Com o intuito de viabilizar, ambiental e economicamente, a mineralização de substâncias fenólicas presentes em águas e efluentes, foram estudadas as moléculas do timol (C10H14O TOH, a 200 mg L-1) e do bisfenol-A (C15H16O2 BPA, a 25 mg L-1) utilizando Processos Oxidativos Avançados (POA), no caso, ozônio (O3), radiação ultravioleta (UV) e peróxido de hidrogênio (H2O2) que, quando combinados, ou em condições específicas, promovem a geração de radicais hidroxila (OH), um poderoso oxidante. O sistema de tratamento utilizado foi desenvolvido no próprio Laboratório de Tratamento de Resíduos do CENA/USP. O TOH e o BPA foram submetidos a tratamento em pH 3 e 11, com O3 (1,98 g h-1) e UV (0, 8 e 32 watts). Adicionalmente, o TOH foi tratado também com H2O2 (0, 1.176 e 2.352 mg), totalizando 18 tratamentos para o TOH e 6 para o BPA. A eficiência dos tratamentos foi avaliada a partir da porcentagem de remoção do carbono orgânico total (TOC). Para ambas as moléculas, a combinação 1,98 g h-1 de O3, 32 watts UV e ausência de H2O2, em pH 3, apresentou os melhores resultados de conversão de TOC a CO2, especificamente 99,6 ± 0,6% em 90 minutos para o timol e 93,9 ± 0,6% de mineralização de bisfenol-A em 60 minutos de tratamento. Este tratamento foi então reproduzido no resíduo de timol gerado pelos laboratórios do CENA/USP e o resultado obtido foi de 92,64 ± 1,2%, um pouco inferior ao obtido para a solução de TOH, provavelmente devido à presença de outras substâncias. As soluções (TOH e BPA) e o resíduo (TOH) tratados foram submetidos à análise de fenóis totais, obtendo-se resultados inferiores ao exigido (0,5 mg L-1 de fenóis totais) pelas resoluções CONAMA 357/2005 e 397/2008 para a disposição em corpos hídricos. Realizaram-se também ensaios de toxicidade com os organismos Pseudokirchneriella subcapitata, Daphnia magna e Hydra attenuata (que representam os distintos níveis tróficos da cadeia alimentar), que evidenciaram redução da toxicidade das soluções de TOH e BPA após tratamento, sendo que o mesmo não ocorreu para o resíduo de timol, provavelmente devido à sua constituição. Os resultados indicam que o tempo de tratamento seria uma variável importante a ser estudada no tratamento dos resíduos de TOH gerados nos laboratórios do CENA/USP. Os POA (O3/UV e O3/UV/H2O2) propostos no presente trabalho mostraram-se uma alternativa adequada, eficiente e com custos competitivos em relação a outras tecnologias no tratamento destes compostos fenólicos / In order to facilitate, environmentally and economically the mineralization of phenolic substances present in water and wastewater, a study was carried out with the molecules of thymol (C10H14O TOH, in a concentration of 200 mg L-1) and bisphenol-A (C15H16O2 BPA, in a concentration of 25 mg L-1) using Advanced Oxidation Processes (AOP). The AOP used were ozone (O3), ultraviolet radiation (UV) and hydrogen peroxide (H2O2) which, when combined or in specific conditions, promote a hydroxyl radicals (OH) formation, a powerful oxidant. The line system used was developed in the Residues Treatment Laboratory at CENA/USP. The TOH and BPA were submitted to the treatment at pH 3 and 11, with O3 (1.98 g h-1) and UV (0.8 and 32 watts). Additionally, the TOH was also treated with H2O2 (0, 1,176 and 2,352 mg), totalizing 18 treatments for TOH and 6 for BPA. The treatments efficiency was assessed by the percentage of total organic carbon (TOC) removed. For both molecules, the combination of 1.98 g h-1 of O3, 32 watts of UV and absence of H2O2, at pH 3, showed the best conversion of TOC to CO2, specifically 99.6 ± 0.6% of TOH in 90 minutes and 93.9 ± 0.6% of BPA in 60 minutes of treatment. This treatment was reproduced in the TOH residue generated by the CENA/USP laboratories. The TOC removal was 92.6 ± 1.2%, slightly lower than that obtained for the solution of TOH, probably due to the presence of other substances. The solutions (BPA and TOH) and the residue (TOH) treated were submitted to the total phenols analysis, resulting in