Cette thèse est centrée sur le bupirimate, utilisé dans la région de Souss Massa comme fongicide dans la culture de tomates et propose l'étude de différents aspects liés à son utilisation comme son élimination par voie électrochimique des effluents aqueux d'origine agricole et son impact environnemental dans l'atmosphère. L'étude de surveillance des résidus de pesticides sur les fruits de tomates dans cette région du Maroc proposée dans cette thèse montre que sur les 194 échantillons analysés, il y a présence de bupirimate (10%), endosulfan (7%), bifenthrine (4%), L. cyhalothrine (3%), iprodione (3%), procymidone (3%), deltamethrine (2%), tetradifon (2%), cypermethrine (1%), chlorothalonil (1%), tau-Fluvalinate (1%) et de composés dont les concentrations sont inférieures à la limite de détection (63%). Le bupirimate fortement utilisé, est donc susceptible de se retrouver dans les effluents de lavage agricole, d'où l'intérêt de l'étude de sa dégradation électrochimique en phase aqueuse. Nous avons ainsi mis en évidence que la cinétique de dégradation et les rendements de minéralisation de ce pesticide peuvent être significativement augmentés, par variation des différents paramètres expérimentaux (concentration de l'électrolyte, valeur du courant imposé, et température). Nous avons également déterminé au cours de ce travail que la constante cinétique d'oxydation du pesticide est de l'ordre de 109.10-4 min-1. Les analyses de DCO ont démontré que le taux de minéralisation par électrooxydation dépasse 70 %. Les résultats de l'étude de la minéralisation par la CPG montrent que la vitesse de l'électro-Dégradation du bupirimate est plus élevée que celle obtenue par la DCO. Le rendement d'élimination est de l'ordre de 86%. Ce résultat est confirmé par l'analyse UV. La réactivité hétérogène de bupirimate vis-À-Vis de l'ozone, en phase hétérogène, est également étudiée. Les résultats obtenus montrent que la valeur de la constante cinétique est de 3.07x10-18 cm3.molécules-1.s-1 vis-À-Vis de l'ozone. Cette valeur implique une durée de vie atmosphérique de l'ordre de quelques jours. Les spectres UV et la réactivité homogène vis-À-Vis des radicaux OH du 4-Méthylpyrimidine, de la pyrimidine, du pyrrole, et de la pyridine (produits gazeux attendus de la dégradation des pesticides), ont été déterminés. Les études cinétiques ont été réalisées dans plusieurs chambres atmosphériques. Les résultats obtenus montrent que pour les composés possédant des hétérocycles à 6 atomes, avec 1 ou 2 atomes d'azote, les constantes de vitesse avec le radical OH sont du même ordre de grandeur. La présence des atomes dans le cycle aromatique a un effet désactivant sur la réactivité de ces composés avec les radicaux OH. Par ailleurs, le composé hétérocyclique aromatique à 5 atomes est hautement plus réactif vis-À-Vis les radicaux OH. Les durées de vie atmosphériques de ces composés, déduites de nos mesures cinétiques et spectroscopiques montrent que ces espèces ont tendance à s'éliminer rapidement par les différentes voies photochimiques. / The research study discussed in this thesis concerns the determination of the kinetic rate constants of the electrochemical and heterogeneous degradations of bupirimate. In this study we report the atmospheric fate of four compound heterocyclique by ozone and OH-Radicals using the technique of a simulation chamber coupled to a different analytical system.194 samples tomato samples from an agricultural region of the souss (Agadir, Morrocco) were analyzed for bupirimate (10%) endosulfan (7%), bifenthrine (4%), L. cyhalothrine (3%), iprodione (3%), procymidone (3%), deltamethrine (2%), tetradifon (2%), cypermethrine (1%), chlorothalonil (1%), tau-Fluvalinate (1%) and the concentration of author compounds is less of limits of detection (63%).The electrochemical oxidation of bupirimate is examined by bulk electrolyses at boron doped diamond (BDD) electrode. The influence of operating conditions on the reaction trend is investigated and suitable conditions for oxidative demolition of Bupirimate are individuated. The study also presents the results from bupirimate oxidation at BDD and SnO2 anodes. The COD of bupirimate solution was observed to fall with the first-Order kinetics. We also determined during this work that the constant kinetics of pesticide is about 109.10-4 min-1. In this study, we highlighted that the kinetics of degradation and the outputs of mineralization of bupirimate could be significantly increased, by variation of the various experimental parameters (concentration of electrolyte, value of the imposed current, and concentration of pesticide). The results of mineralization showed that the speed of degradation of the bupirimate by proceeds electrochemical is higher, one has obtains an output of elimination of 84% by the analyses of chromatography.UV spectra and the homogeneous reactivity vis-À-Vis the OH group of 4-Methylpyrimidine, pyrimidine, pyrrole, and pyridine (gaseous products of expected degradation of pesticides), were determined. Kinetic studies were carried out in several atmospheric chambers. The results show that for compounds 6 atoms aromatic ring, with 1 or 2 nitrogen atoms, the rate constants with OH radicals are of the same order of magnitude. The presence of atoms in the aromatic ring has a deactivating effect on the reactivity of these compounds with OH radicals. Moreover, the heterocyclic aromatic having 5 atoms is more highly reactive with OH radicals. The atmospheric lifetimes of these compounds, derived from our spectroscopic and kinetic measurements show that these species tend to be eliminated rapidly by different photochemical ways.

