Tesis sobre el tema "Composés biogéniques volatiles"
Crea una cita precisa en los estilos APA, MLA, Chicago, Harvard y otros
Consulte los 29 mejores tesis para su investigación sobre el tema "Composés biogéniques volatiles".
Junto a cada fuente en la lista de referencias hay un botón "Agregar a la bibliografía". Pulsa este botón, y generaremos automáticamente la referencia bibliográfica para la obra elegida en el estilo de cita que necesites: APA, MLA, Harvard, Vancouver, Chicago, etc.
También puede descargar el texto completo de la publicación académica en formato pdf y leer en línea su resumen siempre que esté disponible en los metadatos.
Explore tesis sobre una amplia variedad de disciplinas y organice su bibliografía correctamente.
Oumami, Safae. "Impact d'un climat à +2°C sur les émissions des composés biogéniques volatils et sur la qualité de l'air". Electronic Thesis or Diss., Université de Toulouse (2023-....), 2024. http://www.theses.fr/2024TLSEP013.
Texto completoOnce Volatile Organic Compounds (VOCs) are released into the atmosphere, they play a major role in altering its chemistry and composition, consequently impacting the global climate. VOCs released from natural sources account for 90% of the total emitted VOCs, which makes Biogenic Volatile Organic Compounds (BVOCs) a key contributor to the formation of several air pollutants. The influence of BVOCs goes beyond air quality concerns, as they can impact the climate through the formation of aerosols which have a cooling effect and greenhouse gases which have a warming effect, thus effecting the Earth's net radiative forcing. Conversely, climate can effect the release of biogenic species through global warming, land cover and land use change, drought and increasing atmospheric CO2 concentrations. The present work aims to evaluate how BVOCs emission will evolve in a +2°C climate change conditions and how this change will effect air quality in the future.For this purpose, a consequent work was undertaken to couple the SURFEX (SURface Externalisée in French) and MEGAN (Model of Emission of Gases and Aerosols from Nature) models. The coupled model SURFEX-MEGAN will allow the simulation of future emissions of biogenic species along with other important emission key drivers such as leaf area index, soil moisture, soil temperature, etc.The impact of climate change on isoprene emissions was assessed by conducting two global simulations representing present- and future-climate conditions over 2010-2014 and 2046-2050, respectively. The results of this study indicate a global increase of isoprene emissions by 13% (40Tg). This change account for the effect of temperature, solar radiation and atmospheric CO2 concentrations. Temperature have the highest positive effect. Solar radiation have a negative effect as it decreased under the SSP3-7.0 scenario and CO2 concentrations have both positive and negative effects. The former arises from the CO2 fertilization effect and the latter from the CO2 inhibition effect. The SURFEX-MEGAN results were confronted to other projections from CMIP6 models. Most of the models predicted a positive trend in future isoprene emissions. The disparities in model results are attributed to variations in isoprene schemes, resolution, vegetation distribution, and density, but most importantly, each model’s output of temperature and solar radiation differed, despite employing the same SSP scenario.The study of the impact of climate change on future ozone levels showed that the ozone burden will increase by 5% in 2050 compared to 2013. This change is mainly due to the change in human-induced NOx and VOC emissions. Although ozone's sensitivity to isoprene is high, the inclusion of future changes in isoprene emissions have only a marginal effect on global ozone trends. However, this effect is significant at regional and local scales, where ozone is positively and negatively correlated to isoprene trends in high and low NOx regions, respectively. The impact of isoprene emissions in future air quality is most significant when neglecting the inhibitory effect of CO2 on isoprene emissions. In this case air quality was predicted to improve at a global scale and in tropical regions particularly in the future compared to a future-climate scenario with present-climate isoprene emissions
Chrayteh, Mhamad. "Caractérisation physico-chimique de composés organiques volatils biogéniques et de leurs hydrates". Thesis, Lille, 2018. http://www.theses.fr/2018LIL1R054.
Texto completoOur study deal on the physicochemical properties of molecules of atmospheric interest in the gas phase, in particular the microsolvation process, which could be useful to better understand what leads to the formation of secondary organic aerosols. We studied the mechanism of hydration of several oxidation products of monoterpenes, which include myrtenal and perillaldehyde, which are two unsaturated aldehydes of close structures, with the verbenone and the fenchone, which are two ketones. The structures of many conformers (up to 3 molecules of water bound to molecules) have been optimized by quantum chemistry calculations at MP2 / 6-311++G(d,p) and B3LYP-D3BJ / def2-TZVP levels of theory. The hydrates cohesion is done thanks to hydrogen bonds and Van der Waals interactions. We were able to evidence of the existence of many of them by supersonic jet mircowave spectroscopy in the range of frequencies 2 - 20 GHz and determine their experimental structure. For the myrtenal, we recorded and analyzed the pure rotation spectra, as well as those of isotopologists in natural abundance (13C and 18O ). With the support of quantum chemistry calculations, we have determined its molecular structure in the gas phase. Regarding the hydrates of myrtenal, we analyzed the spectra of 2 mono-, 2 di- and a trihydrate, while for perillaldehyde 4 mono- and 2 dihydrates are characterized. With ketones, we analyzed the spectra of 2 mono-, 2 di- and 1 trihydrate of verbenone, while for the microhydration of fenchone, we characterized2 mono-, 2 di- and 3 trihydrates. In order to confirm the structure of the complexes, we used water enriched with oxygen 18, which allowed us through the constants of rotation of the isotopomers to calculate the structure of the detected hydrates by determining the position of the oxygen atoms by calculating their substitution coordinates, as well an effective structure limited to the arrangement of water molecules around the substrate
Chrayteh, Mhamad. "Caractérisation physico-chimique de composés organiques volatils biogéniques et de leurs hydrates". Electronic Thesis or Diss., Université de Lille (2018-2021), 2018. http://www.theses.fr/2018LILUR054.