values lower than demanded (0.5 mg L-1 of total phenols) by the law in force (CONAMA 357/2005 and 397/2008), which regulates the discharge of wastewater in the environment. We carried out also toxicological tests with the organisms Pseudokirchneriella subcapitata, Daphnia magna and Hydra attenuate (representing species in different levels of the food chain). The toxicity of solutions (TOH and BPA) decreased after treatment, but the same results were not observed in the TOH residue, probably due to its composition. The results show that treatment time is an important variable that should be studied for treatment of TOH residue generated in the CENA/USP laboratories. The AOP (O3/UV and O3/UV/H2O2) proposed showed up as a suitable alternative in terms of efficiency and cost-competitive when compared with other technologies to treatment of these phenolic compounds

Incineração pode ser considerado um método terminal para a disposição de resíduos. Apesar de toda vantagem que possa apresentar, a oposição a este tipo de tratamento tem sido frequentemente renovada em função de traços de dioxinas cloradas, furanos clorados e outros compostos detectados nos efluentes gasosos de incineradores de resíduos. A eficiência de Incineradores é medida pela remoção e destruição de compostos e pela emissão de produtos de combustão incompleta -PCI (ex. Dioxinas, Furanos, etc). Neste trabalho propomos a utilização do reagente de Fenton como sistema de oxidação auxiliar em um incinerador com forno de camara rotativa. O objetivo deste trabalho foi aumentar a Eficiência de Destruição e Remoção de compostos e diminuir a emissão de PCIs. A reação de Fenton é dada pela equação [1]. Fe2+ + H2O2 ←→ Fe3+ + *OH + OH- [1] Em condições ácidas o radical hidroxila apresenta potencial de oxidação Eo = 2,33 v. No processo oxidativo de Fenton normalmente 40 a 60 % do carbono é convertido a CO2 , dependendo da quantidade de Fe2+, peróxido e da temperatura da solução. Durante os testes foram efetuados 12 coletas dos efluentes gasosos, 6 com a utilização do reagente de Fenton e 6 sem o seu uso. Houve redução em 79 % da Taxa de emissão de compostos orgânicos e 97 % na redução da taxa de emissão de Dioxinas e Furanos (PCIs). 12 amostras de efluentes líquidos industriais contendo solventes também foram tratadas a temperatura ambiente com reagente de Fenton. Os resultados obtidos mostraram redução de 100 % a 47 % na concentração dos solventes. / Incineration can be considerate a terminal method for residue disposition. Beside the advantage that it could show the oposition to this kind of treatment has been frequently renovated based on chlorinated dioxines, chlorinated furanes traces and others detectable compounds that apear on the waste gases from incinerators. The efficience of incinerators is measered by the destruction and remotion of feed in compounds (DRE - Destruction and Remotion Efficiency) and emission of products formed by incomplete combustion (ICP), e.g. Dioxinas, Furanos etc. In this work we propose the use of Fenton\'s reagent as an auxiliar oxidation system in a rotatory kiln incinerator. The aim was increase the efficience of destruction and remotion (DRE) and decrease ICP emission. Fenton\'s reaction can be defined in the equation [1]. Fe2+ + H2O2 ←→ Fe3+ + *OH + OH- [1] On acidic conditions the hydroxyl radical show oxidation potential Eo = 2,33 v. On the Fenton\'s oxidative process normaly 40 to 60 % of the carbon is converted to CO2 , depending on Fe2+ and peroxide concentration and solution\'s temperature. During the experimental step 12 samples from waste gases were taken, 6 of them using Fenton\'s treatment and other 6 without auxiliary oxidation. There were a reduction of 79 % on the emission of organic compounds and a reduction of 97 % on the emission of Polychlorinated Dioxines e Furanes (ICPs). 12 samples of industrial waste water were also treated with Fenton\'s reagent at room temperature. The results showed solvent concentration reduction from 100 % to 47 %.