Several phenomena in the middle latitude stratosphere are studied in the thesis. The reanalyses are utilized as a source of data for our study. Different reanalyses are compared each other and with observations and problems of reanalyses are shown. We are interested in connection between ozone, dynamics and other phenomena (Sudden Stratospheric Warmings, solar cycle, NAO etc.) in the stratosphere, mainly from 1979 to present using ERA-Interim, NCEP/NCAR reanalyses or satellite observations. The linear connection between total ozone difference and 100 hPa eddy heat flux is found in winter middle latitudes. Ozone trends in Europe and China are analysed. The meridional and zonal wind is also studied using MERRA reanalysis and model output (CCM SOCOL v3.0). The comparison of geographical distribution of geopotential height and meridional wind is done. Differences between MERRA and CCM SOCOL v3.0 has been observed for geopotential hight and meridional wind for winter season.

The study summerizes methods of ozone AOT40 index estimation from time intergarated passive sampler measurements in forests. Ground-level ozone is a highly phytotoxic atmospheric pollutant. In recent years negative impacts of elevated concentrations of ground-level ozone on vegetation and ecosystems have been studied and atmospheric levels of ozone have been measured. There is a noticeable negative impact of elevated concentrations of ground-level ozone on forests in the Czech Republic, mainly in rural areas that are far away from the emission sources. The AOT40F exposure index is a tool to assess the geographical areas with vegetation potentially at risk due to elevated ground-level ozone concentrations. The AOT40 index is the accumulated hourly exposure during daytime hours above cut-off concentration of 40 ppb, during the growing season. Passive samplers are used for measuring ground-level ozone in high spatial resolution. Passive samplers are easy to use. However this metod provides time intergrated values of pollutant concentrations (1-2 weeks). It is not possible to estimate AOT40 index by using just data of mean ozone concentrations over the sampling period. Three methods were used to estimate the exposure index AOT40F for forests by mean ozone concentrations measured in the Jizerské Hory...

