Os hidrocarbonetos policíclicos aromáticos (HPAs) e seus derivados nitrados (nitro-HPAs) e oxigenados (oxi-HPAs) são compostos de grande interesse devido seus efeitos deletérios à saúde. Estes compostos são encontrados associados ao material particulado atmosférico e são formados durante a combustão de compostos orgânicos, no caso dos HPAs, e também por reações in situ através dos HPAs precursores, no caso dos nitro- e oxi-HPAs. Para avaliar a influência da queima de cana-de-açucar, amostras de material particulado foram coletadas nas cidades de Ourinhos e Araraquara (Estado de São Paulo), regiões afetadas pela queima de cana-de-açucar. Os filtros carregados foram submetidos à extração por Soxhlet, o extrato orgânico foi fracionado por HPLC e as frações de interesse foram analisadas por cromatografia a gás. Foram investigados 12 HPAs, 7 nitro-HPAs e 3 oxi-HPAs. Na cidade de Ourinhos coletou-se material particulado total (MPT) e material particulado em diferentes tamanhos. Os HPAs e a benzantrona (oxi-HPA) apresentaram concentrações maiores nas partículas menores, ao passo que nitro-HPA e os outros dois oxi-HPAs estudados (9-fluorenona e 9,10-antrona) predominaram nas partículas maiores. Em Araraquara foram coletadas amostras de MPT nos períodos diurno e noturno, e amostras de 24h nos períodos de safra e entressafra. Os HPAs e a benzantrona apresentaram predominância no período noturno, sugerindo que esses compostos devem ter sido provenientes de emissões da queima da cana-de-açucar, ao passo que os outros dois oxi-HPAs estudados (9-fluorenona e 9,10-antraquinona) não apresentaram esse comportamento. Os nitro-HPAs foram detectados em poucas amostras noturnas, provavelmente devido ao processo de remoção destes compostos por fotólise durante o dia. As correlações altas entre HPAs e alguns nitro-HPAs sugerem que tais compostos são provenientes provavelmente das mesmas fontes que os HPAs, embora alguns nitro-HPAs possam também ser formados in situ. Os compostos oxi-HPAs apresentaram correlações com alguns HPAs, mas devem ser também oriundos de outras fontes de emissão além da queima da cana-de-açúcar. De um modo geral, a queima desse tipo de biomassa parece influenciar nos níveis atmosféricos dos compostos estudados. / The polycyclic aromatic hydrocarbons (PAH) and their nitrated (nitro-PAH) and oxygenated (oxy-PAH) derivatives are compound of great interest due to their noxious effects on health. These compounds are found associated to the atmospheric particulate matter and are formed during the organic compound combustion, in case of PAH, and also by in situ reactions through the PAH precursors, in case of nitro- and oxy-PAH. In order to evaluate the sugar cane burning influence, particulate matter samples were collected at Ourinhos and Araraquara cities and submitted to Soxhlet extraction, frationating by HPLC and analized by gas-chromatography. 12 PAH, 11 nitro-PAH and 3 oxy-PAH were investigated. Total particulate matter and particulate matter in different particle sizes were collected at Ourinhos. Particulate matter in different particle sizes presented maximum concentration of PAH and benzanthrone (oxi-PAH) in the smaller particles, while nitro-PAH and the two other oxy-PAH (9-fluorenone and 9,10-anthraquinone) predominated in the larger particles. The sampling of total particulate matter in Araraquara was carried out in daytime and nighttime periods and also 24h sampling in harvest and post-harvest seasons. The PAH and the benzanthrone presented predominance in the nighttime period, suggesting sugar cane burning emissions. Moreover, the other two oxy-PAH (9-fluorenone and 9,10-anthraquinone) did not show that behavior. The nitro-PAH were detected in a few samples, and only at nighttime period in some cases. This is probably due to removal by photolysis during the daytime. The correlations between the compounds suggest a commom source between PAH and some nitro-PAH, although nitro-PAH can also be formed in situ. The oxy-PAH presented some correlations with PAH, but it seems that oxygenated PAH have another emission sources appart from burning. Biomass burning seems to influenciate the PAH and derivative levels in atmosphere.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-10-24T12:57:59Z No. of bitstreams: 1 PATRICIA_DISSETAÇÃO_MESTRADO_GEOQUIMICA_2009.pdf: 4047978 bytes, checksum: b2a1f62ef245a5a0d8afcc3ae828bf17 (MD5) / Made available in DSpace on 2017-10-24T12:57:59Z (GMT). No. of bitstreams: 1 PATRICIA_DISSETAÇÃO_MESTRADO_GEOQUIMICA_2009.pdf: 4047978 bytes, checksum: b2a1f62ef245a5a0d8afcc3ae828bf17 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo a Pesquisa do Estado do Rio de Janeiro / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / A cidade de São José dos Campos localizada no Vale do Paraíba é considerada uma área altamente suscetível à poluição do ar devido à geografia desta região, caracterizada por cadeias montanhosas que dão origem a Serra do Mar e Mantiqueira, dificultando a circulação