O trabalho desenvolvido consistiu na síntese eletroquíca de 4 polímeros conjugados da família dos PPVs, substituídos por cadeias laterais formadas por unidades - CORS (tioéster) com grupos R de comprimentos distintos. A caracterização desses polímeros foi feita por métodos espectroscópicos, análises térmicas e cromatografia por exclusão de tamanho. Os polímeros foram dopados com ácido canforsulfônico. Sensores foram construídos pela deposição de filmes poliméricos finos sobre eletrodos interdigitados. Suas respostas resistivas, frente à exposição aos vapores de substâncias voláteis, foram estudadas. Um equipamento foi desenvolvido para testar os sensores. Através dessa ferramenta, os sensores foram conectados a condutivímetros, cujas saídas foram lidas e digitalizadas por um microcontrolador, qeu enviou esses dados a um computador (PC). O conjunto de dados colhidos permitiu gerar gráficos de resposta vs. tempo e de PCA (análise das componentes principais), utilizados na avaliação da seletividade dos sensores. Os sensores foram expostos a ar saturado com vapores de compostos orgânicos voláteis. Os resultados mostraram que esses são capazes de distinguir os compostos testados. O arranjo de alguns sensores diferentes gerou padrões distintos de resposta para cada substância analisada, possibilitando o emprego de programas de reconhecimento de padrões na avaliação dos analitos. Em testes com odores mais complexos, os sensores foram expostos aos vapores de diversas marcas de café e de cerveja que evidenciaram a seletividade. O desempenho dos sensores em análises quantitativas foi avaliado por meio da exposição aos vapores de soluções alcoólicas aquosas. Foi verificada a sensibilidade dos sensores à quantidade de etanol presente nas soluções. Através do método de adição de padrão foi possível determinar o teor de etanol em bebidas alcoólicas comerciais. / The electrosynthesis of four conjugated polymers of the PPV family, presenting as side-chains -COSR (thioester) groups of different lengths, is described. These polymers were characterised spectroscopically, by thermal analyses and by size exclusion chromatography (SEC). The polymers were doped with 10-camphorsulfonic acid. Casting thin polymeric films onto interdigitated electrodes assembled sensors whose response and selectivity were evaluated by exposing them to volatile organic compounds (VOCs). The resistance over the contact pairs was continuously monitored with an accurate conductivity meter connected via an analogue-to-digital converter to a PC in which a software enabled plotting resistance vs. time graphs and PCA (principal component analysis) plots. The sensors were able to discriminate the tested VOCs showing a different response pattern for each compound. The sensors also exhibited good selectivity when exposed to complex odours as, for instance, different brands of coffee and beer. They were also tested in quantitative analyses allowing determination of the ethanol content in alcoholic drinks.