Texto completoOur study deal on the physicochemical properties of molecules of atmospheric interest in the gas phase, in particular the microsolvation process, which could be useful to better understand what leads to the formation of secondary organic aerosols. We studied the mechanism of hydration of several oxidation products of monoterpenes, which include myrtenal and perillaldehyde, which are two unsaturated aldehydes of close structures, with the verbenone and the fenchone, which are two ketones. The structures of many conformers (up to 3 molecules of water bound to molecules) have been optimized by quantum chemistry calculations at MP2 / 6-311++G(d,p) and B3LYP-D3BJ / def2-TZVP levels of theory. The hydrates cohesion is done thanks to hydrogen bonds and Van der Waals interactions. We were able to evidence of the existence of many of them by supersonic jet mircowave spectroscopy in the range of frequencies 2 - 20 GHz and determine their experimental structure. For the myrtenal, we recorded and analyzed the pure rotation spectra, as well as those of isotopologists in natural abundance (13C and 18O ). With the support of quantum chemistry calculations, we have determined its molecular structure in the gas phase. Regarding the hydrates of myrtenal, we analyzed the spectra of 2 mono-, 2 di- and a trihydrate, while for perillaldehyde 4 mono- and 2 dihydrates are characterized. With ketones, we analyzed the spectra of 2 mono-, 2 di- and 1 trihydrate of verbenone, while for the microhydration of fenchone, we characterized2 mono-, 2 di- and 3 trihydrates. In order to confirm the structure of the complexes, we used water enriched with oxygen 18, which allowed us through the constants of rotation of the isotopomers to calculate the structure of the detected hydrates by determining the position of the oxygen atoms by calculating their substitution coordinates, as well an effective structure limited to the arrangement of water molecules around the substrate
Renard, Pascal. "Photochimie et oligomérisation des composés organiques biogéniques en phase aqueuse atmosphérique". Thesis, Aix-Marseille, 2014. http://www.theses.fr/2014AIXM4748.
Texto completoAir pollution caused by secondary organic aerosol (SOA) is one of the major challenges of this century. We focus this thesis on SOA , through an innovative approach, i.e. multiphase photochemistry.The photochemical reactor allows to simulate in laboratory, the atmospheric aqueous phase oxidation of biogenic volatile organic compounds (BVOC) and in particular, methyl vinyl ketone (MVK), and thus, to study SOA.We study the reactivity of MVK in the presence of ●OH and its ability to oligomerize under various initial concentrations of oxygen, MVK and ●OH. A wide analytical strategy based on liquid chromatography-mass spectrometry is used to identify the reaction products, and establish a chemical mechanism. We focus on these oligomers systems, formation, yield and aging. Collected data are used as inputs to a multiphase box model to explore the sensitivity of oligomerization to the variations of physical and chemical atmospheric parameters. The photochemistry of pyruvic acid generates radical chemistry and initiates MVK oligomerization. We closely compare this reaction to MVK ●OH oxidation. Then, we measure the surface activity of both systems. The ability of oligomers to partition to the interface could affect the climate. Finally, we used ion mobility - mass spectrometry to observe ●OH co-oligomerization of a mixture of organic compounds most representative of the atmosphere.Atmospheric oligomerization implies (i) a minimal concentration of precursors that could be reached in wet aerosol via the co-oligomerization; (ii) a reactivity in competition with the addition of the dissolved oxygen, whose the atmospheric relevance remains to be explored
Mermet, Kenneth. "Caractérisation physico-chimique et réactivité d'espèces biogéniques sur un site de mesure en forêt des Landes : impacts sur la qualité de l'air". Thesis, Bordeaux, 2019. http://www.theses.fr/2019BORD0363.
Texto completoAt the global scale, forests are the largest emitters of VOCs. Once released into the atmosphere, VOCs will be fastly oxidized to oxygenated compounds. Depending on their volatility and reactivity, these oxidation products may themselves be re-oxidized, remain in the gas phase and/or be transferred to the particulate phase to form secondary organic aerosols (SOAs). This thesis aimed to better characterize biogenic VOC concentrations (BVOCs) and more especially their reactivity with atmospheric oxidants (i.e. the hydroxyl radical (OH), ozone (O3) and the nitrate radical (NO3)), in order to identify the main precursors of SOA formation within a maritime pine forest. The metrological development of a gas chromatographic analyzer has made possible the online and specified measurement of 20 BVOCs including isoprene, α- and β-pinene, 2 and Δ3-carene, α- and γ-terpinene, linalool, camphene, etc. This analyzer and some other instruments for the measurement of trace gases and aerosols were used during the summer of 2017 as part of the LANDEX intensive campaign in one of the largest pine forests in Europe (> 95% Pinus pinaster) located in the southwest of France. A principal component analysis of meteorological data and BVOC measurements showed that BVOC concentrations were mainly dependent on their emissions, the ambient temperature, the solar irradiation and the atmospheric stability. The analysis of the reactivity of the identified VOCs with the main atmospheric oxidants has helped to show the contrast between processes involving OH radical during daytime and ozonolysis at night. Finally, it was determined that the ozonolysis of β-caryophyllene, α-pinene, myrcene, and linalool, and the OH initiated oxidation of isoprene were the main sources of oxidation products, as SOA precursors, within the Landes forest
Baghi, Romain. "Emissions biogéniques de composés organiques volatils en région méditerranéenne - développement instrumental, mesures et modélisation". Phd thesis, Université Paul Sabatier - Toulouse III, 2013. http://tel.archives-ouvertes.fr/tel-00873143.
