The chemical and optical properties of particulate organic compounds remain unclear, which leaves large uncertainties in the estimation of global radiative transfer balance. Gas and find particle (PM2.5) phase formic acid concentrations were measured with online instrumentation during separate one-month studies in the summer of 2010 in Los Angeles (LA), CA, and Atlanta, GA, and the gas-particle partitioning behavior was investigated and compared with that of water-soluble organic compounds (WSOC). The diurnal profiles clearly indicated that the photochemistry production serves as a strong source for the formation of organics, while the correlation between the gas and particle phase suggested that another partitioning route, the aqueous reactions, is also very important. Later, the optical properties of light-absorbing organic compounds were examined. Little is known about the optical importance of light absorbing particulate organic compounds (brown carbon), especially its extent and absorption relative to black carbon throughout the tropospheric column. Mie theory was applied to size-resolved spectrophotometric absorption measurements of methanol and water-extracts from cascade impactor substrates collected at three surface sites around Atlanta, GA, including both urban and rural. These results were applied to similar measurements of brown carbon in extracts from aircraft bulk filter samples collected over central USA. At the surface sites predicted light absorption by brown carbon relative to total absorption (brown carbon plus pure black carbon) was about 10% and 30% at 350 nm, versus 1 and 11% at 450 nm, for water and methanol extracts, respectively. The relative contribution of brown carbon was greater in the free troposphere and significantly increased with altitude. Although this approach has limitations, it demonstrates the ubiquity and significant potential contribution of brown carbon.

Les aérosols fins ont un impact environnemental primordial. Ils influencent notamment la santé, ont un impact sur la visibilité et le climat. Les Aérosols Organiques Secondaires (AOS) représentent une fraction importante des aérosols fins. Les AOS résultent de la conversion d'espèces gazeuses, formées au cours de l'oxydation des composés organiques volatils (COV), en particules par des processus de nucléation et/ou condensation sur des aérosols préexistants. L'oxydation gazeuse des COV implique une myriade de composés secondaires intermédiaires pouvant participer à la formation d'AOS. Les AOS regroupent ainsi une très grande variété d'espèces. Afin d'étudier la formation d'AOS, il est nécessaire de développer des schémas chimiques décrivant explicitement la formation des composés secondaires. Le LISA a développé en collaboration avec le NCAR (National Center of Atmospheric Research) un générateur de schémas chimiques d'oxydation des composés organiques volatils : le GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). Ce travail vise à tester (i) la fiabilité de GECKO-A à reproduire les concentrations d'AOS observées lors d'expériences en chambre de simulation atmosphérique (CSA) et (ii) la sensibilité de la formation d'AOS aux paramètres physico-chimiques tels que les pressions de vapeur saturante, effets de parois des CSA ou encore aux constantes cinétiques de réaction. Afin d'évaluer la pertinence des schémas chimiques générés avec GECKO-A, le modèle a été confronté à des expériences effectuées en CSA visant à évaluer la formation d'AOS. Le paramètre clé du partitionnement des composés organiques semi-volatils est la pression de vapeur saturante (Pvap) des espèces. Les trois méthodes considérées comme les plus fiables disponibles dans la littérature ont été implémentées dans GECKO-A afin de tester la sensibilité de la formation d'AOS à l'estimation des Pvap. Les pressions de vapeur saturantes estimées par les différentes méthodes présentent des valeurs très différentes s'étalant sur plusieurs ordres de grandeur. Malgré ces divergences marquées, la concentration et la spéciation simulées pour l'AOS s'avèrent en définitive peu sensibles à la méthode utilisée pour estimer les pressions de vapeur. Aucune méthode d'estimation de Pvap n'a par ailleurs permis de réconcilier les concentrations modélisées et observées. La concentration d'AOS demeure systématiquement surestimée de l'ordre d'un facteur 2. L'absorption des composés organiques gazeux semi-volatils sur les murs d'une chambre de simulation atmosphérique a ensuite été étudiée. L'intégration de ce processus dans le modèle conduit à diminuer de façon importante les concentrations simulées en AOS, jusqu'à un facteur 2. En outre, les rendements simulés après implémentation de ce processus apparaissent en bon accord avec les rendements mesurés en CSA. L'hypothèse d'une mauvaise représentation de certains processus en phase gazeuse a également été testée via des tests de sensibilité. En particulier, la sensibilité de la formation d'AOS aux constantes de réactions entre les COV et le radical OH a été explorée. Le système a montré une grande sensibilité à la variabilité des constantes cinétiques de réaction des COV avec le radical OH, que ce soit au niveau de l'estimation de la constante cinétique ou au niveau de la détermination du site d'attaque du radical OH. La sensibilité à l'estimation des constantes de décomposition des radicaux alkoxyles a également été testée. Cette étude n'a en revanche montré que peu d'effets sur le rendement en AOS formé / Fine aerosols have an important impact on health, visibility and climate. Secondary Organic Aerosols (SOA) represent an important fraction of fine aerosol composition. SOA are formed by nucleation or condensation onto pre-existing particles of gaseous species formed during the oxidation of emitted volatile organic compounds (VOC). VOC oxidation implies a huge number of secondary intermediates which are potentially involved in SOA formation. In order to study SOA formation, it is necessary to develop chemical schemes describing explicitly the formation and condensation of the gaseous secondary intermediates. The LISA has thus developed in collaboration with NCAR (National Center of Atmospheric Research) a generator of explicit chemical schemes : GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). This work aims at testing (i) the reliability of GECKO-A to simulate observed SOA concentrations in Atmospheric Simulation Chamber (ASC) and (ii) exploring the SOA sensitivity to physico-chemical parameters such as saturation vapour pressures, chamber walls effects or kinetics rate constants. In order to assess GECKO-A's chemical schemes, the model has been confronted to chamber experiments performed to study SOA. Saturation vapour pressure (Pvap) is the key parameter controlling the gas/particles partitioning of organic compounds The three Pvap estimation methods considered as the more reliable in the literature have been implemented in GECKO-A. Pvap estimated by the three methods differs highly, up to several orders of magnitude. Despite of these discrepancies, simulated SOA concentration and speciation show a low sensitivity to the method used to estimate the Pvap. Moreover, none of the methods were able to make the model fit the observations. SOA concentration is systematically overestimated of a factor 2. Semi volatile organic compounds deposition on a chamber walls has been investigated. The implementation of this process in the model leads to a significant decrease of the simulated SOA concentrations, up to factor of 2. Simulated SOA yields are in good agreement with measured SOA yields. The hypothesis of a misrepresentation of some gaseous processes has then been investigated through sensitivity tests. SOA formation sensitivity to COV+ OH reactions rate constants has been explored. Results exhibited a high sensitivity to the rate constants estimations (regarding the rate constants values estimation, as well as the determination of the OH attack sites). The estimated alkoxy radicals decomposition rate constants have also been tested. This test showed however no significant impact on the simulated SOA yields

