Chemistry of secondary organic aerosol

The photooxidation of volatile organic compounds (VOCs) in the atmosphere can lead to the formation of secondary organic aerosol (SOA), a major component of fine particulate matter. Improvements to air quality require insight into the many reactive intermediates that lead to SOA formation, of which only a small fraction have been measured at the molecular level. This thesis describes the chemistry of secondary organic aerosol (SOA) formation from several atmospherically relevant hydrocarbon precursors. Photooxidation experiments of methoxyphenol and phenolic compounds and C₁₂ alkanes were conducted in the Caltech Environmental Chamber. These experiments include the first photooxidation studies of these precursors run under sufficiently low NO_x levels, such that RO₂ + HO₂ chemistry dominates, an important chemical regime in the atmosphere. Using online Chemical Ionization Mass Spectrometery (CIMS), key gas-phase intermediates that lead to SOA formation in these systems were identified. With complementary particle-phase analyses, chemical mechanisms elucidating the SOA formation from these compounds are proposed.

Three methoxyphenol species (phenol, guaiacol, and syringol) were studied to model potential photooxidation schemes of biomass burning intermediates. SOA yields (ratio of mass of SOA formed to mass of primary organic reacted) exceeding 25% are observed. Aerosol growth is rapid and linear with the organic conversion, consistent with the formation of essentially non-volatile products. Gas and aerosol-phase oxidation products from the guaiacol system show that the chemical mechanism consists of highly oxidized aromatic species in the particle phase. Syringol SOA yields are lower than that of phenol and guaiacol, likely due to unique chemistry dependent on methoxy group position.

The photooxidation of several C₁₂ alkanes of varying structure n-dodecane, 2-methylundecane, cyclododecane, and hexylcyclohexane) were run under extended OH exposure to investigate the effect of molecular structure on SOA yields and photochemical aging. Peroxyhemiacetal formation from the reactions of several multifunctional hydroperoxides and aldehyde intermediates was found to be central to organic growth in all systems, and SOA yields increased with cyclic character of the starting hydrocarbon. All of these studies provide direction for future experiments and modeling in order to lessen outstanding discrepancies between predicted and measured SOA.

Investigations of secondary organic aerosol formation in laboratory chambers

Secondary organic aerosol (SOA) is produced in the atmosphere by oxidation of volatile organic compounds. Laboratory chambers are used understand the formation mechanisms and evolution of SOA formed under controlled conditions. This thesis presents studies of SOA formed from anthropogenic and biogenic precursors and discusses the effects of chamber walls on suspended vapors and particles.

During a chamber experiment, suspended vapors and particles can interact with the chamber walls. Particle wall loss is relatively well-understood, but vapor wall losses have received little study. Vapor wall loss of 2,3-epoxy-1,4-butanediol (BEPOX) and glyoxal was identified, quantified, and found to depend on chamber age and relative humidity.

Particles reside in the atmosphere for a week or more and can evolve chemically during that time period, a process termed aging. Simulating aging in laboratory chambers has proven to be challenging. A protocol was developed to extend the duration of a chamber experiment to 36 h of oxidation and was used to evaluate aging of SOA produced from m-xylene. Total SOA mass concentration increased and then decreased with increasing photooxidation suggesting a transition from functionalization to fragmentation chemistry driven by photochemical processes. SOA oxidation, measured as the bulk particle elemental oxygen-to-carbon ratio and fraction of organic mass at m/z 44, increased continuously starting after 5 h of photooxidation.

The physical state and chemical composition of an organic aerosol affect the mixing of aerosol components and its interactions with condensing species. A laboratory chamber protocol was developed to evaluate the mixing of SOA produced sequentially from two different sources by heating the chamber to induce particle evaporation. Using this protocol, SOA produced from toluene was found to be less volatile than that produced from a-pinene. When the two types of SOA were formed sequentially, the evaporation behavior most closely represented that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA particles resembles a core of SOA from the first precursor coated by a layer of SOA from the second precursor, indicative of limiting mixing.

