Chapter 1. Background: Asthma is the most common chronic childhood disease and is characterized by recurrent airway obstruction, bronchial hyper-responsiveness, and airway inflammation. Asthma is the leading cause of childhood hospitalization and school absenteeism in the United States. The associations between adverse respiratory effects and exposure to indoor nitrogen dioxide (NO2) and other byproducts of combustion such as particulate matter (PM) in particular ultrafine particulates (UFP), Ozone (O3) and Sulfur Dioxide (SO2), have been the focus of many epidemiological studies in recent years. Indoor exposure to NO2 and other pollutants from combustion may increase the risk of acute and chronic respiratory disease, reduce lung function, initiate and exacerbate asthma in children. The levels of exposure to NO2 indoors are of public health concern because children spend nearly 70% of their time indoors at home. According to the 2010 US Census report, approximately 39% of US households use natural gas for cooking, and the primary source of residential NO2 is a gas-fuel cooking appliance. Indoor levels of NO2 where NO2 sources are present can be much higher than outdoors, where the primary source of NO2 is vehicular traffic. Epidemiological studies in developed countries suggest that gas stoves used for cooking and/or heat are associated with an increased risk of asthma and respiratory symptoms in children. While there are numerous, epidemiological studies supporting an association between increased NO2 levels and gas stoves and asthma symptom severity in children, there are other studies that have examined the relationship in homes that did not observe significant associations. A better understanding of how NO2 and other indoor environmental (e.g., environmental tobacco smoke (ETS), allergens) exposures contribute to asthma morbidity in inner city preschool children will allow interventions to more effectively designed and implemented. To date, there are conflicting results on the role of exposure to indoor NO2 and its association with new-onset asthma in young inner-city children. The recent studies assessing the effects of indoor NO2 on asthma morbidity were limited to inner-city children, largely older, who were diagnosed with asthma. A gap in knowledge remains regarding the role indoor NO2 plays on the development of asthma in children not previously diagnosed. The scientific and public health rationale for conducting this dissertation was to describe the association of exposure to indoor NO2 and primary sources with the initiation and exacerbation of asthma symptoms among pre-school children with and without diagnosed asthma. The data analyzed in the current research come from a larger study of Endotoxin, Obesity, and Asthma (EOA) in the New York City Head Start Program, funded in the summer of 2002. The primary research objective of that study was to identify modifiable risk factors associated with asthma and asthma persistence among preschool children from low-income families living in select New York City neighborhoods with high pediatric asthma hospitalization rates. We conducted a cross-sectional analysis of data collected from the study questionnaire and home visit sampling at study enrollment. The analyses were performed in two phases: the first phases used data collected at study enrollment and the second phase used data collected 12-months after study baseline. Henceforth, the dissertation will refer to the first analyses as the baseline study and the second as the follow-up study. The research evaluated the association of NO2 exposure with asthma status among New York City Head Start children with and without asthma at study enrollment and with respiratory symptoms among children with asthma at 12-month follow-up. Chapter 2. Baseline Study: We conducted a cross-sectional analysis of data collected from the study questionnaire and home visit sampling at study enrollment. Specifically, the research sought to evaluate the association of NO2 exposure with asthma status among New York City Head Start children with and without asthma at study enrollment and with respiratory symptoms among children with asthma at enrollment. A total of 503 children were included in the baseline study. A total of 105 children (20.9%) met the criteria for both asthma and allergy, and 67 (13.3%) met the criteria for asthma alone. Girls made up 51.7% and boys, 48.3% of the 503 study participants. Descriptive analyses suggested that asthma/allergy status was associated with: male gender, non-Mexican ethnicity/national origin, presence of a smoker in the child’s home, number of smokers in the child’s home, self-reported parental history of asthma, mother’s education level and sensitization to one or more of the four allergens. Logistic regression models were used to investigate the magnitude and direction (as well as trend) of the association between childhood asthma and indoor NO2 sources in the child’s home. Chapter 3. Follow-up Study: Our follow-up study involved the analysis of the 12-month follow-up data from the study of Endotoxin, Obesity, and Asthma in the New York City