This study presents airborne measurements of HO2NO2, HCl and SO2 using chemical ionization mass spectrometry (CIMS) during the Intercontinental Chemical Transport Experiment (INTEX) field campaign, an intensive study to characterize the chemical composition of the troposphere in the eastern United States, Mexico City, and the North Pacific which is the outflow region of Asia. The first direct in situ measurements of HO2NO2 were made in the free troposphere over the eastern U.S. during summer 2004. The highest mean mixing ratio of 76 pptv (median = 77 pptv, = 39 pptv) was observed in the altitude range of 8-9 km. Highly constrained steady state calculations of HO2NO2 using measured HOx levels are poorly correlated with observed HO2NO2 in the upper troposphere (8 km < z < 12 km; the median ratio of [HO2NO2]SS-MEA/[HO2NO2]MEA = 2.9). However, steady state HO2NO2 using model-derived HOx shows reasonable agreement with measurements in the free troposphere ([HO2NO2]SS-MEA/[HO2NO2]MEA = 1.3). The vertical distribution of HCl was measured over the north Pacific during May 2006 from the marine boundary layer (MBL) up to lower stratosphere. Recent stratospheric influence in the upper troposphere (8 km < z < 12 km) was efficiently identified from enhanced HCl (up to ~100 pptv) relative to very low background levels (< 2pptv). In the remote MBL, the acidification of seasalt aerosols by HNO3 appeared to be the major source of HCl, with level consistently over 20 pptv (up to 400 pptv). The distribution of SO2 was measured in the outflow region of the eastern U.S. and Asia; two major anthropogenic SO2 source regions. This study presents vertical and horizontal distributions of SO2 and relevant gas phase and aerosol parameters to characterize SO2 transport in the troposphere. SO2 in the boundary layer was efficiently transported to the upper troposphere by deep convection and frontal uplift processes. High SO2 in convective plume in the upper troposphere were strongly correlated with ultrafine aerosols.Conversely, SO2 from frontal uplift shows a strong correlation with non-volatile aerosols. Comparisons of SO2 products from global 3-D chemical transportation models (GEOS-CHEM and MOZART) with observations suggest that sulfur sources are relatively well described but that the oxidation mechanism needs refinement.

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

We derive tropospheric column BrO during the ARCTAS and ARCPAC field campaigns in spring 2008 using retrievals of total column BrO from the satellite UV nadir sensors OMI and GOME-2 using a radiative transfer model and stratospheric column BrO from a photochemical simulation. We conduct a comprehensive comparison of satellite-derived tropospheric BrO column to aircraft in-situ observations of BrO and related species. The aircraft profiles reveal that tropospheric BrO, when present during April 2008, was distributed over a broad range of altitudes rather than being confined to the planetary boundary layer (PBL). Perturbations to the total column resulting from tropospheric BrO are the same magnitude as perturbations due to longitudinal variations in the stratospheric component, so proper accounting of the stratospheric signal is essential for accurate determination of satellite-derived tropospheric BrO. We find reasonably good agreement between satellite-derived tropospheric BrO and columns found using aircraft in-situ BrO profiles, particularly when satellite radiances were obtained over bright surfaces (albedo >0.7), for solar zenith angle <80 degree and clear sky conditions. The rapid activation of BrO due to surface processes (the bromine explosion) is apparent in both the OMI and GOME-2 based tropospheric columns. The wide orbital swath of OMI allows examination of the evolution of tropospheric BrO on about hourly time intervals near the pole. Low surface pressure, strong wind, and high PBL height are associated with an observed BrO activation event, supporting the notion of bromine activation by high winds over snow. We also provide monthly climatological maps of free tropospheric BrO volume mixing ratio (VMR) derived using the so-called cloud slicing technique. In this approach, the derived slope of the total column BrO versus cloud pressure is proportional to free tropospheric BrO VMR. Estimated BrO VMR shows a minimum in the tropics and greater values at higher latitudes in both hemispheres. High tropospheric BrO VMR at high latitudes in spring could be influenced by near-surface bromine activation.

