varied.

碩士
國立中興大學
化學工程學系所
104
Liquid crystal display (LCD) was widely applied for smartphone, television, computer screen, car navigation system and so on, because it’s thin and portable. However, LCD still needs improvement, such as power consumption, contrast, motion blur, etc. To achieve better image quality and energy saving, nanoparticles were added into the liquid crystal, reducing the elastic constants and increasing the dielectric constants to shorten the response time and lower the threshold voltage. In this research, firstly, we used polyvinylpyrrolidone (PVP) and 4-cyano-4''-pentylbiphenyl (5CB) as protecting agents and then the colloidal silver particles were synthesized by ultraviolet irradiation of an ethanol solution of silver nitrate (AgNO3) through batch and cycle process respectively; finally, we doped as-fabricated colloidal silver nanoparticles into the 5CB to observe the influence of colloidal silver nanoparticles on the liquid crystal phase by polarized optical microscopy (POM). We applied ultraviolet-visible absorption spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and ion selective electrode (ISE), to identify the growth of colloidal silver nanoparticles, protecting agent''s functional group bonding with silver particles, crystal structure of silver particles, silver particles morphology, elemental composition, and conversion of the silver particles from silver ions, respectively. By means of ultraviolet irradiation with 85mW/cm2 and exposure time of 60min, this study summarized the following significant remarks: (1) The UV-Vis spectrum of the as-prepared silver nanoparticles shown a surface plasmon resonance at 440~450nm; and FTIR confirmed that the silver nanoparticles bonding with protecting agents, PVP colloidal silver nanoparticles C=O was shifted from 1662cm-1 to 1652cm-1, but 5CB colloidal silver nanoparticles got a new absorption peak at 2246cm-1 near group of C≡N. (2) As the ratio of protecting agent to precursor with room temperature in batch process was varied from 1 to 60, mean diameter of PVP and 5CB colloidal silver nanoparticles decreased from 6.4±3.5nm to 4.2±1.3nm and from 4.5±2.4nm to 3.7±0.8nm. (3) When the ratio of protecting agent to precursor with room temperature in cycle process was varied from 1 to 60, average diameter of PVP and 5CB colloidal silver nanoparticles decreased from 5.5±1.8nm to 3.2±0.8nm and from 3.6±0.9nm to 3.3±0.7nm. The size and distribution of synthesized silver particle from the cycle process were smaller and narrower than that from the batch process. This result was attributed to the reacting flow fluid, causing to reduce the exposure time, therefore, the synthesized silver particles were coated with protecting agent immediately and then prevented particles growth. (4) As 5CB added colloidal silver nanoparticles from 0.01wt% to 1wt%, PVP and 5CB colloidal silver nanoparticles caused clearing point of 5CB from 33.5°C to 31.9°C and from 33.7°C to 33.3°C respectively. This difference between PVP and 5CB colloidal silver nanoparticles were because of the particles had a better solubility in isotropic solution and the particles caused the liquid crystal to reduce the directivity respectively.

abstract: Banded iron formations (BIFs) are among the earliest possible indicators for oxidation of the Archean biosphere. However, the origin of BIFs remains debated. Proposed formation mechanisms include oxidation of Fe(II) by O2 (Cloud, 1973), photoferrotrophy (Konhauser et al., 2002), and abiotic UV photooxidation (Braterman et al., 1983; Konhauser et al., 2007). Resolving this debate could help determine whether BIFs are really indicators of O2, biological activity, or neither. To examine the viability of abiotic UV photooxidation of Fe, laboratory experiments were conducted in which Fe-bearing solutions were irradiated with different regions of the ultraviolet (UV) spectrum and Fe oxidation and precipitation were measured. The goal was to revisit previous experiments that obtained conflicting results, and extend these experiments by using a realistic bicarbonate buffered solution and a xenon (Xe) lamp to better match the solar spectrum and light intensity. In experiments reexamining previous work, Fe photooxidation and precipitation was observed. Using a series of wavelength cut-off filters, the reaction was determined not to be caused by light > 345 nm. Experiments using a bicarbonate buffered solution, simulating natural waters, and using unbuffered solutions, as in prior work showed the same wavelength sensitivity. In an experiment with a Xe lamp and realistic concentrations of Archean [Fe(II)], Fe precipitation was observed in hours, demonstrating the ability for photooxidation to occur significantly in a simulated natural setting. These results lead to modeled Fe photooxidation rates of 25 mg Fe cm-2 yr-1—near the low end of published BIF deposition rates, which range from 9 mg Fe cm-2 yr-1 to as high as 254 mg Fe cm-2 yr-1 (Konhauser et al., 2002; Trendall and Blockley, 1970). Because the rates are on the edge and the model has unquantified, favorable assumptions, these results suggest that photooxidation could contribute to, but might not be completely responsible for, large rapidly deposited BIFs such those in the Hamersley Basin. Further work is needed to improve the model and test photooxidation with other solution components. Though possibly unable to fully explain BIFs, UV light has significant oxidizing power, so the importance of photooxidation in the Archean as an environmental process and its impact on paleoredox proxies need to be determined.
Dissertation/Thesis
Masters Thesis Biochemistry 2017