Head Start Program funded in the summer of 2002. We focused on assessing the magnitude and direction of the associations of exposure to indoor NO2 levels (based on baseline NO2 measurements) with children’s asthma status and with symptom severity among asthmatics at 1-year follow-up. For the follow-up study, we categorized children by whether their asthma status had changed since baseline. Descriptive analyses were performed looking at key characteristics by “change in asthma status.” Children’s asthma status at baseline and at follow-up, were based on responses to the questionnaire. We analyzed indoor NO2 level measurements at baseline in relation to asthma outcomes on follow-up. We did not have enough data on NO2 levels at follow-up to analyze them in relation to asthma status on follow-up. Unless the family had relocated since baseline and/or reported changes since baseline in the use of gas appliances or the number of smokers in the home, we assumed that baseline NO2 levels in the participating children’s homes were reasonable proxies for current exposures. We looked at the number of children who moved since baseline and whether the move (for example, looking at gas stove status, age of new building) may have impacted indoor NO2 levels. Of the 503 children who were included in the baseline analyses, 47.3% had data on asthma status on follow-up. A total of 238 children (111 male, 127 female) were grouped into the four mutually exclusive outcome categories: 122 (51.3%) did not have asthma at baseline or on follow-up, 34 (14.3%) had asthma on follow-up but not at baseline, 65 (27.3%) had asthma at baseline but not on follow-up, and 17 (7.1%) had asthma at baseline and on follow-up. The mean age at 1-year follow-up was 59.5 months (6.95), and neither age nor gender was associated with asthma. The distribution of ethnicity/national origin among the 238 children remained the same as at baseline; no one ethnicity group experienced disproportionate loss to follow-up, and asthma status remained associated with non-Mexican ethnicity/national origin, although 44.1% with new-onset asthma were of Mexican background. Asthma was also associated with self-reported parental history of asthma and allergy in children, but nearly 80% of children with new-onset asthma had no such parental history of asthma. More parents of children with new-onset (35.3%) or persistent asthma (23.5%) than of other children reported making efforts to reduce risk factors or triggers for asthma exacerbations in the past 12 months. Chapter 4. Dissertation Conclusion : The primary objective of the dissertation research was the examination of the relationship between asthma and asthma severity and exposure to gas cooking and residential NO2. In both our baseline and 12-month follow-up studies, exposure to indoor NO2 was represented by the baseline measurement of NO2 and the NO2 surrogate, gas stove. Asthma status of children was based on parental responses on the questionnaire regarding asthma symptoms and urgent care visits due to respiratory distress over the course of each 12-month period prior to the conducting study questionnaires. For both studies, we did not find an association between exposure to NO2 levels at baseline and asthma status or severity. Our findings contradict the results of most recent studies of both NO2 levels and residential sources of NO2 and their effects on asthma symptoms in very young children. However, it remains difficult to compare our results we those of previous published studies because those studies primarily focused on children who were diagnosed with asthma, whereas our research included preschool aged children with and without asthma. Based on our findings and the fact they conflict with other epidemiological studies, of which there were also conflicting results, we feel that the relationship between asthma symptoms and NO2 exposures remains ambiguous. The lack of consistent results of epidemiological research raises questions that should be the focus of future epidemiological studies. What are the roles of co-pollutants and co-risk factors? Does NO2 work alone or in concert with other indoor pollutants? There exists a real lack of understanding on the possible synergistic effects of exposure to NO2 and other combustion byproducts. Important to furthering our knowledge of the role of exposure to indoor NO2 and asthma is determining whether NO2 acts as a surrogate for co-pollutants that are considered risk factors for asthma and other respiratory conditions. Another focus of future indoor pollution studies should be the development of effective methods and technologies for measuring the constituents of the complex mixture of pollutants in indoor air; these methods and technologies can then be applied in personal monitoring of exposure to indoor pollutants in epidemiological studies that would help to determine with much more accuracy the effects of individual indoor pollutants on asthma and other respiratory symptoms. This knowledge would help in the development of more effective public health and environment policies towards reducing the burden of childhood asthma.

