Literatura científica selecionada sobre o tema "Atmospheric lifetime"

Thesis: S.M. in Atmospheric Science, Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences, 2014.<br>In title on title-page. double-underscored "x" appears as subscript. Cataloged from PDF version of thesis.<br>Includes bibliographical references (pages 42-49).<br>A 3-D chemical transport model with coupled oxidant-aerosol chemistry (GEOSChem) is used to analyze the influence of recent (2001 to 2010) growth in Asian NOx and Asian SO 2 emission on transpacific transport of Asian particulate matter, especially sulfate, by quantifying and analyzing the details of chemistry and its sequential influence on transpacific transport during spring and summer. From 2001 to 2010, the spring averaged Asian sulfate enhancement in the western US model surface layer increases by 0.01-0.03 [mu]g M-3 (about 4% of the surface sulfate concentration over the US at 2010 emission level). The net chemical production rate increases in the troposphere over Asia but decreases over the Pacific Ocean. The sulfate production pathway shifts toward gas phase production by OH (7-8% increase-China; 2-3% increase-Upper atmosphere Pacific Ocean) with corresponding reductions in aqueous phase production by H202 ; resulting in a switch of the most important production pathway from aqueous production by H202 to gas phase production by OH. Almost doubling the Asian NO. emission during the period has a negligible influence on Asian sulfate enhancement over the US; this change in Asian NOx emission causes the net chemical production rate to increase in the Asian boundary layer, but to decrease in the upper Asian atmosphere, and in the atmosphere over the Pacific Ocean and the US. This is because the Asian NOx emission growth strengthens the oxidizing power in the Asian boundary layer to more actively form sulfate (mostly removed by wet scavenging), reducing available SO2 for further production away from the source. The Asian NOx emission growth is the major driver in changing the sulfate production pathways toward the gas phase. The 20% increase in Asian SO 2 emission during the period is the primary driver in increasing Asian sulfate enhancement over the US; this change accelerates net sulfate production rate, and makes a minor contribution to shifting toward gas phase production by OH over the course of the transpacific transport. The calculated sulfate column burden shows a notable increase as a response to the changes in Asian emissions. However, the shifts in sulfate lifetime over China due to changes in Asian SO 2 and/or Asian NO, emission are almost negligible (generally 1-2%), and lifetimes over the upper level Pacific Ocean are generally reduced by 3-4%.<br>by Flora Min.<br>S.M. in Atmospheric Science

The focus of this work was on the use of otolith microchemistry and fish eye lens chemical profiles to measure fish movement and provided indirect support for the use of otolith microchemistry to examine exposure to crude oil. Chapter 1 provides an introduction to the applications of otolith microchemistry and eye lens isotopic profiles. In the second chapter, which examined associations between metal exposure and lesion formation in fishes collected after the Deepwater Horizon (DWH) oil spill, I did not observe any change in oil-associated metal concentrations in otoliths coinciding with the timing of the DWH oil spill. This suggests that either the technique used is not sensitive enough to detect any transient changes that may have occurred because of exposure to the oil spill or that the fish examined were not exposed to the oil spill. However, I did find that lesioned fish may have been exposed to a persistent source of trace-metals in the GoM prior to, during, and after the oil spill, and metal-induced immunomodulation may have occurred in these fish. These interactions between the physiological and environmental modulation of otolith element incorporation were explored further in Chapter 3 in which multiple tests demonstrated that physiology explained more of the variation in otolith chemical tags than ambient water chemistry. These findings suggest that the use of otolith microchemistry alone to track fish movement and potential exposure to harmful metals may be complicated by physiological control of otolith microchemistry. Thus, in Chapter 4, I pursued a novel method to evaluate the movement of fish across isoscapes of varying δ15N. I validated the use of fish eye lenses as potential lifetime recorders of isotopic histories and in Chapter 5 compared the use of fish eye lens δ15N profiles to otolith microchemistry profiles to examine fish movement. Both techniques suggested similar patterns of movement in Red Snapper from the northern GoM to the West Florida Shelf. This is the first study to use these complimentary techniques to track fish movement.

