A qualidade do ar dos grandes centros urbanos é impactada diretamente pela emissão de poluentes dos veículos automotores. São dois os principais indicadores da deterioração da qualidade do ar: a concentração de material particulado e de ozônio. A concentração desses poluentes frequentemente atinge valores preocupantes, em especial na Região Metropolitana de São Paulo. O ozônio é um poluente secundário formado a partir de reações fotoquímicas em ambiente com a presença de compostos orgânicos voláteis e óxidos de nitrogênio, dentre os principais compostos precursores emitidos pela combustão dos motores dos veículos. A metodologia desenvolvida busca caracterizar o impacto da circulação dos veículos utilizando um índice, baseado na especiação, quantificação e reatividade dos precursores de ozônio emitidos. Esse índice pode identificar o impacto de um modelo de veículo e atender a demanda por rotulagem ambiental ou o impacto de um conjunto de veículos e subsidiar políticas públicas de redução das emissões / Air quality in large urban centers is directly impacted by the emission of pollutants from motor vehicles. There are two main indicators of the deterioration of air quality: the concentration of particulate matter and ozone. The concentration of these pollutants often reaches alarming values, particularly in São Paulo Metropolitan Area. Ozone is a secondary pollutant formed by photochemical reactions in atmosphere with the presence of volatile organic compounds and nitrogen oxides, precursors compounds emitted by combustion in vehicle engines. The methodology developed seeks to characterize the impact of the movement of vehicles using an index based on speciation, quantification and reactivity of emitted ozone precursors. This index can identify the impact of a vehicle and meet the demand for environmental labeling or the impact of a set of vehicles and support public policies to reduce emissions

Les composés organiques semi-volatils (COSV) font l’objet d’une attention croissante depuis une dizaine d’années. Utilisés dans de nombreux produits et matériaux du quotidien, ils sont émis dans les bâtiments par dispersion lors de l’usage, par évaporation ou abrasion. Du fait de leurs caractéristiques physico-chimiques, ces composés se répartissent à la fois dans l’air, en phases gazeuse et particulaire, et dans les poussières déposées au sol, sur le mobilier et les objets. Compte tenu du temps passé par la population dans les bâtiments, en particulier par les populations sensibles comme les enfants, les femmes enceintes et les personnes âgées, l’exposition à ces substances mérite d’être documentée, tenant compte des voies d’exposition en jeu : inhalation, ingestion et contact cutané. La thèse a porté sur les COSV présents en phase particulaire dans les logements. L’objectif de la thèse visait à exploiter les mesures de 66 COSV dans les particules en suspension de diamètre inférieur à 10 µm (PM10) et de 48 COSV dans les poussières au sol de taille inférieure à 100 µm considérées comme étant celles adhérant à la peau. Ces mesures ont été réalisées dans le cadre de deux campagnes nationales : la campagne « Logements » de l’Observatoire de la qualité de l’air intérieur conduite en 2003-2005 et l’enquête Plomb-Habitat dont les prélèvements ont eu lieu en 2008-2009. Une hiérarchisation des molécules jugées prioritaires au regard de leur impact sanitaire potentiel avait permis au préalable d’établir la liste des COSV à mesurer. L’exploitation de ces données de contamination a notamment porté sur l’identification d’éventuelles spécificités françaises au regard des molécules en présence et/ou des concentrations mesurées. Elle a permis de mettre en lumière un ensemble de facteurs déterminants de l’exposition (influence de la taille des particules, du type de poussières collectées, de leur bioaccessibilité), qui ne sont pas toujours considérés et qui limitent par ailleurs la comparabilité des résultats. Les concentrations mesurées ont aussi permis d’évaluer rétrospectivement la hiérarchisation sanitaire et d’en confirmer la pertinence. Les concentrations des COSV quantifiés à la fois dans l’air et au sol ont été mises en perspective afin d’examiner dans quelle mesure les particules en suspension et les poussières déposées sont similaires en termes de concentrations et de mélanges de COSV en présence. Enfin, l‘estimation des doses d’exposition aux COSV à partir d’équations simples, de variables humaines d’exposition et des données de contamination a permis une première évaluation des contributions respectives de l’inhalation et de l’ingestion aux expositions domestiques des enfants et adultes à ces composés en phase particulaire. / Semi-volatile organic compounds (SVOCs) refer to a broad spectrum of molecules from different chemical families that have numerous