Análisis y mejora de la gestión y organización del equipo Formula Student Bizkaia usando como referencia el modelo EFQM

[ES]El presente trabajo de fin de grado tiene como objetivo analizar y mejorar la gestión y organización del equipo Formula Student Bizkaia, de tal manera que le permita ser más competitivo frente al resto de universidades. Para su realización, en primer lugar, se exponen las distintas alternativas que existen para evaluar la calidad de gestión del equipo. En segundo lugar, una vez se haya escogido el modelo más conveniente, se prosigue al estudio de los distintos criterios clave en los que se basa. En tercer lugar, cuando se haya llevado a cabo el estudio de los puntos fuertes, así como evidencias y áreas a mejorar, se procede a realizar una evaluación que permita determinar las fortalezas y debilidades, para de esta manera potenciarlas y solventarlas, respectivamente. Por último, se presenta un desglose de los gastos que conlleva realizar la elaboración de un estudio de estas características, así como un desglose de las diferentes tareas a llevar a cabo y su respectiva duración.

Secondary Organic Aerosol Composition Studies Using Mass Spectrometry

Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NO_x and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH₄)₂SO₄ seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

Our understanding of the processes and mechanisms by which secondary organic aerosol (SOA) is formed is derived from laboratory chamber studies. In the atmosphere, SOA formation is primarily driven by progressive photooxidation of SOA precursors, coupled with their gas-particle partitioning. In the chamber environment, SOA-forming vapors undergo multiple chemical and physical processes that involve production and removal via gas-phase reactions; partitioning onto suspended particles vs. particles deposited on the chamber wall; and direct deposition on the chamber wall. The main focus of this dissertation is to characterize the interactions of organic vapors with suspended particles and the chamber wall and explore how these intertwined processes in laboratory chambers govern SOA formation and evolution.

A Functional Group Oxidation Model (FGOM) that represents SOA formation and evolution in terms of the competition between functionalization and fragmentation, the extent of oxygen atom addition, and the change of volatility, is developed. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation.

A critical aspect of the environmental chamber is the presence of the wall, which can induce deposition of SOA-forming vapors and promote heterogeneous reactions. An experimental protocol and model framework are first developed to constrain the vapor-wall interactions. By optimal fitting the model predictions to the observed wall-induced decay profiles of 25 oxidized organic compounds, the dominant parameter governing the extent of wall deposition of a compound is identified, i.e., wall accommodation coefficient. By correlating this parameter with the molecular properties of a compound via its volatility, the wall-induced deposition rate of an organic compound can be predicted based on its carbon and oxygen numbers in the molecule.

Heterogeneous transformation of δ-hydroxycarbonyl, a major first-generation product from long-chain alkane photochemistry, is observed on the surface of particles and walls. The uniqueness of this reaction scheme is the production of substituted dihydrofuran, which is highly reactive towards ozone, OH, and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. A spectrum of highly-oxygenated products with carboxylic acid, ester, and ether functional groups is produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the alkane-derived SOA.

The vapor wall loss correction is applied to several chamber-derived SOA systems generated from both anthropogenic and biogenic sources. Experimental and modeling approaches are employed to constrain the partitioning behavior of SOA-forming vapors onto suspended particles vs. chamber walls. It is demonstrated that deposition of SOA-forming vapors to the chamber wall during photooxidation experiments can lead to substantial and systematic underestimation of SOA. Therefore, it is likely that a lack of proper accounting for vapor wall losses that suppress chamber-derived SOA yields contribute substantially to the underprediction of ambient SOA concentrations in atmospheric models.