Este trabalho apresenta os resultados de um estudo comparativo das concentrações de alguns elementos de origem antrópica e de constituição, na forma lixiviada e total, em amostras de sedimentos, coletadas no Canal de São Sebastião e Ubatuba, litoral norte de São Paulo. Dois métodos de dissolução de amostras foram usados: EPA 3051 para a fração lixiviada e o método EPA 3052, seguido por uma etapa de digestão em vaso aberto com adição de ácido bórico, para a determinação dos elementos na forma total. A determinação dos elementos Al, Fe, Na, K, Mg, Ti, Ca, S, P, V, Cr, Mn, Ni, Zn, Sr, Co, Cu, Cd, Mo e Pb foi feita por ICP-OES, depois de elaboração de programas analíticos adequados, levando em conta possíveis interferências de matriz e usando materiais de referência certificados. Muito embora a Ilha Anchieta, em Ubatuba, compreenda uma região não poluída, os resultados indicam um processo de deposição, causado por atividades antrópicas locais, perto da área continental. O estudo comparativo entre os dois locais revelou um processo de deposição no Canal de São Sebastião causado pela influência de atividades antrópicas nessa área, principalmente devido à presença de um terminal marinho de descarga de óleo e despejos de esgotos. / This work presents the results of a comparative study of some anthropic and constituent elements. Their concentrations were determined as leachable and total form, in sediments samples, collected in São Sebastião\'s Channel and Ubatuba, north coast of São Paulo, Brazil. Two methods of samples dissolution were used: EPA 3051 for leachable fraction and the method EPA 3052, followed by an open vessel digestion step with addition of boric acid, for the total ones. The determination of the elements Al, Fe, Na, K, Mg, Ti, Ca, S, P, V, Cr, Mn, Ni, Zn, Sr, Co, Cu, Cd, Mo and Pb was made through ICP-OES, after elaboration of suitable analytical programs, taking into account the possible matrix interference, using certified reference materials. Although Ilha Anchieta, in Ubatuba, comprises a not polluted region, the results indicated a deposition process, caused by anthropic local activities, near the continental area. The comparative study among the two sampling sites, revealed a certain depositional process in São Sebastião\'s Channel, caused by the influence of anthropic activities in this area, mainly due a presence of a marine terminal of oil and sewage discharges.

A ligação de Cu(II) à superfície de espécies mistas e liofilizadas da microalga Spirulina foi estudada em pH 6.0 por titulação potenciométrica com eletrodo íon-seletivo para Cu(II). Três materiais foram estudados: a suspensão completa da alga (Suspensão Total), a água de lavagem obtida por centrifugação da suspensão total (Fração Solúvel) e a suspensão das células lavadas com água (Fração Insolúvel). Os métodos de Scatchard e de Funções Diferenciais de Equilíbrio (DEF) foram usados para tratamento de dados. Os gráficos de Scatchard possibilitaram a determinação de duas classes de sítios de complexação, sendo que os valores de log K* para os sítios mais fortes variaram entre 7,3 e 7,9. Para os sítios mais fracos os valores de log K* foram determinados entre 3,5 e 3,9. As concentrações totais dos sítios de ionização foram determinadas em pH 6,0 por titulação potenciométrica com solução de NaOH, resultando 1,6±0, 1; 1,5±0,5 e 0,92±0,08 mmol g-1 para a Suspensão Total, Fração Solúvel e Fração Insolúvel, respectivamente. O método DEF revelou uma variação linear dos valores de log KDEF em função do log θ (θ = grau de ocupação dos sítios de complexação), sendo que os valores de log KDEF decresceram de 9 para 4 em conseqüência do aumento de log θ de -2,5 para -0,25. Os graus de heterogeneidade determinados por DEF ficaram na faixa entre 0,4 e 0,5 para os três materiais estudados. / The binding of Cu(II) to the surface of mixed species of lyophilized Spirulina was studied at pH 6.0 by potentiometric titration monitored with a copper ion selective electrode. Three materials were studied: the total suspension of alga (Total Suspension), the washing water that resulted from centrifugation of the total suspension {Soluble Fraction), and the water-washed cells (Insoluble Fraction). The Scatchard method and the Differential Equilibrium Functions (DEF) were used for the treatment of the titration data. The Scatchard plots determined two classes of binding sites, with log K* values for stronger sites varying between 7.3 and 7.9. For the weaker sites the log K* values ranged between 3.5 and 3.9. The total concentration of binding sites at pH 6.0 were determined by potentiometric titration with NaOH solution, resulting 1.6±0.1, 1.5±0.5 and 0.92±0.08 mmol g-1 for the Total Suspension, Soluble Fraction, and Insoluble Fraction, respectively. The DEF approach revealed a linear variation of log KDEF as a function of log θ (θ = degree of site occupation), with log KDEF decreasing from 9 to 4 as a consequence of increasing log e from -2.5 to -0.25. The degree of site heterogeneity determined by the DEF approach was between 0.4 and 0.5 for the three materials studied.