Texto completoBaghi, Romain. "Émissions biogéniques de composés organiques volatils en région méditerranéenne : développement instrumental, mesures et modélisation". Toulouse 3, 2013. http://thesesups.ups-tlse.fr/2248/.
Texto completoVolatile Organic Compounds (VOC) play an important role in atmospheric chemistry and are involved in the formation of secondary atmospheric pollutants as ozone and organic aerosols. Biogenic emissions of volatile organic compounds are tenfold greater than anthropogenic emissions on a global scale but their characterization remains uncertain regionally. Advances in atmospheric chemistry modeling rely on better emission inventory which needs in situ flux measurement. This work focuses on biogenic VOC emissions from Mediterranean vegetation in the frame of ChArMEx (Chemistry and Aerosol Mediterranean Experiment) that aims to concentrate scientific effort to study atmospheric chemistry and aerosols in the Mediterranean region. The Eddy Covariance (EC) method allows direct measurement of trace gas exchange between the surface and the atmosphere. EC is a reference method for flux measurement but is adapted to only a limited number of trace gas species because it requires simultaneous fast measurement (~ 0. 1 s) of the species concentration and vertical wind speed. In order to broaden the range of applicability of this method, several other methods derived from EC have been proposed. Among these, the Disjunct Eddy Covariance (DEC) method relaxes the constraint on fast concentration measurement while preserving good accuracy on the flux calculation. In the frame of this PhD work, a sampling system dedicated to the DEC method for VOC flux measurement was developed. This device called MEDEE (Mesures par Échantillonnage Disjoint des Échanges d'Espèces en trace) relies on a novel technology that allows the rapid capture of an air parcel and insures its transfer at a constant pressure towards an on-line analyzer. It is composed of two mechanical syringes moved by electric actuators with an alternated functioning to supply continuously the analyzer. Three solenoid valves are installed on each reservoir to drive the sample flow depending on the cycle. A micro controller chip is used to give the rhythm of the whole system with millisecond accuracy. This sampling system has been built in chemically inert materials to avoid sample contamination or destruction; this makes MEDEE fully compatible with reactive species. MEDEE has been tested and validated on ground and aboard an aircraft, during two field campaigns. It was coupled to a fast isoprene sensor for BVOC flux measurements during two field campaigns in summers 2010 and 2011 above a downy oak forest. A Neural Network (NN) approach has been used to derive a biogenic VOC emission algorithm from these canopy level measured fluxes and concurrent environmental parameters. Isoprene emission modeling has been validated for the observed environmental conditions. In the future, such emission parameterization will be implemented in a coupled chemistry-dynamics model to study the impact of biogenic VOC emissions on air quality
Bernard, François. "Etude du devenir atmosphérique de composés organiques volatils biogéniques : réactions avec OH, O3 et NO2". Phd thesis, Université d'Orléans, 2009. http://tel.archives-ouvertes.fr/tel-00517365.
Texto completoGonzaga, Gomez Lais. "Échange de composés volatils biogéniques entre l'atmosphère et les cultures de blé, maïs et colza". Electronic Thesis or Diss., Sorbonne université, 2020. http://www.theses.fr/2020SORUS319.
Texto completoVolatile Organic Compounds (VOC) play a key role in atmospheric chemistry influencing climate and air quality. Vegetation is the main source of VOC, accounting for 90% of biogenic emissions (BVOC). Agricultural crops in Europe are estimated to contribute 27% of total BVOC emissions but remain poorly studied. In this work, we study the exchange of BVOC by wheat, rapeseed and maize, the main agricultural species in France in terms of cultivated area. The fluxes were measured in the field at the plant level with dynamic automated chambers coupled to a PTR-Qi-Tof-MS spectrometer. Fluxes of up to 997 compounds could be measured with this highly sensitive instrument. Chapter 1 presents a review of BVOC emission mechanisms, flux measurement methods, experimental results on BVOC exchanges in agricultural systems, and mathematical models of emissions. Chapter 2 describes the measurement site and the experimental setup. Chapter 3 presents BVOC fluxes measured during one week for each species. Emissions were dominated by methanol (55-85% of total emissions) followed by acetone and acetaldehyde. The 10 most emitted compounds excluding methanol accounted for more than 50% of total emissions and the 100 most emitted compounds accounted for more than 90%. The measured fluxes showed little intra-species variation but large inter-species variations with total net fluxes of 0.11±0.02 µg_BVOC g_DW^(-1) h^(-1) for maize, 1.5±0.7 µg_COVB g_MS^(-1) h^(-1) for wheat, and 9.1±2.4 µg_COVB g_MS^(-1) h^(-1) for rapeseed. Finally, standard emission factors for isoprene and monoterpenes were evaluated for each species, constituting the first known estimates for rapeseed. Chapter 4 examines the influence of developmental stages, and particularly of senescence, on BVOC emissions from wheat. We report a doubling of total emissions during senescence compared to maturation, with, in particular, an increase in the contribution of acetaldehyde (1.6% of total emissions during maturation and 9.7% during senescence) and acetic acid (0.7% during maturation and 2.7% during senescence). In Chapter 5 the main parameters of the MEGAN 2.1 model are estimated for the three species and the fluxes of six main compounds measured for rapeseed at the plant level by the dynamic chambers are compared with measurements by Eddy Covariance at the ecosystem level in order to evaluate the representativeness of chamber measurement. This work shows the heterogeneity of BVOC exchanges by agricultural plants and the data generated should contribute to the improvement of emission models
Dutaur, Laure. "Caractérisation des sources biogéniques des composés organiques volatils contribuant à la pollution photochimique dans le bassin méditerranéen". Toulouse, INPT, 1996. http://www.theses.fr/1996INPT024G.