In Sweden, the dominating source for emissions of degradable organic substances to water is the pulp and paper industry. The organic substances increase oxygen consumption in the recipient which subsequently threatens aquatic species. Improved process engineering, process closures and use of external treatments have in recent years drastically lowered the Biological Oxygen Demand (BOD). However, the Chemical Oxygen Demand (COD) has not been reduced to the same extent, as some organic substances are more persistent and must be treated with more advanced techniques. Chemical precipitation, which can bind large parts of the remaining COD into solid matter, making it possible to be removed from the effluent by various separation technologies, contributes to an efficient COD removal. However, the direct operating cost for the treatment is high as large amount of chemicals are used in the process, and large quantities of sludge generated. In the near future EU pulp and paper industry will have to meet new regulatory demands on COD discharges, and pulp mills in Asia, South-America and Oceania will meet stringent discharge demands. It is therefore of interest to review alternative treatments in regards to technical, environmental and economical feasibility in the treatment of pulp and paper mill wastewaters. Much interest has been shown for Advanced Oxidation Processes (AOP), which is why these techniques have been evaluated in this thesis. The first part of the report consists of a literature review where processes with the following oxidants have been reviewed: 1. Ozone (O3); 2. Ozone + Hydrogen peroxide (O3/H2O2); 3. Fenton’s reagent (Fe2+/ H2O2); 4. Ozone + Ultraviolet light (O3/UV); 5. Hydrogen peroxide + Ultraviolet light (H2O2/UV); 6. Photo-Fenton’s reagent (Fe2+/ H2O2/UV); 7. Titanium dioxide + Ultraviolet light (TiO2/UV). Ozone treatment (1) and ozone in combination with hydrogen peroxide (2) were chosen for further experimental studies. The experiments were conducted at Wedecos (Xylem Water Solutions) laboratory in Germany and tested on wastewater from three different Swedish mills: A, B and C. The experimental results indicate that treatment with ozone is an efficient method for elimination of COD from pulp and paper mill wastewaters. A relatively high COD reduction (41 % for Mill A, 31% for Mill B and 53% for Mill C) was achieved for all wastewaters with an applied ozone dosage of 0.2g O3/L, without an appreciable impact on other parameters such as pH, N-tot, NO2-, NO3-, NH4+, P-tot and PO43-. There are indications that the nature of the wastewater has an impact on the COD removal efficiency and that TMP wastewater is easier to oxidize in comparison to wastewater from sulphate mills. The combination with hydrogen peroxide did not show any further COD reduction compared to ozone treatment alone, thus confirming the results Ko et al. showed in their study in 2009. Oxidation with ozone is seen as more environmental alternative in comparison to chemical treatment (precipitation/flocculation) because contaminants in the wastewater are destructed rather than concentrated or transferred into a different phase, which leads to the decrease of COD, colour and toxicity without the need to handle large amounts of sludge. However, a subsequent biological treatment may be necessary for removal of BOD as a BOD increase is registered for all wastewater treated in this study. The costs are on the other hand higher in comparison to chemical treatment even though there are indications of cases when treatment with ozone can be profitable (e.g. if the cost for sludge handling increases in the future, price for chemicals increases and electricity price decreases). There are some uncertainties regarding the system and there is no clear evidence that toxic by-products are not formed. More research must be done and more full-scale installations must be reported before the pulp and paper industry is willing to invest in oxidation technology. / I Sverige, är massa- och pappersindustrin den dominerande utsläppskällan av nedbrytbart organiskt material till vatten. När det organiska materialet når recipienten ökar syreförbrukningen eftersom stora mängder syre erfordras för nedbrytningen av materialet. Detta leder i sin tur till att de vattenlevande organismerna hotas och utsätts för syrebrist. Förbättrad processteknik, ökad processlutning och utbyggnad av extern avloppsvattenrening har under de senaste åren drastiskt sänkt den biokemiska syreförbrukningen (BOD). Däremot har den kemiska syreförbrukningen (COD) inte reducerats i samma utsträckning då delar av det organiska materialet är mer persistent och måste behandlas med mer avancerad teknik. Kemisk fällning kan idag binda stora delar av det kvarvarande COD till fast material som sedan kan avlägsnas via olika separationsmetoder. En stor nackdel med den här typen av rening är att stora mängder kemikalier används som i sin tur genererar stora mängder slam som måste tas om hand, vilket introducerar höga driftkostnader. Inom en snar framtid kommer massa- och pappersbruk inom EU att möta nya regulatoriska krav för COD utsläpp, och bruk i Asien, Sydamerika och Oceanien kommer även de att möta väldigt hårda utsläppskrav. Det är därför av intresse att granska alternativa reningsmetoder och utvärdera dess tekniska, miljömässiga och ekonomiska genomförbarhet vid behandling av avloppsvatten från massa- och pappersbruk. Mycket intresse har visats för Avancerade Oxidationsprocesser (AOP), varför dessa tekniker valts att utvärderas i detta examensarbete. Första delen av rapporten innefattar en litteraturstudie där processer med följande oxidanter studerats: 1. Ozon (O3); 2. Ozon + Väteperoxid (O3/H2O2); 3. Fenton’s reagens (Fe2+/ H2O2); 4. Ozon + Ultraviolett ljus (O3/UV); 5. Väteperoxid + Ultraviolett ljus (H2O2/UV); 6. Foto-Fenton’s reagens (Fe2+/ H2O2/UV); 7. Titaniumdioxid + Ultraviolett ljus (TiO2/UV). Utav dessa valdes ozon behandling (1) och ozon i kombination med väteperoxid (2) för vidare experimentella studier. Behandlingarna har utförts vid Wedecos (Xylem Water Solutions) laboratorium i Tyskland och undersökts på avloppsvatten från tre olika svenska bruk; A , B och C. Experimentella resultat tyder på att ozonering är effektiv behandlingsmetod för reducering av COD i avloppsvatten från massa- och pappersbruk. En relativt hög COD reducering (41% för bruk A, 31% för bruk B, och 53% för bruk C)  uppvisades för samtliga avloppsvatten med en tillämpad ozondosering på 0.2 g O3/L, utan någon märkbar inverkan på andra parametrar så som pH, N-tot, NO2-, NO3-, NH4+, P-tot och PO43-. Det förekommer indikationer om att typ av avloppsvatten har en inverkan på COD reduktionen och att TMP avloppsvatten är lättare att oxidera i jämförelse mot avloppsvatten från sulfatmassabruk. Kombinationen av ozon och väteperoxid uppvisade ingen ytterligare COD reduktion i jämförelse mot ozon som enda oxidant, och bekräftade därmed de resultat Ko et al. uppvisade i sin studie 2009. Ozonering ses som ett miljövänligare alternativ till kemisk rening (fällning/flockning) eftersom föroreningarna i vattnet destrueras istället för att koncentreras, vilket innebär att COD, färg och toxicitet kan minskas utan att stora mängder slam genereras. Dock kan en efterföljande biologisk behandling vara nödvändig för avskiljning av BOD då en BOD ökning uppvisats för samtliga avloppsvatten i denna studie i takt med att COD brutits ned till lättnedbrytbart biologisk material. Kostnaderna är däremot höga i jämförelse mot kemisk fällning även om det förekommer indikationer på fall när behandlingen kan vara lönsam (t ex om slamhanteringskostnaderna blir högre i framtiden, inköpspriset för kemikalier ökar och elpriset sjunker). Det råder vissa tveksamheter gällande systemet och det finns inga konkreta bevis på att toxiska biprodukter inte bildas. Mer forskning måste utföras och fler fullskaliga installationer måste rapporteras och innan massa- och pappersindustrin är villig att investera i oxidationstekniken.