Centenas de compostos orgânicos são emitidos para a atmosfera por uma variedade de fontes biogênicas e antrópicas. Essa mistura complexa causa preocupação devido ao impacto que esses compostos podem provocar na saúde e no ambiente. Apesar de constituírem 10-70% da massa do aerossol atmosférico, a caracterização dos compostos orgânicos particulados permanece ainda deficitária. A contribuição das principais fontes de emissão para a poluição a nível regional pode ser diagnosticada através da utilização de marcadores moleculares específicos. De acordo com esta necessidade, o objetivo do presente trabalho é a caracterização de compostos orgânicos do aerossol atmosférico coletado em sítios de cidades da América do Sul. As amostragens do material particulado (MP10) foram realizadas em duas áreas em Bogotá na Colômbia, uma de influência industrial (BOI) e outra veicular (BOV) em 2007, e em áreas urbanas em São Paulo no Brasil em 2007 (SPA 07) e 2008 (SPA 08), e em Buenos Aires (BAI) na Argentina em 2008. Diferentes classes de compostos orgânicos foram determinadas: n-alcanos e hidrocarbonetos policíclicos aromáticos (HPA) por cromatografia a gás com detecção por ionização em chama (CG-DIC), n-alcanais e n-alcanonas por cromatografia a gás com detecção por espectrometria de massas (CG/EM). A composição e concentração do aerossol atmosférico foram afetadas substancialmente pelo transporte de massas provenientes de regiões com queima de biomassa e pelas condições meteorológicas locais. Em SPA 08, BOI e BAI foram encontradas as maiores concentrações de MP10 onde as amostragens foram realizadas em época de seca, favorecendo a acumulação dos poluentes. A constituição orgânica do MP10 nos sítios estudados reflete a incorporação nas amostras de marcadores moleculares biogênicos como n-alcanos com número ímpar de carbonos. Dentre os traçadores antrópicos, foram identificadas a presença de pristano e fitano, a mistura complexa não-resolvida (MCNR) e HPA de queima de combustíveis fósseis. Em SPA 08 foi identificada a presença do reteno, um traçador da queima de biomassa. As maiores concentrações de n-alcanais e n-alcanonas foram observadas no sítio BOV. Os n-alcanais (< C20) identificados nos sítios deste trabalho podem ser originados a partir da oxidação de alcanos e alcenos, e as n-alcanonas (< C20) podem ter como origem atividades antrópicas, processos oxidativos na atmosfera ou atuação microbiana sobre outros compostos. / Hundreds of organic compounds are emitted to the atmosphere by biogenic and anthropogenic sources. This complex mixture generates concern due to the impact of these compounds on health and environment. In spite of accounting for 10-70% of the atmospheric aerosol mass, particulate-phase organic compounds are not yet well characterized. The contribution of the major emission sources to regional particulate pollution can be diagnosed by using specific molecular markers. According to this necessity, the present work has as objective the characterization of organic compounds from atmospheric aerosol collected in sites of South American cities. The particulate matter (PM10) sampling were accomplished in two areas in Bogota (Colombia), one with industrial (BOI) and other with vehicular (BOV) influence in 2007, and in urban areas in Sao Paulo (Brazil) in 2007 (SPA 07) and 2008 (SPA 08), and in Buenos Aires (BAI), Argentina, in 2008. Different organic classes were determined: n-alkanes and polycyclic aromatic hydrocarbons (PAH) by gas chromatograph with flame ionization detection (GC-FID), n-alkanals and n-alkanones by gas chromatograph with mass spectrometer detection (CG/MS). The aerosol atmospheric composition and concentration were substantially affected by mass transport from biomass burning regions and by the local meteorological conditions. In SPA 08, BOI and BAI were found the highest PM10 concentrations where the samplings were accomplished in dry period, contributing for the pollutants accumulation. The PM10 organic composition at studied sites reflects the incorporation from biogenic molecular markers in the samples like n-alkanes with odd carbon number. Among the anthropogenic tracers, were identified the presence of pristane and phytane, the unresolved complex mixture (UCM) and PAH from fossil fuel combustion. In SPA 08 was observed the presence of retene, a biomass burning tracer. Higher concentration from n-alkanals and n-alkanones were observed at the BOV site. The n-alkanals (< C20) identified at sites from this work may be originated from oxidation of alkanes and alkenes, and n-alkanones (< C20) are derived from anthropogenic activity, atmospheric oxidative processes or microbial action over other compounds.