Introdução: A poluição do ar é resultado de complexas interações que envolvem emissões de poluentes atmosféricos e que sabidamente causam consequências negativas para a saúde humana. De acordo com alguns estudos, a exposição à poluição, durante a gestação, pode afetar o peso ao nascimento, contudo, não há ainda conhecimento sedimentado sobre as janelas críticas de exposição à poluição durante a gestação e quais os efeitos no crescimento fetal e no fluxo placentário. Objetivos: Visando investigar, mais profundamente, o impacto da poluição na vida intrauterina, o objetivo deste estudo foi avaliar a influência da exposição à poluição, nos três trimestres da gestação, no crescimento fetal e na hemodinâmica feto-placentária avaliados no terceiro trimestre da gestação. Métodos: Foi realizado um estudo prospectivo com 386 gestantes, na cidade de São Paulo, intitulado ProcriAR. Os poluentes dióxido de nitrogênio (NO2) e ozônio (O3) foram medidos durante cada trimestre da gestação por meio da utilização de amostradores passivos individuais. No terceiro trimestre, foi realizada ultrassonografia fetal na qual foram avaliados: o diâmetro biparietal, a circunferência craniana, a circunferência abdominal, o comprimento do fêmur, o peso fetal, o índice de líquido amniótico e os índices de pulsatilidade (IP) de sonograma das artérias umbilical, cerebral média e uterinas. Foi realizada análise multivariada, controlada por idade materna, no momento da concepção, índice de massa corporal (IMC), paridade, tabagismo, consumo de álcool, cor, nível de escolaridade, estado civil, idade gestacional no momento do exame e sexo fetal. Resultados: Menor circunferência cefálica foi associada com a exposição ao O3 no primeiro trimestre (p = 0,012; beta = -0,005; intervalo de confiança de 95% (IC 95%), - 0,008, -0,001), e maior circunferência cefálica foi associada com a exposição ao NO2 no primeiro trimestre (p = 0,033; beta = 2,5 x 10-4; IC 95%, 2 x 10-5, 4,8 x 10-4). A exposição ao O3 no segundo trimestre foi associada a maiores valores de IP da artéria umbilical (p = 0,006; beta = 0,018; IC 95%, 0,005, 0,030), porém a exposição ao O3 no terceiro trimestre foi associada a menores valores de IP da umbilical (p = 0,004; beta = - 0,022; IC 95%, -0,037, - 0,007). Conclusão: Nossos resultados sugerem que, no ambiente de São Paulo, o O3 pode interferir no crescimento do polo cefálico e na resistência vascular placentária / Background: Air pollution may influence fetal growth and placental flow according to trimester-specific exposure. Objectives: To determine the influence of maternal air pollution exposure during each trimester of pregnancy on fetal growth and fetoplacental hemodynamics. Methods: ProcriAR, a prospective cohort study of 386 pregnant women, was conducted in the city of São Paulo. Nitrogen dioxide (NO2) and ozone (O3) were measured during each trimester using passive personal monitors. In trimester 3, we evaluated the biparietal diameter, head circumference, abdominal circumference, femur length, fetal weight, amniotic fluid index and Doppler velocimetry data of the umbilical, middle cerebral and uterine arteries. Multivariate analysis was performed, controlling for maternal age at conception, body mass index, parity, smoking, alcohol consumption, race, highest education level completed, and marital status and the fetus\'s gestational age and sex. Results: Reduced head circumference was associated with O3 exposure in trimester 1 (p = 0.012; beta = -0.005; 95% confidence interval (CI), -0.008, -0.001), and increased head circumference was associated with NO2 exposure in trimester 1 (p = 0.033; beta = 2.5 x 10-4; 95% CI, 2 x 10-5, 4.8 x 10-4). Exposure to O3 during the second and third trimesters was associated with higher (p = 0.006; beta = 0.018; 95% CI, 0.005, 0.030) and lower (p = 0.004; beta = -0.022; 95% CI, -0.037, -0.007) umbilical artery pulsatility values, respectively. Conclusion: Our results suggest that in the environment of São Paulo, O3 may interfere with fetal growth and vascular resistance