Thesis (Ed.D.)--Teachers College, Columbia University, 1995. / Typescript; issued also on microfilm. Sponsor: Warren E. Yasso. Dissertation Committee: O. Roger Anderson. Includes bibliographical references (leaves 95-109).

Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 196-214).

Doctorat en Sciences / info:eu-repo/semantics/nonPublished

A major opportunity for using satellite observations of tropospheric chemical concentrations is to improve our scientific understanding of atmospheric processes by integrated analysis of satellite, aircraft, and ground-based observations with global and regional scale models. One endpoint of such efforts is to reduce modeling biases and uncertainties. The idea of coupling these observations with a regional scale air quality model was the starting point of this research. The overall objective of this research was to improve the NOₓ emission inventories by integrating observations from different platforms and regional air quality modeling. Specific objectives were: 1) Comparison of satellite NO₂ retrievals with simulated NO₂ by the regional air quality model. Comparison of simulated tropospheric gas concentrations simulated by the regional air quality model, with aircraft and ground-based observations; 3) Assessment of the uncertainties in comparing satellite NO₂ retrievals with NOₓ emissions estimates and model simulations; 4) Identification of biases in emission inventories by data assimilation of satellite NO₂ retrievals, and ground-based NO, NO₂ and O₃ observations with an iterative inverse method using the regional air quality model coupled with sensitivity calculations; 5) Improvement of our understanding of NOₓ emissions, and the interaction between regional and global air pollution by an integrated analysis of satellite NO₂ retrievals with the regional air quality model. Along with these objectives, a lightning NOₓ emission inventory was prepared for two months of summer 2004 to account for a significant upper level NOₓ source. Spatially-resolved weekly NO₂ variations from satellite retrievals were compared with estimated NOₓ emissions for different region types. Data assimilation of satellite NO₂ retrievals, and ground-based NO, NO₂ and O₃ observations were performed to evaluate the NOₓ emission inventory. This research contributes to a better understanding of the use of satellite NO₂ retrievals in air quality modeling, and improvements in the NOₓ emission inventories by correcting some of the inconsistencies that were found in the inventories. Therefore, it may provide groups that develop emissions estimates guidance on areas for improvement. In addition, this research indicates the weaknesses and the strengths of the satellite NO₂ retrievals and offers suggestions to improve the quality of the retrievals for further use in the tropospheric air pollution research.

Halogen-driven ozone and nonmethane hydrocarbon losses in springtime Arctic boundary layer are investigated using a regional chemical transport model (CTM). Surface observation of O3 at Alert and Barrow and aircraft observations of O3 and hydrocarbons during the TOPSE experiment from February to May in 2000 are analyzed. We prescribe halogen radical distributions based on GOME BrO observations and calculated or observed other halogen radical to BrO ratios. GOME BrO shows an apparent anti-correlation with surface temperature over high BrO regions. At its peak, area of simulated near-surface O3 depletions (O3 LT 20ppbv) covers GT 50% of the north high latitudes. Model simulated O3 losses are in agreement with surface and aircraft O3 observations. Simulation of halogen distributions are constrained using aircraft hydrocarbon measurements. We find the currently chemical mechanism overestimate the Cl/BrO ratios. The model can reproduce the observed halogen loss of NMHCs using the empirical Cl/BrO ratios. We find that the hydrocarbon loss is not as sensitive to the prescribed boundary layer height of halogen as that of O3, therefore producing a more robust measure for evaluating satellite column measurement. Tropospheric tracer transport and chemical oxidation processes are examined on the basis of the observations at northern mid-high latitudes and over the tropical Pacific and the corresponding global 3D CTM (GEOS-CHEM) simulations. The correlation between propane and ethane/propane ratio is employed using a finite mixing model to examine the mixing in addition to the OH oxidations. At northern mid-high latitudes the model agrees with the observations before March. The model appears to overestimate the transport from lower to middle latitudes and the horizontal transport and mixing at high latitudes in May. Over the tropical Pacific the model reproduces the observed two-branch slope values reflecting an underestimate of continental convective transport at northern mid-latitudes and an overestimate of latitudinal transport into the tropics. Inverse modeling using the subsets of observed and simulated data is more reliable by reducing (systematic) biases introduced by systematic model transport model transport errors. On the basis of this subset we find the model underestimates the emissions of ethane and propane by 14 5%.