Neste trabalho realizou-se a síntese e caracterização de materiais contendo óxidos de lantanóides incorporados em sílica mesoporosa ordenada, os quais foram utilizados como catalisadores no processo de ozonização de compostos orgânicos poluentes. Empregando-se o método de impregnação úmida, realizou-se a incorporação de óxido de cério e óxido de lantânio no suporte mesoporoso, do tipo SBA-15. Utilizaram-se diferentes precursores dos óxidos metálicos, a fim de verificar a influência que a fonte do cátion metálico exerça tanto nas características estruturais, texturais e morfológicas dos materiais quanto na atividade catalítica. A caracterização destes materiais mostrou que em todas as amostras não houve colapso da estrutura ordenada de mesoporos da SBA-15. Porém nos materiais incorporados observou-se a diminuição da área superficial específica e o volume de poro, devido à presença do CeO2 ou do La2O3 tanto na superfície do suporte quanto no interior dos mesoporos. Também foi possível identificar as fases cristalinas destes óxidos após a etapa de incorporação. Os catalisadores foram empregados na degradação de um azocorante, Preto Remazol B. Para todos os materiais verificou-se que a ozonização catalítica heterogênea proporcionou o aumento da mineralização em relação ao processo de ozonólise. Para os catalisadores que continham CeO2, os melhores resultados de mineralização do azocorante foram obtidos para os catalisadores cujos precursores eram complexos metálicos. Para estes materiais obteve-se um incremento de 65% em comparação com a ozonólise, sem que houvesse um grande aumento no consumo de ozônio. Para os materiais que continham La2O3, o catalisador cujo precursor do óxido foi um dos sais inorgânicos utilizados (nitrato de lantânio hidratado) apresentou o melhor teor de mineralização, sendo 72% superior em relação à ozonólise, ao final de 60 minutos. Os catalisadores contendo óxido de cério incorporado à SBA-15 também foram empregados no processo de ozonização catalítica de mais duas espécies orgânicas de grande relevância ambiental: fenol e ácido salicílico. Para o primeiro, houve um incremento mínimo na remoção da matéria orgânica de 70%, para todos os catalisadores testados, em relação à ozonólise, após 60 minutos. Entretanto, apenas dois deles (SBA-Ce(Gly) e SBA-Ce(Cl)) apresentaram um consumo de ozônio semelhante à ozonólise, o que indica que estes eram os mais eficientes. Na degradação do ácido salicílico a sinergia entre o suporte mesoporoso ordenado de elevada área superficial com o óxido de cério mais uma vez mostrou-se eficiente na mineralização da espécie orgânica, sendo obtidos teores de mineralização superiores a 90% para a ozonização catalítica contra 60% para a ozonólise, ao final de 60 minutos de tratamento / The aim of this work was the synthesis and characterization of materials with lanthanide oxides incorporated in ordered mesoporous silica, which were used as catalysts on the ozonation of organic pollutants. The incorporation of cerium and lanthanum oxides on the mesoporous support, SBA-15 type, was made by wet impregnation method. Different metal oxides precursors were used in order to investigate the influence in structural, textural and morphological characteristics of the materials and in catalytic activity. No collapse in the ordered mesopores structure of SBA-15 was observed after lanthanide oxides incorporation. However the hybrid compounds presented lower specific surface area and pore volume. It was observed the presence of CeO2 and La2O3 in the external support surface and in the interior of the mesopores. It was also possible to identify crystalline phases of these oxides after the incorporation step. The catalysts were employed on the degradation of an azo dye, Remazol Black B. For all samples it was found that the heterogeneous catalytic ozonization provided an increase in the mineralization levels of this organic species compared with the results of the ozonolysis. For the CeO2-based materials, the best results were achieved for the catalysts whose precursors were the metal complexes. For these materials the mineralization of the Remazol Black B was, at least, 65% superior to ozonolysis alone, without a great increase in the consumption of ozone. For the La2O3-based materials, the best result