Introdução: A poluição do ar é associada a alterações no crescimento fetal, especialmente à restrição de crescimento fetal. Porém, não há estudos que tenham avaliado a exposição individual ao NO2 e O3 em relação ao padrão de crescimento fetal esperado de acordo com a curva personalizada de crescimento fetal. Objetivo: Avaliar a influência da poluição, nutrientes antioxidantes e fatores socioeconômicos no padrão de crescimento fetal. Métodos: Estudo prospectivo com 301 gestantes entre março de 2011 e dezembro de 2013, incluídas no projeto PROCRIAR, provenientes de quatro Unidades Básicas de Saúde da zona oeste da cidade de São Paulo. Os critérios de inclusão foram: gestação única, idade gestacional inferior a 14 semanas no momento da primeira ultrassonografia, ausência de doenças maternas preexistentes, concordância com o Termo de Consentimento Livre e Esclarecido (TCLE).Os critérios de exclusão foram: diagnóstico de abortamento, morte fetal, malformação fetal, diabetes mellitus gestacional, pré-eclâmpsia, mudança de endereço para fora da área de recrutamento, desistência da participação, não comparecimento aos exames ultrassonográficos subsequentes, Amostradores Passivos Individuais (API) sem condições adequadas para análise e impossibilidade de definir o padrão de crescimento fetal (mudança nas faixas de classificação do crescimento fetal em todas as medidas ultrassonográficas e de peso no nascimento).Os poluentes (NO2 e O3) foram avaliados através de amostradores passivos individuais que as gestantes carregavam na semana anterior a avaliação ultrassonográfica, em cada trimestre gestacional. O peso fetal foi estimado através do diâmetro biparietal, circunferência cefálica, circunferência abdominal e comprimento do fêmur e o crescimento fetal foi avaliado através da curva de peso fetal personalizada e posteriormente os fetos foram classificados de acordo com o padrão de crescimento fetal em estável, diminuído ou aumentado. Foram avaliadas a influência dos fatores socioeconômicos, nutricionais e da poluição nos trimestres gestacional. Resultados: Escolaridade com menos de oito anos de estudo e a maior exposição do O3 no segundo e terceiro trimestre foram associados à diminuição do padrão de crescimento fetal (p=0,003, p=0,044 e p=0,007, respectivamente). Não observamos relação entre os níveis de NO2 e mudanças no padrão de crescimento fetal. Em relação aos nutrientes antioxidantes não foi encontrada relação com o padrão de crescimento fetal. Conclusão: Níveis mais elevados O3 no segundo e terceiro trimestre e escolaridade com menos de 8 anos de estudo associam-se à diminuição no padrão crescimento fetal / Background: Air pollution is associated with changes in fetal growth, particularly fetal growth restriction. However, no studies have evaluated the association between individual exposure to nitrogen dioxide (NO2) and ozone (O3) and the expected fetal growth pattern according to the individualized fetal growth curve. Objectives: The objective of the present study was to evaluate the effects of pollution, nutrition and socioeconomic factors on fetal growth. Methods: A prospective study with 301 pregnant women between March 2011 and December 2013, included in the PROCRIAR project, from 4 primary care centers of the western area of São Paulo. Inclusion criteria were single gestation, gestational age less than 14 weeks at the time of first ultrasound, absence of preexisting maternal diseases, and signing the Informed Consent Document. Exclusion criteria were a diagnosis of