碩士
國立成功大學
環境工程學系
105
Abstract Silver nanoparticles (AgNPs) are a commonly used nanoparticle and have useful characteristics such as excellent antibacterial property. A recent survey indicates that AgNPs are one of the most frequently used (24%) nanomaterials in the consumer products available on the markets across 32 countries. AgNPs once released into the environment could be oxidized to form silver ions which could be bound to dissolved organic matter (DOM). It has been shown that silver ions can be photoreduced to form AgNPs by natural organic matter (NOM) under sunlight conditions. Given that there is a range of DOMs that could be found in the environment, the aim of this thesis is to evaluate the effect of DOM samples isolated from soils, rivers, wastewater effluents, and lakes on the photoreduction of silver ion to form AgNPs. In this study, we used ten different DOM samples isolated from soils, rivers, wastewater effluents, and lakes. We evaluated the characteristics of DOMs including spectral slopes (S275-295, S350-400, and S290-600), slope ratio, SUVA 254, SUVA 280 and E2/E3 in relation to their photoreduction of silver ions to form AgNPs. The result indicated that the sources of DOM significantly affected the formation of AgNPs in aqueous solutions. It was shown that molecular weight, DOM size, and the degree of humification played a role in the photochemical formation of AgNPs. The linear regression result of slope ratio, S275-295 and E2/E3 indicated that DOM samples with higher molecular weights and degree of humification correlated with their greater capabilities to effect photoreduction of silver ions. Keywords : dissolved organic matter sources, formation of AgNPs, silver nanoparticles, UV-visible absorbance.

COS and CS₂ are sulfur compounds that are formed in natural waters. These compounds are also volatile, which leads them move into the atmosphere and serve as critical precursors to sulfate aerosols. Sulfate aerosols are known to counteract global warming by reflecting solar radiation. One major source of COS and CS₂ stems from the ocean. While previous studies have linked COS and CS₂ formation in these waters to the indirect photolysis of organic sulfur compounds, much of the chemistry behind how this occurs remains unclear. This study examined this chemistry by evaluating how different organic sulfur precursors, water quality constituents, and temperature affected COS and CS₂ formation in natural waters.

In the first part of this thesis (chapters 2 and 3), nine natural waters ranging in salinity were spiked with various organic sulfur precursors (e.g. cysteine, cystine, dimethylsulfide (DMS) and methionine) exposed to simulated sunlight over varying exposures. Other water quality conditions including the presence of O₂, CO and temperature were also varied. Results indicated that COS and CS₂ formation increased up to 11× and 4×, respectively, after 12 h of sunlight while diurnal cycling exhibited varied effects. COS and CS₂ formation were also strongly affected by the DOC concentration, organic sulfur precursor type, O₂ concentration, and temperature while salinity differences and CO addition did not play a significant role.

To then specifically evaluate the role of DOM in cleaner matrices, COS and CS₂ formation was examined in synthetic waters (see chapters 4 and 5). In this case, synthetic waters were spiked with different types of DOM isolates ranging from freshwater to ocean water along with either cysteine or DMS and exposed to simulated sunlight for up to 4 h. Surprisingly, CS₂ was not formed under any of the tested conditions, indicating that other water quality constituents, aside from DOM, were responsible for its formation. However, COS formation was observed. Interestingly, COS formation with cysteine was fairly similar for all DOM types, but increasing DOM concentration actually decreased formation. This is likely due to the dual role of DOM on simultaneously forming and quenching the reactive intermediates (RIs). Additional experiments with quenching agents to RIs (e.g. ³DOM* and ·OH) further indicated that ·OH was not involved in COS formation with cysteine but ³DOM* was involved. This result differed with DMS in that ·OH and ³DOM* were both found to be involved. In addition, treating DOM isolates with sodium borohydride (NaBH₄) to reduce ketone/aldehydes to their corresponding alcohols increased COS formation, which implied that the RIs formed by these functional groups in DOM were not involved. The alcohols formed by this process were not likely to act as quenching agents since they have been shown to low in reactivity. Since ketones are known to form high-energy-triplet-states of DOM while quinones are known to form low-energy-triplet-states of DOM, removing ketones from the system further supported the role of low-energy-triplet-states on COS formation. This was initially hypothesized by findings from the testes on DOM types. In the end there are several major research contributions from this thesis. First, cysteine and DMS have different mechanisms for forming COS. Second, adding O₂ decreased COS formation, but it did not stop it completely, which suggests that further research is required to evaluate the role of RI in the presence of O₂. Lastly, considering the low formation yields of COS and CS₂ formation from the organic sulfur precursors tested in this study, it is believed that some other organic sulfur precursors are missing which are likely to generate these compounds to higher levels and this needs to be investigated in future research.