was obtained for the catalyst which oxide precursor was one of the inorganic salt (lanthanum nitrate hydrate). The mineralization was 72% higher than the ozonolysis alone after 60 minutes of treatment. The catalysts containing cerium oxide incorporated into the SBA-15 were also employed in the catalytic ozonization of two other organic species of great environmental importance: phenol and salicylic acid. For the first, there was a minimal increase in the removal of the organic matter when compared with ozonolysis alone. However, only two of them (SBA-Ce(Gly) e SBA-Ce(Cl)) showed a consumption of ozone similar to ozonolysis, indicating that these were the most efficient. In salicylic acid degradation, the mineralization achieved was greater than 90% for the catalytic ozonation versus 60% for the ozonolysis alone, after 60 minutes of treatment

Atmospheric aerosols affect climate change by altering the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. While the formation of secondary organic aerosol (SOA) from gas phase precursors is relatively well understood, it does not account for the abundance of SOA observed during field measurements. Recently it has become apparent that in-aerosol aqueous chemical reactions likely provide some of the missing sources of SOA production, and many studies of aqueous phase processes are underway. This work explores the fates of the simplest 2-oxocarboxylic acids, glyoxylic acid (GA) and pyruvic acid (PA), under simulated solar irradiation in the aqueous phase. Field measurements have revealed that mono-, di-, and oxocarboxylic acids are abundant species present in atmospheric waters. Of particular interest are 2-oxocarboxylic acids because their conjugated carbonyl moieties result in significant UV-visible absorption above 300 nm, allowing absorption of sunlight in the lower troposphere, thereby initiating radical photochemistry and leading to formation of SOA. In Chapter 2 of this work, GA is demonstrated to primarily undergo α-cleavage, producing CO, CO2, formic acid, and the key SOA precursor glyoxal. Trace amounts of oxalic acid and tartaric acid are also quantified. Additionally, the dark thermal aging of glyoxylic acid photoproducts, studied by UV-visible and fluorescence spectroscopies, reveals that the optical properties of the solutions are altered radically by the glyoxal produced. The optical properties display periodicity during photolytic-dark cycles, reflecting behavior expected for aerosols during nighttime and daytime cycles. In contrast, Chapter 3 shows that PA photoreacts via a proton-coupled electron transfer (PCET) mechanism that produces CO2 and organic acids of increased complexity with 6 to 8 carbons. A combination of analytical techniques including 1H and 13C NMR; 13C gCOSY NMR; mass spectrometry; chromatography; and isotope substitutions allows the organic products to be identified as: 2,3-dimethyltartaric acid; 2-hydroxy-2-((3-oxobutan-2-yl)oxy)propanoic acid; and the quasi-intermediate 2-(1-carboxy-1-hydroxyethoxy)-2-methyl-3-oxobutanoic acid. In Chapter 4, PA irradiation is also shown to consume dissolved oxygen so fast that solutions become depleted within a few minutes depending on reaction conditions. This fast process directly produces the atmospheric oxidant singlet oxygen, which enhances the oxidizing capacity of the atmosphere. Additionally, PA photochemistry only proceeds under very acidic conditions (pH ≤ 3.5), like those in most atmospheric aerosols. Finally, we require a thorough understanding of the behavior of 2-oxocarboxylic acids at the air-water interface of aerosols because much of the GA and PA present in the atmosphere is produced in the gas phase and needs to partition into the aqueous phase to undergo photoreaction. Therefore, Chapter 5 uses surface sensitive online electrospray ionization mass spectrometry (OESI-MS) to demonstrate that carboxylic acids delivered from the gas phase onto the surface of aqueous microdroplets display enhanced acidities relative to bulk water solutions. This work demonstrates that aqueous photolysis is a very competitive atmospheric fate for both GA and PA. It also shows that these photoreactions are capable of contributing substantially to SOA formation by building chemical complexity and forming oxidants directly.