Texto completoKalogridis, Athina-Cerise. "Caractérisation des composés organiques volatils en région méditerranéenne". Thesis, Paris 11, 2014. http://www.theses.fr/2014PA112314/document.
Texto completoVolatile organic compounds (VOCs) are key components in atmospheric chemistry. They participate in photochemical reactions in the lower atmosphere and thus play a major role in the formation of tropospheric ozone and secondary organic aerosols. Biogenic VOCs (BVOCs) constitute approximately 90% of global VOC emissions. In the Mediterranean region, the emissions and reactivity of BVOCs are enhanced due to high temperatures and sunny conditions. In this context, this work proposes, through intensive field campaigns, the experimental characterization of BVOCs and their oxidation products in two rural sites where the vegetation is representative of the Mediterranean region. Within the framework of the CANOPEE program (ANR-JCJC 2011-2014) an intensive field campaign took place at the Oak Observatory of the Observatoire de Haute Provence (O3HP). Measurements of concentrations and emission fluxes were carried out in order to quantify the export of BVOC off the canopy and study in-Canopy processes. High concentrations of isoprene were measured with daily maximum ambient concentrations ranging between 2-16 ppbv inside the forest. According to the emission factor of 7.2 mg m-2 h-1 determined, downy oak forest of the O3HP is one of the strongest emitters of isoprene worldwide. Evidence of direct emission of methanol was also found exhibiting an average emission rate equal to 0.3 2 mg m-2 h-1. One of the strengths of this work consisted in the study of transport and intra-Canopy chemistry. In-Canopy chemical oxidation of isoprene was found to be weak and did not seem to have a significant impact on isoprene concentrations and fluxes above the canopy. The second field campaign is part of the ChArMEx (Chemistry-Aerosol Mediterranean Experiment) program. It took place on the remote site of Cap Corse, characterized by a strong diversity of plant species. The rich dataset obtained allowed the quantification and speciation of many BVOCs. A great contrast in the signature emissions was observed between the two study sites. Thus, while isoprene is responsible for over 90% of BVOCs in terms of concentrations at the O3HP, it represents only 35% of their total concentrations in Cap Corse. The remaining 65% are composed of many monoterpenes. These results have also highlighted the rapid chemistry of BVOCs and the importance of their contribution to the formation of secondary oxygenated compounds under intense photochemistry conditions, typical of the summertime in the Mediterranean basin. Biogenic BVOCs represented the dominant hydroxyl radicals sink at the O3HP as well as in Cap Corse. In the presence of NOx, the potential of the measured BVOCs to produce ozone has been estimated at about 10 ppbv on average
Zannoni, Nora. "OH reactivity measurements in the Mediterranean region". Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS163/document.
Texto completoThe total OH reactivity is the total loss rate of the hydroxyl radical with the reactive gases in ambient air. It represents the measure of the total loading of reactants in a given environment.Here we present an experimental work focusing on the technical improvements of the Comparative Reactivity Method to measure the OH reactivity on the field and field measurements of OH reactivity at two targeted sites in the Mediterranean basin.The measured OH reactivity was high at both sites. At a receptor site in Corsica (France) during summer 2013, we observed that the OH reactivity was maximum 17 s-1, on average 5.5 s-1 and during one week only 50% was explained by the complementary measurements in the gas phase.At a forest of downy oak trees, high isoprene emitters, in the south of France, we observed that the OH reactivity was maximum 69 s-1, in agreement with the reactivity calculated from the measurements of reactive gases only during daytime.This thesis work highlights that: (i) the Mediterranean basin is a strong emitter of reactive gases, (ii) the reactivity measured in these two sites in the Mediterranean was strongly impacted by the biogenic emissions, (iii) there are still many unknowns associated to measures of biogenic volatiles primary emitted and secondary produced. Such unknowns might be reduced in the future by coupling the measurement of the OH reactivity with plants enclosures and chambers studies as well as modelling approaches
Duncianu, Marius. "Réacteur à écoulement pour l’étude de la formation des aérosols organiques secondaires par ozonolyse de composés organiques volatils : développement analytique, validation cinétique et ozonolyse d’un composé biogénique". Thesis, Lille 1, 2012. http://www.theses.fr/2012LIL10039/document.
Texto completoA steady flow reactor equipped with a mobile injection head was developed at the Chemistry and Environment Department, Ecole des Mines de Douai, to better understand the formation processes of secondary organic aerosols (SOA) following the gas phase oxidation of certain species particularly reactive and/or abundant in the atmosphere. In contrast to atmospheric simulation chambers the flow reactor allows to observe in stationary conditions the product formation in the early stages of the reaction at ambient pressure and temperature.The foremost part of this work was to characterize the reactor flow, and to develop and optimize the methods used for the gas phase analysis. In a second stage a kinetic study of the ozonolysis of methylated pentenes and α-pinene was performed to validate the system. The rate coefficients were determined in pseudo first order conditions with excess alkene and showed a good agreement with literature values. The expected oxidation pathways were identified and quantified for one alkene (in good agreement with the only study available), and a nonoxidized intermediate coming from the rearrangement of a Criegee biradical, has been found for short reaction times. Finally, the SOA formation from α-pinene ozonolysis was investigated with simultaneous characterization of the gas phase concentrations of reactants and products (by ozone analyzer and TD/GC/FID-MS), of the particle size distribution (by SMPS and HR-ToF-AMS), and of the average chemical composition of particles (HR-ToF-AMS)
Duncianu, Marius. "Réacteur à écoulement pour l’étude de la formation des aérosols organiques secondaires par ozonolyse de composés organiques volatils : développement analytique, validation cinétique et ozonolyse d’un composé biogénique". Electronic Thesis or Diss., Lille 1, 2012. http://www.theses.fr/2012LIL10039.