miscarriage, stillbirth, fetal malformation, gestational diabetes mellitus, preeclampsia, change of address out of the recruiting area, withdrawal from participation, absent at subsequent ultrasound examinations, Personal Passive Samplers without adequate conditions for analysis and an inability to define the fetal growth pattern (change in the fetal growth classification bands in all ultrasound and birthweight measurements). The pollutants (NO2 and O3) were evaluated through personal passive samplers that the pregnant women carried in the previous week of the ultrasonographic evaluation, in each gestational trimester. Fetal weight was estimated through biparietal diameter, cephalic circumference, abdominal circumference and femur length, and fetal growth was assessed using the custom fetal weight curve and the fetuses were then classified according to the fetal growth pattern as stable, decreased or increased. The influence of socioeconomic, nutritional and pollution factors in the gestational trimesters were evaluated. Results: We evaluated 301 patients. Lower levels of education and higher O3 concentrations in the second and third trimesters were associated with decreased fetal growth (p=0,003, p=0,044 e p=0,007, respectively). We did not observe a relationship between NO2 levels and changes in the fetal growth pattern. No correlation between the levels of antioxidant nutrients and fetal growth pattern was observed. Conclusions: Higher O3 levels in the second and third trimesters and less than 8 years of education are associated with a decrease in the fetal growth pattern

<p>This thesis studied environmental factors in relation to asthma and respiratory symptoms among schoolchildren in two countries. In Sweden, 1014 pupils (5-14 year) in 8 schools participated. Wheeze was reported by 7.8%, current asthma by 5.9%, doctor-diagnosed asthma by 7.7%, cat allergy by 6.8% and dog allergy by 4.8%. Current asthma was less common among those consuming more fresh milk and fish. Doctor-diagnosed asthma was less common among those consuming olive oil. Cat, dog and horse allergens were common in settled dust and related to respiratory symptoms. Pupils consuming butter and fresh milk had less respiratory symptoms in relation to allergen exposure. In schools with increased levels of microbial volatile organic compounds and selected plasticizers (Texanol and TXIB) asthma and respiratory symptoms were more common.</p><p>In Korea, 2365 pupils (9-11 year) in 12 schools participated (96%). In total, wheeze was reported by 8.0%, current asthma by 5.7%, doctor-diagnosed asthma by 5.4%, cat allergy by 2.6% and dog allergy by 4.9%. Contamination of dog and mite (<i>Dermatophagoides farinae</i>) allergen was common while cat allergen was uncommon. Remodelling, changing floor and building dampness at home were positively associated with asthma and respiratory symptoms. The strongest associations were found for floor dampness. Indoor/outdoor concentration of NO₂, formaldehyde and ultrafine particles (UFP) at schools were positively associated with asthma and respiratory symptoms. </p><p>When comparing Sweden and Korea, Korean pupils had more breathlessness and asthma but reported less cat and pollen allergy. Swedish schools had CO₂-levels below 1000 ppm, while most Korean schools exceeded this standard. Since both home and school environment may affect pupil’s asthma and respiratory symptoms, air quality should be an important health issue. Moreover, changes in dietary habits may be beneficial to decrease asthma and allergies. Furthermore, interaction between diet and environment needs to be further investigated.</p>