We present the dielectric function of a bcc-In2O3 thin film in the wide spectral range from nearinfrared to vacuum-ultraviolet and for temperatures 10 K–300K, determined by spectroscopic ellipsometry. From the temperature dependence of electronic transition energies, we derive electron-phonon coupling properties and found hints that the direct parabolic band-band transitions involve In-d states. Further we discuss possible excitonic contributions to the dielectric function.

We determined the dielectric function of the alloy system (InxGa1−x)2O3 by spectroscopic ellipsometry in the wide spectral range from 0.5 eV to 8.5 eV and for In contents ranging from x = 0.02 to x = 0.61. The predicted optical transitions for binary, monoclinic β-Ga2O3, and cubic bcc-In2O3 are well reflected by the change of the dielectric functions’ lineshape as a function of the In content. In an intermediate composition range with phase-separated material (x ≈ 0.3…0.4), the lineshape differs considerably, which we assign to the presence of the high-pressure rhombohedral InGaO3-II phase, which we also observe in Raman experiments in this range. By model analysis of the dielectric function, we derived spectra of the refractive index and the absorption coefficient and energy parameters of electronic band-band transitions. We discuss the sub-band gap absorption tail in relation to the influence of the In 4d orbitals on the valence bands. The data presented here provide a basis for a deeper understanding of the electronic properties of this technologically important material system and may be useful for device engineering.

The relative contributions of PM2.5 and ozone precursor emissions to air pollution-related premature mortality modulated by climate change are estimated for the U.S. using sensitivities of air pollutants to precursor emissions and health outcomes for 2001 and 2050. Result suggests that states with high emission rates and significant premature mortality increases induced by PM2.5 will substantially benefit in the future from SO2, anthropogenic NOX and NH3 emissions reductions while states with premature mortality increases induced by O3 will benefit mainly from anthropogenic NOX emissions reduction. Much of the increase in premature mortality expected from climate changeinduced pollutant increases can be offset by targeting a specific precursor emission in most states based on the modeling approach followed here.