Texto completoA steady flow reactor equipped with a mobile injection head was developed at the Chemistry and Environment Department, Ecole des Mines de Douai, to better understand the formation processes of secondary organic aerosols (SOA) following the gas phase oxidation of certain species particularly reactive and/or abundant in the atmosphere. In contrast to atmospheric simulation chambers the flow reactor allows to observe in stationary conditions the product formation in the early stages of the reaction at ambient pressure and temperature.The foremost part of this work was to characterize the reactor flow, and to develop and optimize the methods used for the gas phase analysis. In a second stage a kinetic study of the ozonolysis of methylated pentenes and α-pinene was performed to validate the system. The rate coefficients were determined in pseudo first order conditions with excess alkene and showed a good agreement with literature values. The expected oxidation pathways were identified and quantified for one alkene (in good agreement with the only study available), and a nonoxidized intermediate coming from the rearrangement of a Criegee biradical, has been found for short reaction times. Finally, the SOA formation from α-pinene ozonolysis was investigated with simultaneous characterization of the gas phase concentrations of reactants and products (by ozone analyzer and TD/GC/FID-MS), of the particle size distribution (by SMPS and HR-ToF-AMS), and of the average chemical composition of particles (HR-ToF-AMS)
Luchetta, Laurent. "Caractérisation et quantification dans la basse atmosphère de composés organiques volatils biogéniques et anthropiques contribuant à la pollution de l'air". Toulouse, INPT, 1999. http://www.theses.fr/1999INPT015H.
Texto completoClément, Bruno. "Dispositif automatique de dosage des composés organiques volatils (COV) biogéniques. Application à l'étude des terpènes atmosphèriques au cours de la campagne BIATEX/EUROTRAC". Toulouse, INPT, 1990. http://www.theses.fr/1990INPT010G.
Texto completoCarrasco, Nathalie. "Etude, en atmosphère simulée, de la réactivité de trois composés biotiques d' impact atmosphérique majeur : l' isoprène, le MBO et le sabinène". Paris 7, 2005. https://tel.archives-ouvertes.fr/tel-00011147.
Texto completoDetournay, Anaïs. "Etude de COV oxygénés et biogéniques en milieu rural : du développement métrologique à l’évaluation de l’impact sur la chimie atmosphérique". Thesis, Lille 1, 2011. http://www.theses.fr/2011LIL10139/document.
Texto completoVolatile Organic Compounds (VOC) constitutes a heterogeneous compounds class, which play a significant part in atmospheric chemistry, impacting climate, environment and health. Recent studies have suggested the implication of biogenic and oxygenated VOCs in the formation processes of secondary species, such as ozone or Secondary Organic Aerosols. Little is known about those compounds, well represented in remote areas; mostly toward their ambient levels and diurnal and seasonal evolutions. This thesis’ objectives are to improve the current knowledge about their behavior in remote areas, for a better understanding of their part in atmospheric chemistry. The method adopted consisted in metrological development and field campaigns, to constitute a representative data base. Measurement methods were optimized and/or developed for the measure of: 54 NMHCs from C2 to C10, using préconcentration/thermodesorption coupled with GC/FID on-line analysis; 21 carbonyl compounds from C1 to C6, by chemical derivatization and chemical desorption coupled with HPLC/UV analysis; and 5 aromatic compounds, 6 aldehydes from C6 to C11, 6 monoterpenes and 6 alkanes from C9 to C16; by preconcentration coupled with thermodesorption and GC/FID-MS analysis. Those methods were used during two measurement campaigns, in March and June 2009, at the remote site of Peyrusse-Vieille (Gers, France). They permitted to collect an important database, whose analysis allowed determining the target compounds’ ambient levels, temporal variations, and the parameters inducing these observations. A thorough analysis then underlined the part transport mechanisms and importance of biogenic species in remote areas
Kalalian, Carmen. "Réactivité atmosphérique des composés organiques volatils oxygénés biogéniques (aldéhydes et alcools insaturés). Etudes cinétiques de la réaction entre les radicaux peroxyles et le radical nitrate". Thesis, Reims, 2018. http://www.theses.fr/2018REIMS023/document.