This thesis studied environmental factors in relation to asthma and respiratory symptoms among schoolchildren in two countries. In Sweden, 1014 pupils (5-14 year) in 8 schools participated. Wheeze was reported by 7.8%, current asthma by 5.9%, doctor-diagnosed asthma by 7.7%, cat allergy by 6.8% and dog allergy by 4.8%. Current asthma was less common among those consuming more fresh milk and fish. Doctor-diagnosed asthma was less common among those consuming olive oil. Cat, dog and horse allergens were common in settled dust and related to respiratory symptoms. Pupils consuming butter and fresh milk had less respiratory symptoms in relation to allergen exposure. In schools with increased levels of microbial volatile organic compounds and selected plasticizers (Texanol and TXIB) asthma and respiratory symptoms were more common. In Korea, 2365 pupils (9-11 year) in 12 schools participated (96%). In total, wheeze was reported by 8.0%, current asthma by 5.7%, doctor-diagnosed asthma by 5.4%, cat allergy by 2.6% and dog allergy by 4.9%. Contamination of dog and mite (Dermatophagoides farinae) allergen was common while cat allergen was uncommon. Remodelling, changing floor and building dampness at home were positively associated with asthma and respiratory symptoms. The strongest associations were found for floor dampness. Indoor/outdoor concentration of NO2, formaldehyde and ultrafine particles (UFP) at schools were positively associated with asthma and respiratory symptoms. When comparing Sweden and Korea, Korean pupils had more breathlessness and asthma but reported less cat and pollen allergy. Swedish schools had CO2-levels below 1000 ppm, while most Korean schools exceeded this standard. Since both home and school environment may affect pupil’s asthma and respiratory symptoms, air quality should be an important health issue. Moreover, changes in dietary habits may be beneficial to decrease asthma and allergies. Furthermore, interaction between diet and environment needs to be further investigated.

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

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) was applied to retrieve tropospheric NO2 and aerosol vertical profiles from downtown Toronto, and King City, Ontario during select periods in 2006 – 2010. Linear regression of MAX-DOAS NO2 vertical column density (VCD) versus OMI (satellite) VCD yielded a good correlation (R = 0.88) and MAX-DOAS negative bias of 20%, which was within the reported uncertainty of the MAX-DOAS and OMI VCD. The average regional Toronto VCD (remotely-sensed via MAX-DOAS and OMI) was half of the near-road VCD obtained in-situ (2.4 x 1016 ± 1.2 x 1016 molec/cm2). MAX-DOAS measurements of O4 were coupled with radiative transfer modeling to obtain vertical aerosol extinction profiles and aerosol optical depth (AOD). A strong linear agreement was observed between PM2.5 concentration and aerosol extinction coefficient (R = 0.92), and MAX-DOAS versus sun photometer AOD (slope = 0.94; R= 0.90).

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) was applied to retrieve tropospheric NO2 and aerosol vertical profiles from downtown Toronto, and King City, Ontario during select periods in 2006 – 2010. Linear regression of MAX-DOAS NO2 vertical column density (VCD) versus OMI (satellite) VCD yielded a good correlation (R = 0.88) and MAX-DOAS negative bias of 20%, which was within the reported uncertainty of the MAX-DOAS and OMI VCD. The average regional Toronto VCD (remotely-sensed via MAX-DOAS and OMI) was half of the near-road VCD obtained in-situ (2.4 x 1016 ± 1.2 x 1016 molec/cm2). MAX-DOAS measurements of O4 were coupled with radiative transfer modeling to obtain vertical aerosol extinction profiles and aerosol optical depth (AOD). A strong linear agreement was observed between PM2.5 concentration and aerosol extinction coefficient (R = 0.92), and MAX-DOAS versus sun photometer AOD (slope = 0.94; R= 0.90).