properties. They can be used as pesticides, plasticizers, flame retardants, surfactants, lubricants, etc. Consequently, they are introduced in numerous applications in buildings or used daily by the entire population. Once emitted through evaporation or abrasion in the indoor environment or introduced from the outdoors, their chemical or biological degradation is limited, and they persist indoors. This persistence also explains why some SVOCs that were banned a few years ago are still detected in the air and dust inside buildings. In indoor environments, SVOCs are divided between the gas phase, airborne particles, and dust settled on floors and surfaces. SVOCs are of concern due to their established or suspected health effects and their widespread exposure through different environmental media and pathways. The objective of the thesis was to study the concentrations of 66 SVOCs on airborne particles (PM10) and 48 SVOCs in settled dust in two samples of dwellings randomly selected across France. PM10 were sampled during the nationwide housing survey carried out by the French Observatory of indoor air quality in 2003-2005. The dust samples were collected from vacuum cleaner bags during a nationwide survey carried out in French dwellings where at least one child aged 6 months to 6 years lived (2008-2009). The SVOCs to be analyzed had prior been selected using a ranking method based on their toxicity and indoor concentrations. The data analysis focused in particular on the identification of French specificities in terms of detected molecules and measured concentrations. It highlighted some determinants of exposure, e.g., influence of particle size, type of dust collected, dust bioaccessibility, which are not always considered and limit the comparability of results. The measured concentrations were also used to assess the health ranking implemented prior to this work and to confirm its relevance. The concentrations measured both in the air and in settled dust were compared to study the similarities in terms of concentrations and SVOC mixtures. Finally, the exposure doses to SVOCs were calculated for both a child and an adult to assess the respective contributions of inhalation and ingestion to these compounds in particulate phase in dwellings.

Effective pollution mitigation is the key to successful air quality management. Although states invest millions of dollars to predict future air quality, the regulatory modeling and analysis process to inform pollution control strategy remains uncertain. Traditionally deterministic ‘bright-line’ tests are applied to evaluate the sufficiency of a control strategy to attain an air quality standard. A critical part of regulatory attainment demonstration is the prediction of future pollutant levels using photochemical air quality models. However, because models are uncertain, they yield a false sense of precision that pollutant response to emission controls is perfectly known and may eventually mislead the selection of control policies. These uncertainties in turn affect the health impact assessment of air pollution control strategies. This thesis explores beyond the conventional practice of deterministic attainment demonstration and presents novel approaches to yield probabilistic representations of pollutant response to emission controls by accounting for uncertainties in regional air quality planning. Computationally-efficient methods are developed and validated to characterize uncertainty in the prediction of secondary pollutant (ozone and particulate matter) sensitivities to precursor emissions in the presence of uncertainties in model assumptions and input parameters. We also introduce impact factors that enable identification of model inputs and scenarios that strongly influence pollutant concentrations and sensitivity to precursor emissions. We demonstrate how these probabilistic approaches could be applied to determine the likelihood that any control measure will yield regulatory attainment, or could be extended to evaluate probabilistic health benefits of emission controls, considering uncertainties in both air quality models and epidemiological concentration–response relationships. Finally, ground-level observations for pollutant (ozone) and precursor concentrations (oxides of nitrogen) have been used to adjust probabilistic estimates of pollutant sensitivities based on the performance of simulations in reliably reproducing ambient measurements. Various observational metrics have been explored for better scientific understanding of how sensitivity estimates vary with measurement constraints. Future work could extend these methods to incorporate additional modeling uncertainties and alternate observational metrics, and explore the responsiveness of future air quality to project trends in emissions and climate change.