Texto completoBiogenic volatile organic compounds (BVOC) account for 90% of VOC emissions in the atmosphere. These VOCs can be removed from the atmosphere by reaction with photo-oxidants (OH, NO3, Cl and O3) as well as by photolysis. All these processes are governed by a chain mechanism whose carriers are mainly free radicals such as peroxy radicals RO2. Hence the importance of characterizing the reactivity of these species that play a key role in the atmospheric degradation of VOCs. In this context, this thesis focuses on the determination of the temperature dependent kinetic data as well as the mechanism of the ozonolysis reaction and the UV absorption spectra along the photolysis of six unsaturated oxygenated VOCs (trans- 2-pentenal, trans-2-hexenal, 2-methyl-2-pentenal, 1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol). Likewise, the temperature dependent kinetic parameters of the reaction of three peroxy radicals (CH3OCH2O2, CH3C(O)CH2O2 et (CH3)2C(OH)CH2O2) with nitrate radicals were also determined. Three experimental setups coupled to treatment methods were used to extract these data: an atmospheric simulation chamber coupled to both a Fourier-transform infrared spectroscopy (FTIR) and a gas chromatography connected to a mass spectrometry (GC/MS), a device for measuring UV-Visible spectra and a laser photolysis coupled with UV-visible spectrometry and laser diode spectroscopy. The kinetic parameters were used to estimate the atmospheric lifetimes of the studied species. While the mechanistic data were used to establish their ozonolysis mechanisms. All the collected data enrich kinetic, mechanistic and spectroscopic databases, improving atmospheric models specially those involving VOCs
Grira, Asma. "Atmospheric degradation of oxygenated Volatile Organic Compounds". Thesis, Rennes 1, 2021. http://www.theses.fr/2021REN1S017.
Texto completoOxygenated Volatile Organic Compounds (OVOCs), mainly released from biogenic sources, play a major role in atmospheric chemistry, climate change, environment, and health. These emissions have been recently shown to increase in the case of biotic and/or abiotic stresses. Biogenic OVOCs may undergo a wide variety of reactions, both chemical and photolytic, and they contribute in the formation of Secondary Organic Aerosols (SOAs). These compounds have been detected in various areas, but little is known about their degradation processes under tropospheric conditions. Understanding the oxidation mechanisms of these species is of fundamental interest and yields crucial data for atmospheric models used by policymakers in formulating and deciding strategies for improving air quality. This dissertation aims to improve the current knowledge of those OVOCs behaviors to better understand their impact on atmospheric chemistry. This work reports a detailed study of the atmospheric degradation of C5-C7 unsaturated aldehydes and C5-C8 unsaturated alcohols by ozone, Cl atom, and OH radical. The main objectives were to better understand the reaction mechanism and to feature the SOA formation potential. To achieve these objectives, we focused on four topics: (i) determination of IR and UV spectrum of C5-C7 unsaturated aldehydes, (ii) determination of the rate constant for the studied OVOCs + Oxidant at room temperature, (iii) identification and quantification of the gas-phase products, (iv) determination of the SOA yields. The product studies were investigated both with and without adding an OH radical scavenger. Experiments were performed in eight different static (chambers) or dynamic (flow) reactors, and various analytical techniques were used to investigate the reaction products (FTIR, GC-FID/MS, SPME-GC/MS, HPLC, PTR-ToF-MS, SIFT-MS, PLP-LIF) and SOA formation (SMPS, FMPS)
Denis, Isabelle. "Photodégradation des composés organiques volatils biogéniques dans l'atmosphère : étude de la réactivité du (beta)-pinène vis à vis des radicaux hydroxyles ; cas de la réactivité en milieu hétérogène". Université Joseph Fourier (Grenoble), 1995. http://www.theses.fr/1995GRE10129.
Texto completoBsaibes, Sandy. "Characterization of biogenic volatile organic compounds (BVOCs) and their OH reactivity in various agro-ecosystems". Electronic Thesis or Diss., Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLV093.
Texto completoThe hydroxyl radical OH is the most powerful oxidant in the troposphere, however, characterizing its sinks remains a challenge. One important OH sink, is the oxidation of volatile organic compounds (VOCs), mainly released from biogenic sources, on the global scale. VOCs include a wide variety of chemical species with different lifetimes towards OH. Measuring OH reactivity is a useful tool to evaluate the loading in reactive species and to estimate the amplitude of unmeasured/unidentified compounds. In this context, this PhD work aimed to build and optimize a CRM or Comparative Reactivity method instrument for OH reactivity measurements. Afterwards, the CRM was deployed in a forest and an agricultural ecosystem. OH reactivity in a maritime pine forest showed maxima during night, reaching 99 s-1 inside the canopy, among the highest in forest environments. Relatively lower levels (max 20-30 s-1 at mid-day), were recorded from a dynamic chamber, during the blooming season of a rapeseed field. In these ecosystems, a difference was obtained between measured and calculated OH reactivity from measured compounds. It highlights the presence of a missing fraction of unmeasured primary and secondary compounds. These experiments demonstrate the importance of a detailed information on monoterpenes chemical speciation. In this perspective, a FastGC/PTR-MS system was optimized and deployed in a green oak forest. It allowed to monitor, with a fine time resolution, diurnal cyles of the main monoterpenes, which emissions are dependent on the tree type and on solar radiation
Lavoir, Anne-Violette. "Effet de la limitation en eau sur les émissions de composés organiques volatils chez le chêne vert (Quercus ilex) : approches expérimentales et modélisatrices à différentes échelles spatiales et temporelles". Montpellier 2, 2008. http://www.theses.fr/2008MON20070.
