Detailed investigations of molecular collisions at the gas-surface interface provide insight into the dynamics and mechanisms of important interfacial reactions. A thorough understanding of the fundamental interactions between a gas and surface is crucial to the study of heterogeneous chemistry of atmospheric organic aerosols. In addition to changing the chemical and physical properties of the particle, reactions with oxidizing gases may alter aerosol optical properties, with implications for the regional radiation budget and climate. Molecular beams of CO₂, NO₂ and O₃ were scattered from long-chain methyl (CH₃-), hydroxyl (OH-), vinyl (H₂C=CH-) and perfluorinated (CF₃(CF₂)₈-, or F-) ω-functionalized alkanethiol self-assembled monolayers (SAMs) on gold, to explore the reaction dynamics of atmospherically important triatomics on proxies for organic aerosols. Energy exchange and thermal accommodation during the gas-surface collision, the first step of most interfacial reactions, was probed by time-of-flight techniques. The final energy distribution of the scattered molecules was measured under specular scattering conditions (θi = θf = 30°). Overall, extent of energy transfer and accommodation was found to depend on the terminal functional group of the SAM, incident energy of the triatomics, and gas-surface intermolecular forces. Reaction dynamics studies of O3 scattering from H2C=CH-SAMs revealed that oxidation of the double bond depend significantly on O₃ translational energy. Our results indicate that the room-temperature reaction follows the Langmuir-Hinshelwood mechanism, requiring accommodation prior to reaction. The measurements also show that the dynamics transition to a direct reaction for higher translational energies. Possible environmental impacts of heterogeneous reactions were probed by evaluating the change in the optical properties of laboratory-generated benzo[a]pyrene (BaP)-coated aerosols, after exposure to NO₃ and NO₂, at 532 nm and 355 nm by three aerosol analysis techniques: cavity ring-down aerosol spectroscopy (CRD-AS) at 355 nm and 532 nm, photoacoustic spectroscopy (PAS) at 532 nm, and an aerosol mass spectrometer (AMS). Heterogeneous reactions may lead to the nitration of organic-coated aerosols, which may account for atmospheric absorbance over urban areas. Developing a detailed understanding of heterogeneous reactions on atmospheric organic aerosols will help researchers to predict the fate, lifetime, and environmental impact of atmospherically important triatomics and the particles with which they collide. / Ph. D.

Aerosols contribute the largest uncertainty to estimates of radiative forcing of the Earth’s atmosphere, which are thought to exert a net negative radiative forcing, offsetting a potentially significant but poorly constrained fraction of the positive radiative forcing associated with greenhouse gases. Aerosols perturb the Earth’s radiative balance directly by absorbing and scattering radiation and indirectly by acting as cloud condensation nuclei, altering cloud albedo and potentially cloud lifetime. One of the major factors governing the uncertainty in estimates of aerosol direct radiative forcing is the poorly constrained aerosol single scattering albedo, which is the ratio of the aerosol scattering to extinction. In this thesis, I describe a new instrument for the measurement of aerosol optical properties using photoacoustic and cavity ring-down spectroscopy. Characterisation is performed by assessing the instrument minimum sensitivity and accuracy as well as verifying the accuracy of its calibration procedure. The instrument and calibration accuracies are assessed by comparing modelled to measured optical properties of well-characterised laboratory-generated aerosol. I then examine biases in traditional, filter-based absorption measurements by comparing to photoacoustic spectrometer absorption measurements for a range of aerosol sources at multiple wavelengths. Filter-based measurements consistently overestimate absorption although the bias magnitude is strongly source-dependent. Biases are consistently lowest when an advanced correction scheme is applied, irrespective of wavelength or aerosol source. Lastly, I assess the sensitivity of the direct radiative effect of biomass burning aerosols to aerosol and cloud optical properties over the Southeast Atlantic Ocean using a combination of offline radiative transfer modelling, satellite observations and global climate model simulations. Although the direct radiative effect depends on aerosol and cloud optical properties in a non-linear way, it appears to be only weakly dependent on sub-grid variability.