The photochemical generation of several novel quinone methide-type intermediates has been observed upon photolysis of pyridoxine (150-Vitamin B₆) and its derivatives 151 and 152, hydroxybiphenyl alkenes 153 and 154, and hydroxybiphenyl alcohols 159 and 160. Mechanistic investigations, utilizing product, fluorescence and laser flash photolysis studies, have suggested two distinct pathways for the formation of these reactive intermediates, depending upon the functional groups present on the progenitor. Formal excited state intramolecular proton transfer (ESIPT) between the phenol and the alkene led to quinone methides upon irradiation of the hydroxybiphenyl alkenes, while excited state proton transfer (ESPT) to solvent followed by dehydroxylation was responsible for formation of these intermediates from the hydroxybiphenyl alcohols. The quinone methide-type intermediates obtained from the pyridoxine systems arise from formal loss of water, although it is not certain whether this is through ESIPT or ESPT from the phenol at neutral pH. Studies of the photogeneration of quinone methide-type intermediates from the pyridoxine systems are important due to their biological relevance. Formation of such reactive intermediates in vivo may explain some of the toxicological properties associated with the intake of large doses of the vitamin. Irradiation of 150 or 151 in 1:1 CH₃OH/H₂O gave the corresponding methyl ethers (Φp = 0.18 and 0.21, respectively), consistent with formation of quinone methide-type intermediates. Similarly, photolysis in aqueous CH₃CN with ethyl vinyl ether resulted in the regioselective formation of the respective chroman products through [4+2] cycloaddition. LFP spectra pointed to formation of two quinone methide-type intermediates upon irradiation of both 151 and 152 in neutral aqueous solution, only one of which is present at pH 12. Previous studies on m-hydroxystyrene have suggested that m-quinone methide formation occurs via formal ESIPT between the phenol and the alkene, mediated by a bridging water trimer. Studies on 153 and 154 were undertaken to determine whether this solvent-mediated ESIPT can occur over longer distances. The photochemistry of the related hydroxybiphenyl alcohols (159 and 160) was also investigated, as quinone methides have been observed upon photolysis of similar systems. Irradiation of 153 and 154 in 1:1 CH₃CN/H₂O gave photohydration products (Φp = 0.013 and 0.1, respectively) via attack of water on the respective quinone methides. pH studies implicated formal ESEPT in formation of these reactive intermediates. Photolysis of the analogous methyl ethers of the phenols suggested the intermediacy of carbocations in the observed photohydration reaction, as quinone methides cannot be generated in these systems. Hydroxybiphenyl alcohols 159 and 160 yielded the corresponding photomethanolysis products (Φp = 0.04 and 0.22) in aqueous methanol, through attack of CH₃OH on the respective quinone methides. In this case, pH studies indicated that quinone methide formation occurs via ESPT and dehydroxylation. Significant quenching of fluorescence firom the hydroxybiphenyl alkenes with small amounts of added water implied that H₂O is directly involved in reaction from the singlet excited state. Loss of fluorescence firom 154 was found to depend on [H₂O ]³, however, the distance required for ESIPT in these systems is too large to be bridged by a water trimer. As such, the non-linear quenching has been attributed to deprotonation of the phenol by a cluster of one or two water molecules, with concerted protonation at the alkene by another molecule of water not associated with the cluster. Fluorescence quenching of the hydroxybiphenyl alcohols required much larger [H₂O], and implied a different mechanism of reaction, consistent with the proposal of ESPT and dehydroxylation. LFP studies indicated the assistance of water is required for formation of a long-lived transient (600 nm, t = 150 μs) upon irradiation of 153, however, it cannot be definitively assigned to the quinone methide. Although no evidence was found for quinone methide formation in LFP studies of 154 and 160 due to its suspected short lifetime, the respective carbocation (420 nm, t =8.5 μs) has been observed upon irradiation in 2,2,2-trifluoroethanol.
Graduate