geral da atmosfera e comprometendo a dispersão de poluentes atmosféricos bem como às emissões industriais de alto potencial poluidor proveniente dos parques industriais existente na região e suas vizinhanças. O objetivo do trabalho é caracterizar o material particulado atmosférico fino (PM2,5) e grosso (PM2,5-10) e determinar a composição química dos constituintes inorgânicos solúveis em água associados a estas partículas. As amostras de PM2,5 e PM2,5-10 foram coletadas semanalmente, em período contínuo de 24 h, por intermédio de um amostrador Dicotômico PM10 Sierra-Andersen em São José dos Campos entre fevereiro de 2004 a fevereiro de 2005 totalizando 60 amostragens. As concentrações médias anuais ± desvio padrão de PM2,5 e PM2,5-10 foram respectivamente iguais a 15,7 ± 7,9 e 14,8 ± 8,4 μg m-3. As maiores concentrações de particulado fino e grosso ocorreram no período de estiagem, enquanto que as concentrações mais baixas no período de chuvas, evidenciando o papel fundamental das chuvas na limpeza da atmosfera . Os íons NH4 + e SO4 2- ocorreram predominantemente no particulado fino correspondendo a 62% do total dos constituintes e 20 % da massa; por outro lado, os íons Cl-, Na+ e NO3 - predominaram no particulado grosso equivalendo, juntos, a 54 % dos íons inorgânicos e 11% da massa. Em média, 96% do SO4 2- associado ao PM2,5 equivale ao excesso de SO4 2-, ou seja, a outras fontes naturais e/ou antrópicas não provenientes do sal do mar. A razão NH4 +/ (Exc-SO4 2- + NO3 -) encontrada no PM2,5 igual a 1,08 sugere a formação de aerossóis de (NH4)2SO4 e NH4NO3 provenientes de atividades antrópicas. O déficit médio de cloreto foi de 42% para o PM2,5 e de 39% para o PM2,5-10. O déficit de Cl- para o PM2,5 durante o período de estiagem foi 4 vezes maior do que no período de chuvas, sendo o mesmo não observado para o PM2,5-10. Mais de 90% do K+, Ca2+ e Mg2+ encontrados em ambas as frações finas e grossas representa a parcela não-marinha (natural e/ou antrópica) destes íons. A modelagem hysplit para as retrotrajetórias de massas de ar auxiliou na identificação de episódios de transporte a longa distância, de material particulado de procedência continental e marítima em amostras que apresentaram composição química extremamente alta. A distribuição de chuvas ao longo do período de estudo, foi fundamental para o entendimento do comportamento sazonal das partículas atmosféricas finas e grossas em São José dos Campos. / São José dos Campos, located in the Paraíba Valley, is an area considered highly susceptible to air pollution because of its geography, characterized by mountain ranges that result in Serra do Mar and Mantiqueira, disturbing the general circulation of the atmosphere and threatening the dispersion of air pollutants as well as the high pollution potential emissions from industrial parks that exist in the region and in neighborhood. The objective of this study is to characterize the atmospheric fine (PM2,5) and coarse particulate (PM2,5-10) matter and determine the chemical composition of water-soluble inorganic constituents of these particles. The samples of PM2,5 and PM2,5-10 were weekly collected, in a continuous period of 24 hours with a PM10 dichotomic Sierra-Andersen sampler in São José dos Campos between February 2004 and February 2005, totalizing 60 samples. The annual average concentrations ± standard deviation of PM2,5 and PM2,5-10 were, respectively, 15,7 ± 7,9 and 14,8 ± 8,4 μg m-3. The highest concentrations of fine and coarse particulate matter occurred in the period of drought while lower concentrations were found in rainy period, highlighting the fundamental role of rain in cleaning the atmosphere. NH4 + and SO4 2- ions occurred predominantly in fine particulate matter corresponding to 62% of all constituents and 20% of the mass, on the other hand, Cl-, Na+ and NO3 - ions predominated in coarse particulate matter together amounting 54% of inorganic ions and 11% of the mass. On average 96% of the SO4 2- associated with PM 2,5 equal the Exc-SO4 2-, i.e. other natural and/or anthropic sources not from saltwater. The reason NH4 + / (Exc-SO4 2- + NO3 -) found in PM2,5 equals 1.08 suggesting the formation of (NH4)2SO4 and NH4NO3 aerosols from human activities. The average deficit of chloride was 42% for PM2,5 and 39% for PM2,5-10. The deficit of Cl- for PM2,5 during the drought period was 4 times higher than the one found in the rainy period, the same was not observed for PM 2,5-10. Over 90% of K+, Ca2+ and Mg2+ found in both fine and coarse fractions represent the non-marine parcel (natural and/or antropic) of those ions. The modeling hysplit for air masses retrotrajectories helped identifying long-distance transport episodes, particulate matter of continental and marine origin in samples that showed extremely high chemical composition. The distribution of the rain throughout the study was fundamental for understanding the seasonal behavior of atmospheric fine and coarse particles in Sao Jose dos Campos.