Les spectres d'échantillons naturel et enrichi en 13C du dioxyde de carbone ont été enregistrés entre 5851 et 7045 cm-1 par CW-Cavity Ring Down Spectroscopy à très haute sensibilité. Environ 8000 transitions appartenant à huit isotopologues de CO2 (12C16O2, 13C16O2, 16O12C18O, 16O12C17O, 16O13C18O, 16O13C17O and 12C18O2) ont été mesurées avec une précision estimée de 1 × 10-3 cm-1. Les paramètres spectroscopiques ont été obtenus pour un total de 238 bandes, la plupart nouvellement observées. Un certain nombre de résonances ont été observées et identifiées. Les données expérimentales disponibles dans la littérature et celles obtenues au cours de cette thèse ont été utilisées pour améliorer les paramètres du modèle effectif qui reproduit les positions avec un accord proche de leurs incertitudes expérimentales. Les intensités de 2039 et 952 raies ont été mesurées pour 13C16O2 et 12C16O2. Dans le cas de 12C16O2 la plupart des intensités mesurées appartiennent aux bandes perpendiculaires et "interdites". Ces données expérimentales, combinées à des données publiées, ont été utilisées pour améliorer les paramètres du moment dipolaire effectif de ces deux isotopologues. L'ensemble de ces paramètres reproduit les intensités mesurées aux incertitudes expérimentales près. Quatre cas de résonance interpolyade ont été observés pour la première fois dans le cas de CO2. Cette thèse apporte une contribution importante aux bases de données spectroscopiques du dioxyde de carbone : CDSD et HITRAN. Les résultats obtenus ont été intégrés dans la base de données HITRAN qui fait référence pour la physique de l'atmosphère.

Les propriétés électroniques et d'autoassemblage de deux composés organiques, le DHTAP et le bis-pyrène, ont été étudiées par microscopie à effet tunnel (STM), sous ultra-vide et à basse température. Les propriétés optiques ont été étudiées par spectroscopie en cavité résonnante (CRD), également sous ultravide.La croissance du DHTAP a été étudiée sur différents métaux nobles. La croissance du bis-pyrène a été étudiée sur Au(111). Dans chaque cas, les conditions de température idéales pour la formation d’une première couche organisée ont été déterminées. Différents modèles sont proposés pour les structures observées en première couche. La formation de la seconde couche moléculaire à également été étudiée.L'évolution des propriétés optiques, étudié par CRD, du bis-pyrène déposé sur du verre borosilicate combinée aux informations obtenues par STM ont permit d’associer ces modifications aux interactions des moments dipolaires de transition des molécules de la première et de la seconde couche et on également permit de déterminer le mode de croissance.Finalement, la possibilité d’induire des modifications chimique de la molécule de DHTAP, intégrée dans une couche auto-assemblée, en utilisant le courant tunnel du STM a été observé. Il s’avère que la molécule de DHTAP intégrée en première couche peut subir une double déshydrogénation pour conduire à la formation d’un composé identifié comme étant le 5,7,12,14-tetraazapentacene (TAP). En seconde couche, la formation de deux radicaux, en plus du TAP, a été observé. La molécule de TAP présente un certain intérêt du fait qu’elle n’est pas synthétisable pas les méthodes conventionnelle de chimie organique. / Electronic and self-assembling properties of two organic compound, the DHTAP and the bis-pyrene, have been studied by the means of low temperature scanning tunnelling microscopy (STM) under ultrahigh vacuum conditions. Optical properties have been studied by cavity ring-down (CRD) spectroscopy, also under ultrahigh vacuum conditions.The growth of DHTAP has been studied on different metallic substrate. The growth of bis-pyrene has been studied on Au(111). In each case, the optimal temperature conditions for the formation of a well-ordered first monolayer have been determined. The formation of second monolayers has also been studied. The evolution of the optical properties, studied by CRD, of bis-pyrene deposited on borosilicate glass combined with information obtained from STM allow us to identify these modifications as interactions between transition dipole moments of molecules in the first and in the second layer, and also determine the growth mode.Finally, the possibility to induce chemical modification of DHTAP molecules embedded in an ordered monolayer using the tunnelling current of the STM has been studied. It appears that the molecule embedded in the first ML can be doubly dehydrogenated which leads to the formation of a compound identified as 5,7,12,14-tetraazapentacene (TAP). In the second layer, the formation of two radicals in addition to the TAP has been observed. The TAP molecule is interesting because of that it cannot be synthesized using common organic chemical methods.