Estudio del comportamiento aerodinámico de un alerón trasero de un monoplaza tipo Formula Student

[ES]El proyecto investigador tiene el objeto el estudio del comportamiento de un perfil aerodinámico frente a un flujo turbulento, en este caso el aire. Se trata de evaluar las presiones que se ejercen sobre dicho perfil, que será un alerón de monoplaza tipo Formula Student, para comprobar si aporta alguna mejora en el comportamiento del monoplaza la introducción de este paquete aerodinámico. Con la introducción de este perfil en el monoplaza se pretende ganar un mayor agarre en el paso por curva siendo la resistencia al avance en recta la mínima posible, ya que lo que se pretende es hacer el recorrido del circuito en el menor tiempo posible. Por tanto hay dos variables a tener en cuenta a la hora de diseñar el alerón, por un lado esta mejorar el agarre de los neumáticos sobre el asfalto al tomar una curva, lo que nos permitirá tomar la curva a mayor velocidad y por tanto en menos tiempo, y por otro lado, la oposición que el alerón ejerce en el avance en recta disminuyendo su velocidad máxima. En resumen, se trata de comparar la fuerza horizontal y la fuerza vertical que el aire ejerce sobre el perfil aerodinámico a introducir en el monoplaza y evaluar si es beneficioso para este, es decir, si añadiendo dicho perfil se realiza el trazado del circuito en menor tiempo que sin él. Para ello se realizarán simulaciones con un software de modelado físico de flujos y turbulencias sobre un diseño de un alerón dado, con diferentes tipos de flujo, de forma que se asemeje de mejor forma a las condiciones de la pista y se obtendrán los resultados de las presiones que el flujo de aire ejerce sobre las superficies del perfil. Después se obtendrán las fuerzas puntuales vertical y horizontal y se analizaran los datos obtenidos. Deberán tenerse en cuenta, además de los resultados obtenidos, los materiales a emplear a la hora de su fabricación, el proceso de dicha fabricación y el coste que supone tanto el proceso como los materiales empleados.

Calcareous concretions in the Levriere (tributary of the Epte, secondary tributary of the Seine, Eure department) [Translation from: Bull.Ass.fr.Etud.Quaternaire 1973(2), 79-87, 1973]

From research carried, out on a section of the Levriere, concretions (granules, nodules, which were sometimes joined together) partly covering the river ”bottom” were observed. The authors propose to make besides a petrographic examination of the calcareous precipitations and to see if their origin is connected to a biological activity, or if it is purely a case of a physical-chemical precipitation. The hydrological background of the Levriere, a small river of the Normandy Vexin, is given and conditions of the formation of the concretions studied.

Effects of injection nozzle configuration on secondary injection into supersonic flow

Gaseous nitrogen and argon were injected into a primary stream of air moving at Mach 2.56. The gases were injected at secondary to primary total pressure ratios from 3.2 to 28.6 through four different nozzles. Two nozzles, one sonic and one supersonic (M = 3.26), injected normal to the primary stream; and two sonic nozzles injected at 45° angles to the primary flow, one injecting upstream and the other downstream. Data consisted of static pressure measurements on the wall near the injector, total pressure profiles in the wake of the injectant plume, and concentration measurements downstream of the flow. Scale parameters were calculated based upon an analytical model of the flow field and their validity verified by experimental results. These scale heights were used to compare normalized wall side forces for the different nozzles and to compare the mixing of the two streams.

Técnica do tratamento restaurador atraumatico em estudantes de escola municipal do Rio de Janeiro: avaliação in vitro da influência da proteção superficial e do tempo de entrada em serviço na resistência a tração diametral do cimento de ionômero de vidro utilizado