Dans le cadre du projet DISPATMO (étude de prévision des risques de pollution liés à la dispersion atmosphérique de produits chimiques), des études de risques liés aux incendies et explosions dus aux produits chimiques ont été menées. L’objectif de cette thèse était de réaliser une étude cinétique et mécanistique approfondie afin de déterminer la dégradation en phase gazeuse de l'un des principaux constituants du solvant Tiflex, acétate de 1-méthoxy-2-propyle (MPA), par les radicaux OH et les atomes de Cl. En outre, les constantes de vitesse de réaction de OH et Cl avec une série d' acétates d’alcoxyle largement utilisés dans l'industrie du revêtement et la peinture, l'acétate de méthoxy-2-butyle (2MBA), l'acétate de méthoxy-3-butyle (3MBA), l'acétate de méthoxy-éthyle (MEA), l'acétate d'éthoxy-éthyle (EEE) et l’acétate de n-pentyle (n-PA), ont été déterminées. Les expériences ont été conduites en utilisant la technique de photolyse laser pulsée couplée à la fluorescence induite par laser, un réacteur à écoulement à basse pression couplé à un spectromètre de masse et une chambre de simulation atmosphérique couplé à GC-FID, FTIR et GC-MS en utilisant les méthodes absolue et relative. Les données cinétiques ont été utilisées pour déterminer les expressions Arrhenius pour évaluer le devenir environnemental des composés étudiés tels que leur durée de vie et le potentiel de formation d'ozone. D'autre part, le mécanisme réactionnel a été étudié et les principaux produits de dégradation et leurs rendements ont été déterminés en présence de NO. Les spectres d’absorption UV-Vis de MPA, 2MBA et 3MBA ont également été déterminés afin d'évaluer le potentiel de photolyse de ces composés dans l’atmosphère. Les paramètres cinétiques et mécanistiques ainsi que les durées de vie troposphérique déterminés sont utilisés comme données d'entrée dans les modèles de simulation atmosphériques photochimiques et dans les modèles de dispersion atmosphérique de produits chimiques pour évaluer leur impact atmosphérique<br>In the context of DISPATMO project (forecast study of pollution risks related to the atmospheric dispersal of chemicals), risk studies linked to the fires and the explosions due to chemical storage were conducted. The purpose of this thesis was to perform a thorough kinetic and mechanistic study to determine the gas phase degradation of one of the main component of Tiflex solvent, the 1-methoxy 2-propyl acetate (MPA). Furthermore, the rate coefficients of OH and Cl with a series of alkoxy acetates widely used in painting and coating industries, 2-methoxy-butyl acetate (2MBA), 3-methoxybutyl acetate (3MBA), methoxy ethyl acetate (MEA), ethoxy ethyl acetate (EEA) and n-pentyl acetate (n-PA), were determined. The experiments were performed employing the pulsed laser photolysislaser induced fluorescence technique, a low pressure flow tube reactor coupled with a quadrupole mass spectrometer and an atmospheric simulation chamber coupled with a GC-FID, a FTIR and a GC-MS using complementary absolute and relative rate methods. The kinetic data were used to derive the Arrhenius expressions as well as to evaluate the environmental fate of the studied compounds such as their lifetimes and the Photochemical Ozone Creation Potential. Besides, the reaction mechanism was investigated, while the major degradation products and their yields were determined in presence of NO. In addition, the UV-Vis absorption cross sections of MPA, 2MBA and 3MBA were measured in order to evaluate their potential photolysis in the atmosphere. The investigation of the chemical processes and the tropospheric lifetimes of the compounds are used as input data in photochemical atmospheric simulation models and in chemical agent atmospheric dispersion models to evaluate their atmospheric impact