Η ατμοσφαιρική ρύπανση επηρεάζει την δημόσια υγεία, το φυσικό οικοσύστημα και επιφέρει μεταβολές στις κλιματικές συνθήκες. Το πρόβλημα της αέριας ρύπανσης παρουσιάζεται εντονότερο σε αστικές περιοχές, όπου η συσσώρευση ανθρωπίνων δραστηριοτήτων οδηγεί κατά κανόνα σε αυξημένες εκπομπές αερίων. Κάτω από την επήρεια δυσμενών μετεωρολογικών συνθηκών, τα επίπεδα συγκεντρώσεων των ρύπων μπορούν να ξεπεράσουν τα όρια της Παγκόσμιας Οργάνωσης Υγείας. Για την αποτελεσματική αντιμετώπιση του προβλήματος είναι απαραίτητη η ανάλυση και η σωστή περιγραφή όλων των φαινομένων και παραγόντων που καθορίζουν τις σχέσεις πηγής – αποδέκτη και ατμοσφαιρικών ρύπων. Για το σκοπό αυτό ενδείκνυνται κυρίως μαθηματικά μοντέλα προσομοίωσης μετεωρολογικών φαινομένων και φαινομένων διασποράς και μετασχηματισμού ρύπων. Η έντονη ευαισθητοποίηση της κοινής γνώμης σε θέματα σχετικά με την προστασία του περιβάλλοντος αναγκάζει τις κυβερνήσεις των χωρών να επιβάλλουν την διερεύνηση των συνεπειών έργων και δραστηριοτήτων στο ατμοσφαιρικό περιβάλλον. Τα μοντέλα διασποράς ατμοσφαιρικών ρύπων είναι εύχρηστα εργαλεία που μπορούν να εκτιμήσουν συγκεντρώσεις ρύπων, έτσι ώστε αυτές να είναι αντιπροσωπευτικές στο χώρο και στον χρόνο. Οι μετρήσεις ρύπων με όργανα λαμβάνονται σε συγκεκριμένες θέσεις και ως εκ τούτου δεν είναι αντιπροσωπευτικές για μεγαλύτερες περιοχές. Μέσες τιμές ρύπων για μεγαλύτερες περιοχές υπολογίζονται εύκολα με μοντέλα ατμοσφαιρικής ρύπανσης. Σκοπός αυτής της εργασίας, είναι η πρόβλεψη των συγκεντρώσεων των ρύπων διοξειδίου του θείου SO2, ολικών οξειδίων του αζώτου NOx και της ποσοστιαίας κατανομής της συνεισφοράς των πηγών ρύπανσης στις συγκεντρώσεις των ρύπων που καταγράφονται στις θέσεις των αποδεκτών με την χρήση του λογισμικού AERMOD της Εταιρίας Περιβαλλοντικής Προστασίας (EPA) των ΗΠΑ. Το AERMOD χρησιμοποιεί γκαουσιανά μοντέλα διασποράς. Για τον σκοπό αυτό συγκεντρώνονται και χρησιμοποιούνται πολλά και διαφορετικού τύπου δεδομένα, όπως μετεωρολογικά, γεωγραφικά, κυκλοφορίας αυτοκινήτων και πλοίων, εκπομπές ρύπων κ.α. Επίσης γίνεται η υπόθεση, ότι οι μεγαλύτερες συνεισφορές στην ατμοσφαιρική ρύπανση της Πάτρας γίνονται από την κυκλοφορία των αυτοκινήτων, από τα πλοία του λιμανιού και τις κεντρικές θερμάνσεις των κατοικιών. Η πρόβλεψη που προκύπτει μετά από την επεξεργασία των παραπάνω δεδομένων από το πρόγραμμα AERMOD συγκρίνεται με τα διαθέσιμα αποτελέσματα των μετρήσεων για