Tratamento restaurador atraumático tornou-se uma opção real para o tratamento da cárie dentária em saúde pública no Brasil. O presente estudo teve como objetivo avaliar durabilidade, resistência e eficácia de 70 restaurações em 31 alunos (entre 6 a 12 anos de idade na Escola Municipal Rotary, RJ - Brasil). Depois de CPO-D e ceo-exame de acordo com critérios da OMS, todos os alunos com selecionados receberam TRA com VITRO MOLAR - DFL, juntamente com instruções de saúde bucal. Os critérios de exclusão foram a presença de cavidades muito profundas e exposição pulpar, casos em que os alunos foram encaminhados para o Postos de Saúde Municipal. In vitro avaliou-se a influência do tempo de entrada em serviço e do tipo de cobertura protetora utilizada na resistência coesiva do Cimento de Ionômero de Vidro utilizado, por meio de ensaios de tração diametral. Confeccionou-se para o teste de tração diametral 6 espécimes para cada variante, 72 no total, com dimensões de 4 mm de diâmetro por 8 mm de comprimento, divididos entre os grupos: grupo1 sem protetor (controle); grupo2 vaselina sólida; grupo3 verniz para unhas. Realizou-se ensaios mecânicos em uma máquina universal de ensaios EMIC DL 500 MF, após a confecção e estocagem individual dos espécimes em potes plásticos contendo 5 ml de água deionizada, que formaram os subgrupos descritos a seguir: a - 20 minutos; b - 2 horas; c - 24 horas; d - 7 dias. Os dados obtidos foram tratados por ANOVA e por Student Newman-Keuls (p<0,05). Ao se avaliar a influência dos diferentes protetores de superfície no CIV utilizado no presente trabalho observou-se que, os protetores de superfície tiveram influência no comportamento do material (p=0,000), com o verniz para unhas mostrando um desempenho superior ao da vaselina sólida. Quanto ao tempo, não foi possível verificar ruptura do material no prazo de 20 minutos, pois os corpos de prova sofriam deformação elástica catastrófica não sendo adequado para a finalidade desejada. Os tempos de 24 horas e sete dias foram semelhantes entre si e diferentes do tempo de duas horas. As restaurações foram clinicamente avaliadas depois de 6, 12, e 24 meses após sua alocação. No total 72 restaurações foram realizadas em 31 escolares. Depois de seis meses, 5 restaurações fraturaram e 3 perderam algum material. Após 12 meses, oito restaurações foram perdidas e apenas 1 fraturou. Na avaliação após 24 meses, mais 12 restaurações foram perdidas e 3 perderam material. Não foram registradas lesões cariosas secundarias após esse período, mesmo quando as restaurações foram parcialmente perdidas. Clinicamente conclui-se que quando a técnica do TRA é bem indicada e aplicada corretamente pode haver uma redução significativa no número de dentes perdidos por lesões de cárie nos indivíduos que participaram do nosso estudo.

Primary and secondary threshold intensities of ultraviolet-laser-induced domain nucleation in nearly stoichiometric LiTaO3

The primary and secondary threshold intensities of ultraviolet-laser-induced preferential domain nucleation in nearly stoichiometric LiTaO3 is observed. The primary threshold is the minimum intensity to achieve the instantaneous preferential domain nucleation within the focus by the combined action of irradiation and electric fields. The secondary threshold is the minimum intensity to achieve the memory effect without any irradiation within the original focus. The space charge field created by the photoionization carriers is thought to be responsible for the instantaneous effect. The explanation based on the formation and transformation of extrinsic defect is presented for the memory effect. (c) 2008 American Institute of Physics.

Suspensión trasera progresiva para moto Student: Alternativa Pro-link

El objetivo de este proyecto ha sido el de diseñar un sistema de suspensión englobado en el ámbito de la competición interuniversitaria MotoStudent. Además de la normativa de la competición, dicha suspensión debe cumplir una serie de requisitos extra impuestos por el equipo de MotoStudent de la ETSI de Bilbao. Las características principales de la suspensión en cuestión deben ser las siguientes:  La rigidez del sistema de suspensión debe ser progresiva, de forma que se comporte como una suspensión blanda a bajas solicitaciones, y como una suspensión dura a altas solicitaciones.  A fin de poder adaptar la suspensión de la moto a diferentes circuitos, el esta deberá estar dotada de un sistema de regulación. Para ello el sistema de suspensión elegido es el sistema por bieletas tipo Pro- Link, cuya principal característica es que, en dicha solución, el balancín no solo tiene movimiento angular, sino que tiene también movimiento lineal, de forma que es mucho más versátil a la hora de diseñar. Figura[