Cavity ring-down spectroscopy (CRDS) and cavity enhanced absorption spectroscopy (CEAS) are two well-established absorption spectroscopic techniques originally developed for gas-phase samples. Condensed-phase applications of these techniques still remain rare, complicated as they are by additional background losses induced by condensed-phase samples as well as the intracavity components in which the sample is constrained. This thesis is concerned with the development and application of optical-cavity-based techniques in the condensed phase. Polarization-dependent evanescent wave CRDS (EW-CRDS) has been used to study the molecular orientation at the solid/air and solid/liquid interfaces. An increase in average orientation angle with respect to the surface normal has been observed for both methylene blue and coumarin molecules as a function of coverage at the fused silica/air interface. An orientation-angle-dependent photobleaching of pyridin molecules at the fused silica/methanol interface have also been observed. EW-CRDS has also been used to monitor slow in situ photobleaching of thin dye films deposited on the prism surface. The photobleaching dynamics is interpreted as a combination of first- and second-order processes. A significant fraction of this thesis has been devoted to studying magnetic field effects (MFEs) on the kinetics of the radical pair (RP) reactions in solution, in an effort to understand the ability of animals to sense the geomagnetic field. Two novel optical-cavity-based techniques – broadband CEAS (BBCEAS) and CRDS have been developed for this purpose. BBCEAS uses a supercontinuum (SC) source as the cavity light source and a CCD camera as photodetector, enabling simultaneous acquisition of absorption spectrum across the whole visible region (400 – 800 nm). In CRDS, a tunable optical parametric oscillator has been used as the cavity light source. Combined with the switching of external magnetic field (SEMF) method, this technique allows the decay kinetics of the geminate RPs to be monitored, with nanosecond resolution. Both BBCEAS and CRDS provide sensitivity superior to single-pass transient absorption (TA), a technique traditionally used in the MFE studies. A series of photochemical systems have been studied by BBCEAS and CRDS, respectively, among which, the MFEs of drosophila melanogaster cryptochrome has been observed. Importantly, this is the first time an MFE has been observed in an animal cryptochrome, and provides key supporting evidence for the cryptochrome hypothesis of magnetoreception in animals. Besides the optical-cavity-based techniques, a novel fluorescence detection method of MFEs has also been demonstrated. This technique proved ultrahigh sensitivity when applicable.

This thesis describes the development and application of condensed-phase cavity-based spectroscopic techniques - namely cavity ring-down spectroscopy (CRDS); cavity enhanced absorption spectroscopy (CEAS); broadband cavity enhanced absorption spectroscopy (BBCEAS) and evanescent wave (EW) variants of all three. The recently-developed cavity technique of EW-broadband cavity enhanced absorption spectroscopy (EW-BBCEAS) has been used—in combination with a supercontinuum source (SC) and a sensitive, fast readout CCD detector—to record of the full visible spectrum (400–700 nm) of a silica-liquid interfacial layer (with an effective thickness ca. 1 µm), at rapid acquisition rates (> 600 Hz) that are sufficient to follow fast kinetics in the condensed phase, in real time. The sensitivity achieved (A_min= 3.9 x 10^-5) is comparable with previous EW-CRDS and EW-CEAS studies, but the spectral region accessed in this broadband variant is much larger. The study of liquid|air interfaces using EW cavity-based techniques is also illustrated for the first time. The first application of BBCEAS to the analysis of microfluidic samples, flowing through a microfluidic chip, is illustrated. Proof-of-principle experiments are presented, demonstrating the technique’s ability to provide full visible broadband spectral measurements of flowing microfluidic droplets, with both high detection sensitivity (α_min < 10^-2 cm^-1) and excellent spatial and temporal resolution: an SC light source and sensitive, fast readout CCD allowed measurement repetition rates of 273 Hz, whilst probing a very small sample volume (ca. 90 nL). A significant portion of this thesis is devoted to demonstrating the powerful capabilities of CEAS, CRDS and BBCEAS in monitoring radical recombination reactions and associated magnetic field effects (MFEs) in solution. The efficacy of CEAS as a high-sensitivity MFE detection method has been established in a proof-of-principle study, using narrow band CEAS in combination with phase-sensitive detection: MFE-induced absorbance changes of ca. 10^-6 could be detected using the modulated CEAS technique and the data are shown to be superior to those obtained using conventional transient absorption (TA) methods typically employed for MFE measurements. The powerful capabilities of CRDS in monitoring radical recombination reactions and associated MFEs are also demonstrated. In particular, a pump-probe CRDS variant allows not only high sensitivity (A_min on the order 10^-6), but also sub-microsecond time-resolution. Combined, these features represent significant advantages over TA. Finally, SC-BBCEAS is used to measure full visible spectra of photoinduced reactions and their MFEs. The applicability of this approach to in vitro MFE studies of Drosophila cryptochrome is demonstrated—the results mark the first in vitro observation of a magnetic field response in an animal cryptochrome, a key result supporting the hypothesis that cryptochromes are involved in the magnetic sense in animals.