碩士
明志科技大學
環境與安全衛生工程系環境工程碩士班
105
The interaction of inorganic iodine compounds, iodide (I-) was reacted with manganese oxide, to investigate the distribution of iodine species at various reaction times, pH values, and with/without illumination. The concentration of inorganic iodide was analyzed by high performance liquid chromatography (HPLC). The Mn2+ ion also was measured using ICP-OES to determine the organic matter used the natural organic matter humic acid of the different molecular weight(100-50KD, 50-10KD, under 10KD) effects on the distribution of iodine species. Iodoform and iodoacetic acid were quantitatively determined using GC-ECD. The total organic iodine was then analyzed using a total halogen analyzer. Inorganic iodine system of the study found that iodine ions and manganese oxide with/without light illumination under acidic conditions, the oxidation of iodide is more significant. Addition of natural organic matter humic acid () of the pyrolusite system showed that the addition of high molecular weight resulted in more organic iodine under acidic condition and the organic iodide production decreased with the pH increasing; and addition of natural organic matter humic acid () of the birnessite system that the addition of high molecular weight resulted in more organic iodine under pH5 and the organic matter iodide production decreased with the pH increasing. However, when the pH over 5 that the organic iodide production can’t decreased with the pH increasing. It could be inferred that manganese oxide provide catalytic solid surface for the oxidation and reduction for iodide, iodate. According to the above study found that the humic acid of high molecular weight contain more ketone functional group, so the tests were carried out using the organic matter of one and two ketone functional groups (sodium pyruvate and 2,4-pentandione). The study showed that addition of 2,4-pentandione of reaction system which oxidizes iodide to about 5%. However, addition of sodium pyruvate which oxidizes iodide to about 40%. It could be inferred from test that the organic matter iodide production increased with the ketone functional group increasing.

碩士
國立雲林科技大學
環境與安全工程系碩士班
89
This research has been conducted in Taipei Tunnel and Fude Tunnel on a freeway in Taipei Municipality. Tunnels are a semi-closed space, the constituent and concentration of pollutants measured in tunnels are reflected the actual source of traffic condition. The collected data on these emission concentrations, for some target pollutants, e.g. carbon monoxide (CO), nitrogen oxide (NOX) and hydrocarbon compounds (HC) can be used to study the composition and characteristics of the vehicle. Additionally, the relationships among different volatile organic compounds (VOCS) can be used to analyze and to assess the characteristic ratios for the various pollutants. The results can be further applied into studying the reaction stage of air mass. By using different photochemical reactivity indication, such as maximum incremental reactivity (MIR)、Propyl-Equivalent concentration (PEC) and photochemical ozone creation potential index (POCP), then the ozone formation potential of primary pollutants can be estimated. The two tunnels where this study is conducted on freeway. They have different environmental factors such as size, air flow rate and traffic condition as well as pollutant emission. Fude Tunnel (1760 m long with 96 m2 cross-sectional area) is larger than Taipei Tunnel (800 m long with 60 m2 cross-sectional area). Additionally, Taipei Tunnel does not have much variation in vehicle composition while Fude tunnel has more variation in vehicle composition during morning hours. Fude tunnel is also observed to have a more percentage of heavy vehicles than Taipei Tunnel. The measured concentrations of CO and NOX near the entrance of Taipei Tunnel (1.8 ppm and 174 ppb, respectively) are higher than those for Fude Tunnel (1.1 ppm and 118 ppb, respectively). Since Fude Tunnel is longer than Taipei Tunnel and has more variation in vehicle composition, the accumulative CO and NOX concentrations measured at the tunnel exit are greater for Fude Tunnel (7.9 ppm and 1728 ppb, respectively) than Taipei Tunnel (6.3 ppm and 780 ppb, respectively). Concentrations of hydrocarbon compounds measured at both tunnel’s entrance and exit are higher in Taipei Tunnel (4.1 ppm and 6.4 ppm, respectively) than Fude Tunnel (3.4 ppm and 4.3 ppm, respectively). For the emission of major pollutants is concerned, the emission factor measured in Taipei Tunnel were 3.8±1.3 for CO, 0.6±0.3 for NOX and 1.6±1.3 for NMHC. In Fude Tunnel, the measured emission factor were 3.4±1.7 for CO, 1.0±0.6 for NOX and 0.3±0.2 for NMHC. Characteristic ratios such as Toluene/Benzene (T/B) and Xylene/Benzene (X/B) can be utilized for studying the characteristic ratios of air mass. The estimated results of T/B and X/B are 2.3 and 1.2 at Taipei Tunnel, 1.5 and 2.5 in Fude Tunnel. Another characteristic ratio, NMHC/NOX, is often used as an important index for evaluating the ozone formation potential. The entrance and exit NMHC/NOX ratios for Taipei Tunnel and Fude Tunnel are 18.2, 6.6 and 7.8, 1.1, indicating that the NOX accumulating rate in the tunnels is higher than the NMHC accumulating rate. This phenomenon is especially obvious for Fude Tunnel, because it has a higher percentage of heavy vehicles powered with diesel engines and leads to a low ratio, greater NOX emission and a faster accumulating rate. Overall, both Taipei and Fude are NOX -limited tunnels. As far as the different photochemical reactivity indices for MIR are concerned, the TVOC (total volatile organic compounds) in Taipei Tunnel and Fude Tunnel are 14.1 and 8.4, respectively (higher in Taipei Tunnel) for PEC, the TVOC ratios are 1.0 and 0.4, respectively (also higher in Taipei Tunnel). For POCP, the TVOC ratios are higher in Fude Tunnel (83) than Taipei Tunnel (69). The difference is caused by the variety of organic compounds detected in these two tunnels and that various indices have different weights on the organic compounds in calculating the indices.