With the objective of understanding the relationship between NO2 photolysis and solar global radiation in the Amazon region, and studying the concentration of the gases NO, NO2 and O3, the data collected from July 02 to 28th, 2001, as part of the campaign from the experiment LBA/CLAIRE-2001 (Large Scale Biosphere- Atmosphere / Cooperative LBA Airborne Regional Experiment - 2001) were analyzed. The photolytic reactions have a critical role controlling the abundance of many atmospherical pollutants, decomposing trace gases (that affect the terrestrial radiation balance) and contributing for their removal from the atmosphere. A significant increase of the NO concentration in the beginning of the morning was observed, whereas the NO2 concentration proved to be higher at night. The O3 concentration increases with the sunrise, with its peak at approximately 14h. The curve of NO2 photolysis (J(NO2)) showed similarity to the Rg curve, with the influence of cloudiness. When the NO2 photolysis begins, an inversion of the magnitude of the NO and NO2 with O3 concentration occurs. The NO2 concentration of varied greatly when analyzing the differences between the clear, partially cloudy and cloudy days. / Fundação de Amparo a Pesquisa do Estado de Alagoas / Com o objetivo de entender as relações entre fotólise de NO2 e radiação solar global na região amazônica, e estudar a concentração dos gases NO, NO2 e O3, analisouse os dados coletados durante o período de 02 a 28 de julho de 2001, como parte da campanha do experimento LBA/CLAIRE-2001 (Large Scale Biosphere-Atmosphere / Cooperative LBA Airborne Regional Experiment - 2001). As reações fotolíticas têm um papel crítico no controle da abundância de muitos poluentes atmosféricos, decompondo gases-traço (que afetam o balanço de radiação terrestre) e contribuindo para sua remoção da atmosfera. Observou-se um aumento significativo da concentração de NO no início da manhã, enquanto a de NO2 apresentou-se mais elevada durante a noite. A concentração de O3 aumenta a partir do nascer do sol, diminuindo a partir de aproximadamente, 14h. A curva de J(NO2) apresentou-se semelhante à Rg, com influência da nebulosidade. Quando a fotólise de NO2 se inicia, ocorre uma inversão da grandeza das concentrações do NO e NO2 com a do O3. A concentração de NO2 variou bastante quando analisadas as diferenças entre os dias claro, parcialmente nublado e nublado.

Nitrogen dioxide (NO₂) is a pollutant of interest for study both because of its controlling role in the oxidant capacity of the atmosphere and the health risks it poses. Concerns about the health effects of NO₂ and its role in forming deleterious atmospheric species have made it desirable to have low-cost, sensitive ambient measurements of NO₂. A continuous-wave laser-diode laser-induced fluorescence (LIF) system for NO₂ was developed here which operates at ambient pressure, thereby eliminating the need for an expensive pumping system. The current prototype system has achieved sensitivity several orders of magnitude beyond previous efforts at ambient pressure (limit of detection of 2 ppb, 60 s averaging time). Ambient measurements of NO₂ were made in Portland, Oregon using both the standard NO₂ chemiluminescence method and the LIF instrument and showed good agreement (r² = 0.92). In addition, investigations into surface mediated chemistry involving oxides of nitrogen (namely, NO₂) have stimulated new inquiry into potential heterogeneous sources of NO₂ as well as challenged the stability of permanent sinks for NO₂. The possibility that surface mediated chemistry plays a significant role in NOy chemistry in urban air has for the past few decades received considerable attention. The AP-LIF NO₂ instrument is uniquely suited to measure surface chemistry under near ambient conditions. The so called 'renoxification' reaction of gaseous NO with surface bound HNO₃ yielding NO₂ (2HNO₃(surface) + NO--> 3NO₂ +H₂O(surface)) was suggested as a potentially important source of NO₂ which also degraded the stability of nitric acid as a sink of active oxides of nitrogen. Yet, there is disagreement in the literature as to the importance of this reaction. The disagreement stems from differing measurements of the rate for the renoxification reaction. Because there are differences in experimental setups no one research group has studied the renoxification reaction under ambient conditions, i.e., at moderate concentrations of NOy and in a static cell held at 1 atm. In this work, the production of NO₂ was measured using a novel AP-LIF. This setup made it possible to measure the rate of production of NO₂ due to the heterogeneous reaction of NO with HNO₃ under ambient conditions. Under these conditions it was found that renoxification due to gas-phase NO on surface HNO₃ is not a significant source of NO₂. However, this study did show the importance of water vapor in the renoxification of surface HNO₃.