<p>The Earth–atmosphere energy balance is dictated by incoming solar radiation and outgoing thermal radiation with greenhouse gases (GHG) and aerosols playing a major role in this effect. The atmospheric abundance and properties of airborne particles and gases lead to the redistribution of radiative energy, resulting in a warming or cooling effect. However, the extent of this effect remains to be insufficiently constrained. Improved quantification and characterization of GHG and aerosols are important requirements to inform current climate models. High-precision instrumentation and thoughtful experimental strategies are necessary to yield various analytical measurement datasets, despite complex meteorological and environmental conditions. This dissertation focuses on the assessment of CO₂and atmospheric particles from aircraft-based measurements enabling representative and spatially sampling of local regions of interest.</p> <p>Chapter 1 provides introductory discussion on the atmospheric implication of GHG and aerosols on the climate and related uncertainties. Chapter 2 summarizes the employed experimental techniques for quantification of GHG and characterization of atmospheric particles. We relied on an aircraft platform equipped with an air turbulence probe for 3D wind vector calculation and a high-precision cavity ring-down spectrometer for the quantification of ambient CO₂, CH₄, and H2O_<em>v</em>. Furthermore, the simultaneous composition and morphological information of aerosol samples were assessed using complementary chemical imaging techniques. Chemical composition of elements with Z > 23 was determined using computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM/EDX). Scanning transmission X-ray microscopy coupled with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) was used to determined spatially resolved elemental specific molecular information present in atmospheric particles.</p> <p>Chapter 3 presents our study focused on the characterization of mixed mineral dust and biomass burning (BB) aerosols during an intensive burning event. We identified distinct particle types based on individual elemental contribution pre-, syn-, and post-burning event including highly carbonaceous (54–83%) particles, aged mineral dust (1–6%), and sulfur-containing particles (17–41%). X-ray spectromicroscopy techniques were used to characterize the internal chemical heterogeneity of individual BB particles and the morphology of soot inclusions, as well as changes in the particle organic volume fraction (OVF). An estimation method for particle component masses (i.e., organics, elemental carbon, and inorganics) inferred from STXM measurements was used to determine quantitative mixing state metrics based on entropy-derived diversity measures for particles acquired at different periods of the BB event. In general, there was a small difference in the particle-specific diversity among the samples (<em>D</em>_<em>α</em> = 1.3–1.8). However, the disparity from the bulk population diversity observed during the intense periods was found to have high values of <em>D</em>_<em>γ</em> = 2.5–2.9, while particles collected outside of the burning event displayed lower bulk diversity of <em>D</em>_<em>γ</em> = 1.5–2.0. Quantitative methods obtained from chemical imaging measurements presented here will serve to accurately characterize the evolution of mixed BB aerosols within urban environments.</p> <p>Chapter 4 follows the investigation of the physicochemical properties of atmospheric particles collected onboard a research aircraft flown over the Azores using offline spectromicroscopy techniques. Particles were collected within the marine boundary layer (MBL) and free troposphere (FT) comparing samples after long-range atmospheric transport episodes facilitated by dry intrusion (DI) events. The quantification of the OVF of individual particles derived from X-ray spectromicroscopy, which relates to the multi-component internal composition of individual particles, showed a factor of 2.06±0.16 and 1.11±0.04 increase in the MBL and FT, respectively, among DI samples. We show that supplying particle OVF into the <em>κ</em>-Köhler equation can be used as a good approximation of field-measured <em>in situ</em> CCN concentrations. We also report changes in the <em>κ</em> values in the MBL from <em>κ</em>_{MBL, non-DI} = 0.48 to <em>κ</em>_{MBL, DI} = 0.41, while changes in the FT result in <em>κ</em>_{FT, non-D}_I = 0.36 to <em>κ</em>_{FT, DI} = 0.33, which is consistent with enhancements in OVF followed by the DI episodes. Our observations suggest that the entrainment of particles from long-range continental sources alters the mixing state population and CCN properties of aerosol in the region.</p> <p>Chapter 5 discusses the identification and characterization of fine-mode primary biogenic atmospheric particles (PBAP) from the harvesting of crops. Particle samples were analyzed using complementary chemical imaging techniques to apportion the particle-type population based on their size, morphology, and composition. The contribution of PBAP in the size range of 0.15−1.25 μm is estimated to be 10−12% of ∼39,000 analyzed particles. In addition, particle viscosity and phase state were inferred with X-ray spectromicroscopic analysis has shown that the fine-mode organic particles collected are viscous/semisolid (10²−10¹² Pa s) while the majority of PBAP fragments are solid (>10¹²Pa s). The observation of submicrometer, solid carbonaceous fragments of biogenic origin have implications for the regional CCN and ice nuclei budget. Therefore, the seasonal harvesting of crops may play an important, yet unrecognized, role in regional cloud formation and climate.