Using experimentally measured temperature-process-dependent model parameters, the failure analysis and life prediction were conducted for Atmospheric Plasma Sprayed Thermal Barrier Coatings (APS-TBCs) and electron beam physical vapor deposition thermal barrier coatings (EB-PVD TBCs) with Pt-modified -NiAl bond coats deposited on Ni-base single crystal superalloys. For APS-TBC system, a residual stress model for the top coat of APS-TBC was proposed and then applied to life prediction. The capability of the life model was demonstrated using temperature-dependent model parameters. Using existing life data, a comparison of fitting approaches of life model parameters was performed. The role of the residual stresses distributed at each individual coating layer was explored and their interplay on the coating’s delamination was analyzed. For EB-PVD TBCs, based on failure mechanism analysis, two newly analytical stress models from the valley position of top coat and ridge of bond coat were proposed describing stress levels generated as consequence of the coefficient of thermal expansion (CTE) mismatch between each layers. The thermal stress within TGO was evaluated based on composite material theory, where effective parameters were calculated. The lifetime prediction of EB-PVD TBCs was conducted given that the failure analysis and life model were applied to two failure modes A and B identified experimentally for thermal cyclic process. The global wavelength related to interface rumpling and its radius curvature were identified as essential parameters in life evaluation, and the life results for failure mode A were verified by existing burner rig test data. For failure mode B, the crack growth rate along the topcoat/TGO interface was calculated using the experimentally measured average interfacial fracture toughness.

The instantaneous mortality rate (M) is an important parameter in elasmobranch management and conservation, but is difficult to estimate directly. Thus, indirect estimates based on relatively easily obtained life history parameters are commonly used. Many indirect methods incorporate one or more parameters from the von Bertalanffy growth model (VBGM), which is often criticized for its inability to describe changes in growth associated with maturity. The Lester growth model (LGM) is a biphasic alternative to the VBGM that incorporates trade-offs between reproduction, growth, and survival, and may therefore more accurately estimate M. I used published data from 29 elasmobranch species to compare the performance of the LGM to four conventional growth models and nine conventional methods for indirectly estimating M. For three species (Heterodontus portusjacksoni, Rhizoprionodon taylori, and Carcharhinus limbatus), I obtained direct estimates of M to evaluate the accuracy of indirect M methods. According to AICc, the LGM was the best fitting model for 80.8% of datasets. Using one-sample t-tests, I found that five indirect M methods (two of which are dependent on the LGM) consistently generated estimates of M that were in close agreement with direct estimates. The most common methods in elasmobranch literature appear to be overestimating M by factors of 1.34 – 1.91. However, further research is needed to verify these results across a wider range of species. Overall, I recommend using the LGM to describe the lifetime growth of sharks, and estimating M by averaging across five indirect methods.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences, 1990.<br>Includes bibliographical references (leaves 31-32).<br>by Kevin Robert Gurney.<br>M.S.

The research presented in this thesis is focused around environmentally important chlorine- and fluorine-containing species. The work in this thesis was carried out using data from the ACE-FTS. This work is divided into four principle areas of research. The changes in the volume mixing ratio (VMR) of CCl4, CF4, CFC-11, CFC-12, CFC-113, CH3Cl, ClONO2, COF2, COCl2, COClF, HCFC-22, HCFC-141b, HCFC-142b, HCl, HF and SF6 between 2004 and 2010 in the tropics are presented. In addition to calculating the changes in the VMR of these species during this time, this work allowed a quick comparison between profiles from the new Version 3 ACE-FTS retrieval and from the 3D chemical transport model SLIMCAT. This work acted as a rough validation of these new retrieval schemes. The trends calculated from SLIMCAT and ACE-FTS are in generally in good agreement. They show decreases in CCl4, CFC-11, CFC-12, CFC-113 and CH3Cl and increases in CF4, HCFC-22, HCFC-141b and HCFC-142b. ACE-FTS shows no statistically significant change in COCl2 and COClF, whilst showing an increase in COF2. The total VMRs of stratospheric fluorine and chlorine have been calculated, allowing changes in the