Texto completoBiogenic Volatile Organic Compounds (BVOC) are primarily emitted from plants and consist mainly of isoprenoid compounds. They influence the oxidative capacity and the radiative properties of the troposphere. BVOC emissions are diffuse (sources are represented by all natural landscapes), and variable because of the numerous environmental factors, particularly light and temperature that modulate the emission source strength. In Mediterranean regions, water availability represents a major environmental constraint for vegetation, which causes severe drought during summer and determines the annual pattern of the plant activity together with light and temperature. The objective of this thesis was to characterise the effect of water limitations on biogenic emissions at various temporal and spatial scales on the model species Quercus ilex. In an experimental approach, a strong decrease of the foliar emissions was observed during drought events, in association with dissociation of the temperature and light control on the emissions. The up-scaling of the experimental approach with modelling tools allowed to integrate this negative effect at larger spatial scales (namely canopy and region). As a result, emissions were largely overestimated if the water stress effect was not taken into account. The simulation obtained at regional scale is explicit and quantitative, thus could be used to predict biogenic emissions in the on-going global change context
Fayad, Layal. "Caractérisation de la nouvelle chambre de simulation atmosphérique CHARME et étude de la réaction d’ozonolyse d’un COV biogénique, le γ-terpinène". Thesis, Littoral, 2019. https://documents.univ-littoral.fr/access/content/group/50b76a52-4e4b-4ade-a198-f84bc4e1bc3c/BULCO/Th%C3%A8ses/LPCA/These_Fayad_Layal.pdf.
Texto completoThe study of atmospheric processes is among the central topics of current environmental research. The most direct and significant way to investigate the transformation of pollutants and the formation of aerosols in the atmosphere, is to simulate these processes under controlled and simplified conditions. In this regard, a new simulation chamber, CHARME (CHamber for the Atmospheric Reactivity and the Metrology of the Environment) has been designed in the Laboratory of Physico-Chemistry of the Atmosphere (LPCA) in the University of Littoral Côte d’Opale (ULCO). CHAE is also dedicated to the development and validation of new spectroscopic approaches for the metrology of atmospheric species including gases, particles and radicals.The first aim of this research was to characterize all the technical, physical and chemical parameters of this new chamber and to optimize the methods for studying the atmospheric reactivity of volatile organic compounds (VOCs) and simulating the formation of secondary organic aerosols (SOA). The results of numerous experiments and tests show that CHARME is a convenient tool to reproduce chemical reactions occurring in the troposphere. The second research objective was to investigate the reaction of the biogenic VOC, γ-terpinene, with ozone. The rate coefficient at (294 ± 2) K and atmospheric pressure was determined and the gas-phase oxidation products were identified. The physical state and hygroscopicity of the secondary organic aerosols was also studied. To our knowledge, this work represents the first study on SOA formation from the ozonolysis of γ-terpinene
Fouqueau, Axel. "Réactivité des terpènes avec le radical nitrate : études cinétique et mécanistique en chambres de simulation atmosphérique". Thesis, Paris Est, 2019. http://www.theses.fr/2019PESC0015.
Texto completoBiogenic volatile organic compounds (BVOC) are strongly emitted by forests and crops in the atmosphere. They are very reactive towards nitrate radical, the main tropospheric oxidant during the night, and play a key role in atmospheric chemistry. These reactions lead to the formation of a variety of functionalized products (organic nitrates, carbonyl compounds ...) and to large amounts of secondary organic aerosols. Organic nitrates are the main nitrogen oxides reservoir. They directly influence reactive nitrogen and ozone budgets. Secondary organic aerosol has direct and indirect impacts on climate, due to its formation, its optical and hygroscopic properties and its chemical composition. The aim of this work is to understand these processes at the molecular scale, through kinetic and mechanistic studies of NO3 radical oxidation of several BVOCs.Kinetic and mechanistic studies have been performed for three monoterpenes ((C10H16), γ- and α-terpinene and terpinolene) and one sesquiterpene ((C15H24), β-caryophyllene) in atmospheric simulation chambers. These compounds have been chosen to highlight the influence of their chemical structures on their reactivities and to fill the lack of experimental data about their chemistry in the literature.For the kinetic part, rate constants have been measured with both relative and absolute methods. Due to their high reactivities, this study has requiered the development on the simulation chamber of an IBB-CEAS ((Incoherent Broad Band Cavity Enhanced Absorption Spectroscopy) analysis pathway to measure nitrate radical at the ppt level. Mechanistic studies have been also conducted to identify and quantify the main reaction products. Organic nitrates and SOA yields have been calculated. Detected products allowed proposing reaction mechanisms
Coeur, Cécile. "Contribution à la mesure des émissions biogéniques du pourtour méditerranéen : étude des artefacts analytiques de certains terpènes et de la réactivité de l'acétate de bornyle avec le radical hydroxyl". Université Joseph Fourier (Grenoble ; 1971-2015), 1997. http://www.theses.fr/1997GRE10103.
Texto completoChen, Hui. "Atmospheric chemical processes : reaction of ozone with 2- and 3-carene, evolution of internal mixed combustion particles". Thesis, Orléans, 2014. http://www.theses.fr/2014ORLE2064/document.
Texto completoIn this thesis, we present a complementary work conducted at ICARE-CNRS (Orléans), Part A and at Fudan University (Shanghai), Part B. Part A: 2-and 3-carene are two important biogenic volatile organic compounds present in the atmosphere. The knowledge on their degradation pathways and the corresponding products are still poor. Using complementary reaction systems-ICARE 7300 L and HELIOS 80000 L simulation chambers, vertical laminar flow reactor, their kinetic rate constants for reaction with ozone were determined. Additionally, important product formation yields, hydroxyl radical (OH), formaldehyde (HCHO) and carbon monoxide (CO) have been determined with indication to their corresponding formation routes from the ozonolysis of carene. To have a better understanding on reactions of Criegee intermediates (CIs) generated through ozonolysis in the atmosphere, a horizontal 2-stage laminar flow reactor was set up to measure the rate constants of CIs with SO2, NO2 and O3. Part B: Radiative forcing of black carbon (BC) in the atmosphere, as well as that of brown carbon (BrC), remains to be a major uncertainty in current climate models. Recent reports indicate that the absorption enhancement of BC and BrC particles is determined by evolution of morphology and mixing state during the atmospheric processing. Laboratory-generated BC-BrC mixture particles (BC-BrC) were exposed to sulfuric acid, ammonia/triethylamine, and water vapor sequentially to investigate the alternation in light absorption, morphology and mixing state during simulated atmospheric processing
Osseiran, Noureddin. "Spectroscopic characterization of molecules of atmospheric interest : internal dynamics and microsolvation with hydrogen sulfide (H2S)". Electronic Thesis or Diss., Université de Lille (2018-2021), 2021. http://www.theses.fr/2021LILUR062.