Les aérosols atmosphériques (par exemple les matières particulaires ou PM) sont une source majeure d’incertitude dans les modèles climatiques. Plusieurs études ont démontré que des concentrations élevées de PM réduisent l’espérance de vie. Les aérosols organiques secondaires (Secondary Organic Aerosols en anglais, SOA) sont formés dans l’atmosphère à partir des précurseurs gazeux à travers les réactions chimiques et les SOA représentent des composants majeurs de la masse des PM à l’échelle mondiale. Afin de mieux comprendre les processus chimiques responsables de la formation des SOA, un modèle en 0-D est élaboré pour simuler dynamiquement l’évolution des espèces organiques dans une parcelle d’air qui subit une oxydation photochimique produisant des SOA. Le modèle incorpore des paramètres récemment publiés pour la formation des SOA à partir des composés organiques volatiles (VOCs), ainsi que des composés organiques semi-volatiles et des composés organiques à volatilité intermédiaire (SVOCs et IVOCs). Le modèle est restreint par plusieurs mesures de précurseurs, incluant des mesures récemment développées qui fournissent des contraintes grandement améliorées sur les concentrations des précurseurs, et les prédictions sont comparées par rapport aux mesures des SOA prises au cours de la campagne CalNex. Lorsque les effets des pertes sur les parois des chambres à smog sont considérés pour les rendements des VOCs, la quantité et la vitesse de la formation des SOA dans le modèle sont plus en accord avec les observations. Les résultats de cette étude indiquent que les SVOCs et les IVOCs primaires sont responsables de la majorité (70 à 86 %) de la masse de SOA modélisée, accentuant leur grande contribution en tant que précurseurs des SOA. Cependant, la masse de SOA simulée est sous-estimée à des temps courts d’oxydation lorsque comparée aux données sur le terrain, mais à des temps plus longs, un accord modèle/mesures est observé. Cet écart peut être dû à un ΔIVOC/ΔCO ratio d’émission bas ou une sous-estimation basse des constantes d’oxydations des IVOCs, ce qui met en évidence la nécessité de poursuivre les études sur le terrain et dans les laboratoires de ces composés.
Atmospheric aerosols (i.e. particulate matter or PM) are a major source of uncertainty in climate models. Many studies have also shown that elevated concentrations of PM reduce life expectancies. Secondary organic aerosol (SOA) is formed in the atmosphere from gaseous precursors through chemical reactions and SOA represents a major component of PM mass globally. To better understand the chemical pathways responsible for SOA formation, a box model is designed to simulate dynamically the evolution of organic species in an air parcel as it undergoes photochemical oxidation producing SOA. The model incorporates recently published parameterizations for the formation of SOA from volatile organic compounds (VOCs), as well as from semi-volatile and intermediate-volatility organic compounds (SVOCs and IVOCs). The model is constrained by several measurements of precursors, including recently developed measurements that provide greatly improved constraints on precursor concentrations, and the predications are compared against measurements of SOA taken during the CalNex campaign. When accounting for the effect of chamber wall-losses on VOC yields, the amount and rate of SOA formation in the model is more consistent with observations. The results of this study also indicate that the primary SVOCs and IVOCs are responsible for a majority (70 – 86 %) of the model SOA mass, emphasizing their high contribution as SOA precursors. However, the SOA mass predicted is underestimated at shorter photochemical ages when compared to field measurements, but at longer ages, model/measurement agreement is observed. This bias may be due to low IVOC/CO emissions ratios or low estimated IVOC oxidation rate constants, which highlights the need for further field and laboratory studies of these compounds.