VMRs of total stratospheric fluorine and chlorine between 2004 and 2010 to be calculated. In addition to this, the changes in the global warming potential-weighted chlorine and fluorine are also presented. This value allows the radiative forcing effects of changes in the VMR of these species to be evaluated. In a similar manner the changes in the ozone depleting potential-weighted total chlorine are also presented. Total fluorine is increasing in all latitudes. Global Warming Potential-weighted fluorine is increasing at a mean rate of 3.85 ± 0.07 % per year in the Northern Hemisphere and 3.58 ± 0.07 % per year in the Southern Hemisphere. Radiative efficiency-weighted total fluorine show smaller increases of between 0.23 ± 0.11 % per year and 0.45 ± 0.11 % per year. In the short term the changes in fluorine-containing species is having a small climatological effect whilst in the long term these changes will have a more significant climatological effect. Total chlorine is decreasing in all latitude bands. Both the global warming potential- and radiative forcing-weighted chlorine is decreasing. Global warming potential-weighted chlorine is decreasing by 0.31 ± 0.08 % per year in the northern hemisphere and 0.23 ± 0.08 % per year in the southern hemisphere. The changes in radiative efficiency-weighted chlorine are smaller with decreases of 0.11 ± 0.04 % per year in the northern hemisphere and 0.06 ± 0.12 % per year in the southern hemisphere. When considered together these results suggest that in the short term there has been very little, if any, change in climatologically effective chlorine. However, in the long term the reduction in the emissions of long lived CFCs and halons will produce a small reduction in the climatological effect of chlorine containing species. Finally, the stratospheric lifetimes of CFC-12 (113 +(-) 26 (18) years), CCl4 (35 +(-) 11 (7) years), CH4 (195 +(-) 75 (42) years), CH3Cl (69 +(-) 65 (23) years) and N2O (123 +(-) 53 (28) years) have been calculated, by correlating the stratospheric VMR of the species of interest against the VMR of CFC-11 at the same altitude.

Les monoterpènes sont des composés organiques volatils biogéniques (COVB) largement émis dans l'atmosphère par les forêts et les cultures végétales, représentant ainsi des acteurs significatifs de la chimie atmosphérique. Leur réactivité importante envers les oxydants atmosphériques a fait sujet de plusieurs études dans la littérature. Cependant, leurs produits de première génération d’oxydation sont moins évalués et pourraient expliquer en partie la réactivité manquante ainsi que la sous-estimation de la formation des AOS par les modèles. Dans ce contexte, cette étude vise à comprendre la réactivité atmosphérique de cinq COVB (nopinone, myrténal, kétolimonène, caronaldéhyde, et limononaldéhyde) qui sont des produits de première génération de l’oxydation des α et β-pinène et du limonène. Ce travail porte sur l’étude des processus de dégradation en déterminant la cinétique et le mécanisme des réactions d'oxydation des COVB visés par le radical OH, le chlore et l’ozone, ainsi que leur potentielle de photolyse au travers de l’étude de leurs spectres d’absorption UV-Vis. Pour ce faire, les réactions d'oxydation des cinq produits de première génération d’oxydation de monoterpènes ont été étudiées en chambre de simulation atmosphérique couplée à différentes techniques analytiques (FTIR, SPME-GC/MS, PTR-MS-ToF).L’étude spectroscopique se concentre sur la détermination des spectres d’absorption UV-visible des cinq composés dans le domaine 200-400 nm à une température de 353 ± 2 K, et à une pression inférieure à la pression de vapeur saturante du COVB. Les spectres montrent une large bande d'absorption située entre 240 et 370 nm, correspondant à la bande n-π* du groupement carbonyle. L'absorption significative de ces composés au-delà de 290 nm suggère qu’ils sont susceptibles d'être décomposés par photolyse en quelques heures au minimum.Les études cinétiques en température réalisées dans cette thèse concernent la réaction (COV+ OH) pour le nopinone, le myrténal, le kétolimonène et le limononaldehdye, la réaction (COV + Cl) pour le nopinone, le myrténal et le kétolimonène et la réaction d’ozonolyse pour le kétolimonène, le myrténal et le