Aerosols affect climate change, the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. Aerosols from natural and anthropogenic sources can be primary organic aerosols (POA), which are directly emitted to the atmosphere, or secondary organic aerosols (SOA) that are formed from chemical reactions of gas-phase precursors. At variance with the well investigated formation of SOA from gas phase precursors, the chemistry of aqueous SOAs that contribute to the total SOA budget remains unknown. Field measurements have revealed that carboxylic, dicarboxylic and oxocarboxylic acids are abundant species present in SOAs. This thesis explores the fate of two such acids, pyruvic (PA) and glyoxylic (GA) acids surrogates of the oxocarboxylic acids in the atmosphere, in their cross reaction under solar irradiation and dark thermal aging. Mixtures of complex photoproducts are identified by ion chromatography (IC) with conductivity and electrospray (ESI) mass spectrometry (MS) detection, direct ESI-MS analysis in the negative ion mode, and nuclear magnetic resonance spectroscopy (NMR) analysis including one-dimensional (1H- and 13C-NMR) and two-dimensional techniques such as gradient correlation spectroscopy (gCOSY) and heteronuclear single quantum correlation (HSQC). A reaction mechanism for the cross reaction is provided based on all experimental observations.

Mobile source emissions are a major contributor to global and local air pollution. Governments and regulatory agencies have been increasing the stringency of regulations in the transportation sector for the last ten years to help curb transportation sector air pollution. The need for regulations has been emphasized by scientific research on the impacts from ambient pollution, especially research on the effect of particulate matter on human health. The particulate emissions from diesel vehicles, diesel particulate matter (DPM) is considered a known or probable carcinogen in various countries and increased exposure to DPM is linked to increased cardiovascular health problems in humans. The toxicity of vehicle emissions and diesel particulate emissions in particular, in conjunction with an increased awareness of potential petroleum fuel shortages, international conflict over petroleum fuel sources and climate change science, have all contributed to the increase of biodiesel use as an additive to or replacement for petroleum fuel. The goal of this research is to determine how this increased use of biodiesel in the particular emission testing setup impacts urban air quality. To determine if biodiesel use contributes to a health or climate benefit, both the size range and general composition were investigated using a comprehensive comparison of the particulate component of the emissions in real time. The emissions from various biodiesel and diesel mixtures from a common diesel passenger vehicle were measured with a cavity ring-down transmissometer (CRDT) coupled with a condensation particle counter, a SMPS, a nephelometer, NOx, CO, CO2, and O3 measurements. From these data, key emission factors for several biodiesel and diesel fuel mixtures were developed. This approach reduces sampling artifacts and allows for the determination of optical properties, particle number concentration, and size distributions, along with several important gas phase species' concentrations. Findings indicate that biodiesel additions to diesel fuel do not necessarily have an air quality benefit for particulate emissions in this emission testing scenario. The often cited linear decrease in particulate emissions with increasing biodiesel content was not observed. Mixtures with half diesel and half biodiesel tended to have the highest particulate emissions in all size ranges. Mixtures with more than 50% biodiesel had slightly lower calculated mass for light absorbing carbon, but this reduction in mass is most likely a result of a shift in the size of the emission particles to a smaller size range, not a reduction in the total number of particles. Evaluation of the extensive optical properties from this experimental set-up indicates that biodiesel additions to diesel fuel has an impact on emission particle extinction in both visible and near-IR wavelengths. The B99 mixture had the smallest emission factor for extinction at 532 nm and at 1064 nm. For the extinction at 532 nm, the trend was not linear and the emission factor peaked at the B50 mixture. Results from intensive properties indicate that emissions from B5 and B25 mixtures have Ångström exponents close to 1, typical for black carbon emissions. The mixtures with a larger fraction of biodiesel have Ångström exponent values closer to 2, indicating more absorbing organic matter and/or smaller particle size in the emissions. Additional experimental testing should be completed to determine the application of these results and emission factors to other diesel vehicles or types of diesel and biodiesel fuel mixtures.