</p> <p>Chapter 6  explores the measurements and quantification of latent heat, sensible heat, and CO₂ fluxes among different land covers in the surrounding area of urban regions using airborne flux techniques. Cities account for the majority of the global CO₂ emissions due to the consumption of energy, resources, infrastructure, and transportation demands. Accordingly, the accurate quantification of these emissions, with exceptional precision, is necessary so that progress towards emission reduction can be monitored. However, a major challenge in quantifying urban emission estimates arises from accurate background emission definitions and apportionment of emission sources in complex urban environments. Airborne eddy covariance measurements were performed to quantify the bidirectional exchange of latent heat, sensible heat, and CO₂ fluxes in the upwind region of Indianapolis within an active biosphere. Here, we observed differences in fluxes across different days and land covers (e.g., corn, soybean, and forests) allowing us to understand the impact of seasonal variability in urban emissions during the full growing season. These experiments illustrate the capability of a research aircraft to perform technically challenging near-direct measurements of atmosphere–surface exchange over local and regional scales.</p> <p>Chapter 7 presents a new method to spatially allocate airborne mass balance CO₂ emissions. We performed seven aircraft measurements downwind of New York City (NYC) quantifying CO₂ emissions during the non-growing seasons of 2018–2020. A series of prior inventories and footprint transport models were used to account for flux contribution outside the area of interest and attribute emission sources within policy-relevant boundaries of the five boroughs encompassing NYC and then employ the modeled enhancement fraction (Φ) to the bulk emission observations from the mass balance approach. Here, we calculated a campaign-averaged source apportioned mass balance CO₂ emission rate of 56±24 kmol/s. The performance and accuracy of this approach were evaluated against other published works including inventory scaling and inverse modeling, yielding a difference of 5.1% with respect to the average emission rate reported by the two complementary approaches. Utilizing the ensemble of emissions inventories and transport models, we also evaluated the overall sources of variability induced by the prior (1.7%), the transport (4.2%), and the daily variability (42.0%). This approach provides a solution to interpreting aircraft-based mass balance results in complex emission environments.</p> <p>Chapter 8 concludes with a brief discussion of technological advances and research outlooks for X-ray spectromicroscopy analysis on atmospheric particles and the quantification of GHG. Opportunities for future applications and novel development of CCSEM/EDX and STXM/NEXAFS to substantially extend the instrument capabilities and improve our understanding of the physicochemical properties of individual atmospheric particles. Chapter 8 also discusses recent developments in satellite-based CO₂ monitoring to complement direct airborne observations. In recent years, significant progress has been made in satellite-based measurements of CO₂ to reveal the spatio-temporal variation in atmospheric CO₂ concentration. The column-averaged dry air CO₂ mole have reached an accuracy of ~1 ppm with a spatial resolution of less than 4 km. Furthermore, column-averaged retrievals can be used to detect and estimate the surface CO₂ fluxes in an active biosphere, quantify anthropogenic emissions over megacities, and monitor the transport of fossil fuel plumes across different continents and seasons.</p>

Cavity ring-down spectroscopy has been used over the last twenty years as a highly sensitive absorption spectroscopic technique to measure light attenuation in gases, liquids, and solid samples. An optical cavity is used as a multi-pass cell, and the decay time of the light intensity in the cavity is measured, thereby rendering the techniques insensitive to light intensity fluctuations. Optical waveguides are used to build the optical cavities presented in this work. The geometries of such waveguides permit the use of very small liquid sample volumes while retaining the advantages of cavity ring-down spectroscopy. In this thesis cavity ring-down measurements are conducted, both, in the time domain and by measuring phase-shifts of sinusoidally modulated light, and the two methods are theoretically connected using a simple mathematical model, which is then experimentally confirmed. A new laser driver, that is compatible with high powered diode lasers, has to be designed to be able to switch from time domain to frequency domain measurements. A sample path length enhancement within the optical cavity is explored with the use of liquid core waveguides. The setup was optimised with respect to the matrix liquid, the geometrical matching of waveguide geometries, and the shape of liquid core waveguide ends. Additionally, a new technique of producing concave lenses at fibre ends has been developed and the output of a general fibre lens is simulated. Finally, liquid core waveguides are incorporated into a fibre-loop ring-down spectroscopy setup to measure the attenuation of two model dyes in a sample volume of <1 µL. The setup is characterized by measuring concentrations of Allura Red AC and Congo Red from 1 µM to a limit of detection of 5 nM. The performance of the setup is compared to other absorption techniques measuring liquid samples. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-04-23 14:08:16.33

科学研究費補助金 研究種目:基盤研究(A)(2) 課題番号:15206012 研究代表者:後藤 俊夫 研究期間:2003-2004年度