limononaldéhyde. Les expériences ont été menées soit en utilisant la méthode cinétique relative ou la méthode cinétique absolue dans le domaine de température 298 – 353 K et à pression atmosphérique. Les résultats cinétiques obtenus ont permis de calculer les durées de vie atmosphérique de ces composés. Leur persistance atmosphérique ne dépasse pas une journée. Ces durées de vie montrent globalement que la principale voie d’élimination des composés étudiés est liée à leur réaction avec les radicaux OH avec une concurrence importante en région côtière des radicaux Cl. Par ailleurs, les études cinétiques en température ont mis en évidence une tendance générale positive avec l'augmentation de la température vis à vis des radicaux OH et de l’ozone et négative avec le chlore.Enfin des études mécanistiques d’ozonolyse concernant l’ozonolyse du kétolimonène, myrténal et limononaldéhyde ont été élaborées. Ces études consistent à suivre l’évolution temporelle des réactifs ainsi que leur produit de formation. Ces données nous ont permis d’extraire le taux de formation des produits formés lors des processus d’ozonolyse. En se basant sur ces résultats des mécanismes réactionnels d’ozonolyse du kétolimonène, myrténal et limononaldéhyde sont proposés<br>Monoterpenes are biogenic volatile organic compounds (BVOCs) widely emitted into the atmosphere by forests and plant crops, thus representing significant players in atmospheric chemistry. Their high reactivity towards atmospheric oxidants has been the subject of several studies in the literature. However, their first-generation oxidation products are less evaluated, and could partly explain the missing reactivity and the underestimation of AOS formation by models. In this context, this study aims to understand the atmospheric reactivity of five VOCBs (nopinone, myrtenal, ketolimonene, caronaldehyde, and limononaldehyde) that are first-generation oxidation products of α- and β-pinene and limonene. This work focuses on the study of degradation processes by determining the kinetics and mechanism of oxidation reactions of the targeted BVOCs by the OH radical, chlorine and ozone, as well as their potential photolysis through the study of their UV-Vis absorption spectra. To this end, the oxidation reactions of five first-generation monoterpene oxidation products were studied in an atmospheric simulation chamber coupled with various analytical techniques (FTIR, SPME-GC/MS, PTR-MS-ToF).The spectroscopic study focused on determining the UV-visible absorption spectra of the five compounds in the 200-400 nm range at a temperature of 353 ± 2 K, and at a pressure below the saturation vapor pressure of COVB. The spectra show a broad absorption band between 240 and 370 nm, corresponding to the n-π* band of the carbonyl group. The significant absorption of these compounds above 290 nm suggests that they are likely to be removed by photolysis in at least a few hours.The temperature kinetic studies carried out in this thesis concern the (VOC+ OH) reaction for nopinone, myrtenal, ketolimonene and limononaldehdye, the (VOC + Cl) reaction for nopinone, myrtenal and ketolimonene and the ozonolysis reaction for ketolimonene, myrtenal and limononaldehyde. Experiments were carried out using either the relative or the absolute kinetic method in the temperature range 298 - 353 K and at atmospheric pressure. The kinetic results obtained made it possible to calculate the atmospheric lifetimes of these compounds. Their atmospheric persistence does not exceed one day. Overall, these lifetimes show that the main route of elimination for the compounds studied is through their reaction with OH radicals, with significant competition in coastal regions from Cl radicals. The study also revealed a generally positive trend for OH radicals and ozone with increasing temperature, and a negative trend for chlorine.Finally, mechanistic ozonolysis studies of ketolimonene, myrtenal and limononaldehyde were carried out. These studies consist of monitoring the temporal evolution of the reagents as well as the reaction product. These data allowed us to extract the formation rate of the products formed during ozonolysis processes. Based on these results, reaction mechanisms of ozonolysis of ketolimonene, myrtenal and limononaldehyde are proposed