Texto completoBiogenic volatile organic compounds (BVOCs), and especially monoterpenes (C10H16), are molecules naturally occurring in the atmosphere, which have been linked to the formation of secondary organic aerosol (SOA). They can alter the physical and chemical properties in the atmosphere, have negative effects on human health and contribute to climate change. There exists a strong relationship between the structure of a molecular system and the inter- and intramolecular interactions present on the molecular scale.Hence, having in-depth information about the gas phase structure and internal dynamics of these molecules, or their molecular complexes, is important to better understand their reaction pathways and complexation patterns.The synergic combination of quantum chemical calculations and Fourier transform microwave (FTMW) spectroscopy has been shown to be a reliable approach to examine the conformational landscape, structure and internal dynamics of several types of molecules of atmospheric interest, their oxidation products and their complexes. In the framework of this thesis, we have applied this theoretical-experimental approach to characterize the complexes of two monoterpenoids: fenchol (C10H18O) and fenchone (C10H16O) with another atmospheric contaminant: the H2S molecule. The gas phase stable conformations were identified in the pure rotational spectrum with the supportof ab initio and DFT calculations. A comparative analysis of the observed complexes with their water analogues confirmed the presence of weaker hydrogen bonds. On top of that, we observed a large amplitude motion, that was qualitatively described. The stabilizing non-covalent interactions of the two complexes were also evaluated.In a similar manner, and within the same general context, we also characterized the conformational landscape and methyl internal rotation in the case of limona ketone (C9H14O), which is a biogenic volatile organic compounds (BVOC) originating from the oxidation limonene. The experimental barrier height of the methyl torsion showed some deviation from the calculated values, which pushed toward a more thorough examination, that revealed the presence of an intermolecular interaction.The second part of this thesis was dedicated to the construction and evaluation of a broadband chirped pulse FTMW spectrometer, operating in the range 6-18 GHz. A detailed technical description of the spectrometer is given herein. Moreover, the preliminary tests performed to evaluate the performance of the spectrometer are reported
Maison, Alice. "Modélisation des impacts des arbres sur la qualité de l’air de l’échelle de la rue à la ville". Electronic Thesis or Diss., Marne-la-vallée, ENPC, 2023. http://www.theses.fr/2023ENPC0034.
Texto completoTrees provide numerous ecosystem services in cities, helping to reduce some of the consequences of urbanization, such as the urban heat island and water run-off. Their thermo-radiative effect improves thermal comfort.Trees can also have an impact on urban air quality through various processes. The deposition of gaseous and particulate pollutants on tree leaves can help to reduce concentrations. However, the aerodynamic effect of trees modifies the airflow in street canyons and limits the dispersion of pollutants emitted in the street. Trees also emit biogenic volatile organic compounds (BVOCs), which can contribute to the formation of O3 and secondary organic aerosols. BVOC emissions vary depending on the tree species, and are influenced by climatic factors (temperature, radiation) and by the tree water status.The objective of this thesis is to quantify the impacts of these different processes on urban air quality. Numerical simulations are performed over the city of Paris during summer 2022 using the CHIMERE/MUNICH model chain in order to quantify the impact of trees on atmospheric concentrations of pollutants at the local and regional scales. The simulated concentrations are compared to measurements.Urban trees are not generally taken into account in air quality models, either at regional or street level. In order to integrate BVOC emissions into the CHIMERE regional model, an inventory is developed using the tree database of the city of Paris. A method is set up to estimate the characteristics of the trees, which are used as input data for the various models (leaf area, dry biomass, crown size, etc.). On average over the months of June and July 2022 in Paris, local biogenic emissions from trees lead to an increase of 1.0% in O3, 4.6% in organic PM1 and 0.6% in PM2.5. Biogenic emissions from urban trees strongly increase concentrations of isoprene and monoterpenes. Compared with measurements, terpene concentrations tend to be underestimated, given the uncertainties associated with emission factors and the missing part of the vegetation in the inventory. Terpene emissions from urban and suburban vegetation greatly influence the formation of organic particles, it is therefore important to characterize them properly in air quality models.The various effects of urban trees on air quality at street level are then added into the MUNICH street network model. The aerodynamic effect of street trees is parameterized using computational fluid dynamics simulations. It leads to an increase in the concentrations of compounds emitted into the street. This increase can reach +37% for NO2 in streets with a large leaf surface and high traffic. Deposition on tree leaves is computed using a resistive approach adapted to the scale of the tree in the street. However, its impact on concentrations remains limited for the gases and particles studied (< -3%).Finally, a coupling between the TEB (urban surface model), SPAC (soil-plant-atmosphere continuum model) and MUNICH models is developed. This coupling provides a better representation of the impacts of the urban micro-climate heterogeneities and of the thermo-radiative effect of trees on gas and particle concentrations. The effects of the micro-climate and of the tree water stress on BVOC emissions are also taken into account in order to refine the calculation of emissions