Recent reports on the formation of hydrogen peroxide (H$_2$O$_2$) in water microdroplets produced via capillary condensation or pneumatic spraying have garnered significant attention. How covalent bonds in water could break under such conditions challenges our textbook understanding of physical chemistry and the water substance. While there is no definitive answer, it has been speculated that ultrahigh electric fields at the air-water interface are responsible for this chemical transformation. This thesis documents the findings of our exploration of this mystery via a comprehensive experimental investigation of H$_2$O$_2$ formation in (i) water microdroplets condensed on hydrophobic and hydrophilic substrates formed via hot water in the 50–70 ℃ range or ultrasonic humidifier under controlled air composition, and (ii) water microdroplets sprayed over a range of liquid flow-rates, the (shearing) air flow rates, and the air composition. Our glovebox experiments, with controlled gas composition, revealed that no H$_2$O$_2$(aq) was produced in water microdroplets condensed via heating water (detection limit ≥ 0.25 μM), regardless of the droplet size or the substrate wettability. In contrast, water droplets condensed via ultrasonic humidification contained significantly higher (~1 μM) H$_2$O$_2$ concentration. We pinpointed that ultrasonic humidifiers induced cavitation of tiny bubbles in water, which is known to form H$_2$O$_2$(aq) and other reactive species. Next, in the case of sprayed water microdroplets, also, we did not detect H$_2$O$_2$(aq) unless O$_3$(g) was present in the ambient atmosphere. In contrast, water microdroplets (sprayed or condensed) exposed to O$_3$(g) concentration in the range 2–5000 ppb formed 2–100 μM H$_2$O$_2$(aq); increasing the gas–liquid surface area, mixing, and contact duration enhanced the H$_2$O$_2$(aq) concentration. Therefore, we submit that the original reports suffered from experimental artifacts due to the high regional O$_3$(g) giving rise to H$_2$O$_2$(aq), and the air–water interface does not spontaneously produce H$_2$O$_2$(aq). The water surface merely facilitates the O$_3$(g) mass transfer, which then undergoes chemical transformations in the water to form H$_2$O$_2$(aq). Taken together, these findings offer an alternative explanation to the mysterious production of H$_2$O$_2$ in water microdroplets; These findings should also advance our understanding of the implications of this chemistry in natural and applied contexts.

京都大学 / 新制・課程博士 / 博士(地球環境学) / 甲第23558号 / 地環博第215号 / 新制||地環||41(附属図書館) / 京都大学大学院地球環境学舎地球環境学専攻 / (主査)教授 梶井 克純, 准教授 田中 周平, 准教授 上田 佳代 / 学位規則第4条第1項該当 / Doctor of Global Environmental Studies / Kyoto University / DFAM

If released in significant amounts, products formed by reactions between ozone (O3) and volatile organic compounds (VOCs) sorbed on activated carbon (AC) filters could degrade indoor air quality (IAQ). Heterogeneous reactions were investigated in laboratory experiments aimed at characterizing reaction products. Effluent air of AC loaded with limonene and exposed to O 3 (5.8 ppm) yielded unreacted limonene (501 ± 197 μg/m 3), low levels of 4-acetyl-1-methylcyclohexene (AMCH) (20 ± 2 μg/m3), and limonene oxides (25 ± 7 μg/m3). Most of the O3-limonene products remained on the AC, and most (58%) of the limonene remained unreacted on the AC after exposure to a stoichiometric excess of O3 for 48 h. Thus, in addition to known homogenous reactions, O3-limonene reactions occur heterogeneously on AC but to a much lesser extent. However, the fate of 95% of the depleted limonene was not determined; much of the missing portion was attributed to desorption from the AC, but the formation of other secondary indoor air pollutants is possible. VOC-loaded AC air filters exposed to O3 seem unlikely, however, to constitute a significant emission source of reaction products. More studies are necessary to investigate other pollutants, effects of environmental conditions, and VOC releases from AC that may be enhanced by O3 exposure.