Atmospheric fine particulate matter (PM2.5), which is mostly formed in the atmosphere from precursor gases, contributes to numerous environmental and health concerns. Quantifying the ambient concentrations of PM2.5 and precursor gases can be challenging. Hence, many scientific questions about the formation, chemical composition, and gas/particle partitioning of PM2.5 remain unanswered. Ambient Ion Monitor - Ion Chromatography (AIM-IC) was characterized and utilized to measure the water-soluble composition of PM2.5 (dominated by pNH4+, pSO42-, and pNO3-) and associated precursor gases (dominated by NH3(g), SO2(g), and HNO3(g)) during two field campaigns. The AIM-IC detection limits for hourly sampling were determined to be 3 - 45 ng m-3. The response time for “sticky” gases was significantly improved with a nylon denuder membrane. A novel inlet configuration for the AIM-IC, which minimizes sampling inlet losses and carryover in sample analyses, was implemented. Measurements from the BAQS-Met 2007 campaign were utilized to assess the accuracy of the AURAMS model and investigate gas/particle partitioning in SW Ontario. Due to high sulphate levels, NH3(g) was the limiting chemical factor in the formation and gas/particle partitioning of PM2.5. The errors in the predictions of relative humidity and free ammonia were responsible for the poor agreement iii between modelled and measured pNO3- values. The AIM-IC measurements from the CalNex 2010 study were compared to the CMAQ model and utilized to investigate the gas/particle partitioning in Bakersfield, CA. Very high NH3(g) concentrations were observed, and the formation and partitioning of PM2.5 was limited by HNO3(g) and H2SO4. Evidence of rapid removal of HNO3(g) by interactions with super-micron dust particles, and possibly with the alkaline surface was found. CMAQ exhibited significant biases in the predicted concentrations of pSO42-, NH3(g) and HNO3(g).

Atmospheric fine particulate matter (PM2.5), which is mostly formed in the atmosphere from precursor gases, contributes to numerous environmental and health concerns. Quantifying the ambient concentrations of PM2.5 and precursor gases can be challenging. Hence, many scientific questions about the formation, chemical composition, and gas/particle partitioning of PM2.5 remain unanswered. Ambient Ion Monitor - Ion Chromatography (AIM-IC) was characterized and utilized to measure the water-soluble composition of PM2.5 (dominated by pNH4+, pSO42-, and pNO3-) and associated precursor gases (dominated by NH3(g), SO2(g), and HNO3(g)) during two field campaigns. The AIM-IC detection limits for hourly sampling were determined to be 3 - 45 ng m-3. The response time for “sticky” gases was significantly improved with a nylon denuder membrane. A novel inlet configuration for the AIM-IC, which minimizes sampling inlet losses and carryover in sample analyses, was implemented. Measurements from the BAQS-Met 2007 campaign were utilized to assess the accuracy of the AURAMS model and investigate gas/particle partitioning in SW Ontario. Due to high sulphate levels, NH3(g) was the limiting chemical factor in the formation and gas/particle partitioning of PM2.5. The errors in the predictions of relative humidity and free ammonia were responsible for the poor agreement iii between modelled and measured pNO3- values. The AIM-IC measurements from the CalNex 2010 study were compared to the CMAQ model and utilized to investigate the gas/particle partitioning in Bakersfield, CA. Very high NH3(g) concentrations were observed, and the formation and partitioning of PM2.5 was limited by HNO3(g) and H2SO4. Evidence of rapid removal of HNO3(g) by interactions with super-micron dust particles, and possibly with the alkaline surface was found. CMAQ exhibited significant biases in the predicted concentrations of pSO42-, NH3(g) and HNO3(g).