ατμοσφαιρικούς ρύπους από το Εργαστήριο Τεχνολογίας του Περιβάλλοντος, που έγιναν στην Πάτρα στο διάστημα από τις 13 Νοεμβρίου του 1997 έως τις 23 Ιανουαρίου του 1998, κατά τις πρωινές (8:30 – 9:30) και βραδινές ώρες (20:30 – 21:30) στα πλαίσια διπλωματικής εργασίας υπό την επίβλεψη του κ. Π. Γιαννόπουλου. Στο Κεφάλαιο 1 αναφέρονται γενικές πληροφορίες για την ατμοσφαιρική ρύπανση, την πόλη της Πάτρας, για τους σημαντικότερους ρύπους της ατμόσφαιρας, αλλά και το πώς τα μετεωρολογικά φαινόμενα επηρεάζουν την διασπορά των ρύπων. Στο 2ο Κεφάλαιο αναφέρονται γενικές πληροφορίες για τα σημαντικότερα μαθηματικά μοντέλα ατμοσφαιρικής διασποράς, ενώ στο 3ο κεφάλαιο γίνεται μία γενική περιγραφή του θεωρητικού υπόβαθρου του προγράμματος AERMOD και του Προγράμματος AERMET. Στο Κεφάλαιο 4 παρουσιάζονται τα γεωγραφικά και μετεωρολογικά δεδομένα, τα δεδομένα για τους φόρτους κυκλοφορίας των οχημάτων στην πόλη της Πάτρας αλλά και πληροφορίες για την κίνηση των πλοίων στο παλιό λιμάνι της Πάτρας. Στο 4ο κεφάλαιο παρουσιάζονται οι υπολογισμοί των εκπομπών των ρύπων από τα αυτοκίνητα, τα πλοία και τις κεντρικές θερμάνσεις των κατοικιών. Επίσης παρουσιάζεται η ποσοστιαία κατανομή των εκπομπών από τις πηγές ατμοσφαρικής ρύπανσης και η συνεισφορά της κάθε μιας στην ρύπανση της ατμόσφαιρας. Τέλος παρουσιάζονται οι προβλέψεις που προκύπτουν για τις συγκεντρώσεις των ρύπων στις θέσεις των αποδεκτών και η σύγκριση αυτών με τις μετρήσεις για ατμοσφαιρικούς ρύπους που είχαν γίνει από το Νοέμβριο του 97 έως τον Ιανουάριο του 98. Στο Κεφάλαιο 5 παρουσιάζονται τα συμπεράσματα της εργασίας. Σαν συμπέρασμα της εργασίας προκύπτει ότι τα γκαουσιανά μοντέλα ατμοσφαιρικής διασποράς είναι χρήσιμα εργαλεία για την βραχυπρόθεσμη πρόγνωση των επιπέδων ρύπανσης, την εκτίμηση της συνεισφοράς των επί μέρους πηγών στην ποιότητα του αέρα και τη βελτιστοποίηση των στρατηγικών αντιρρύπανσης. Επισημαίνεται ότι τα μοντέλα προσομοίωσης αποτελούν την μοναδική μεθοδολογία αναφορικά με την δυνατότητα εκτίμησης της συνεισφοράς των επιμέρους πηγών. Επίσης, από τα αποτελέσματα αυτής της εργασίας προκύπτουν χρήσιμα συμπεράσματα για την προέλευση της ατμοσφαιρικής ρύπανσης στην πόλη της Πάτρας, όπως το ότι το μεγαλύτερο ποσοστό της (65 – 76% για το SO2 και 85 – 92% για NOx) προέρχεται από την κυκλοφορία των οχημάτων, ενώ αξιοσημείωτα είναι και τα ποσοστά των ρύπων που προέρχονται από τις κεντρικές θερμάνσεις (17 – 29% για το SO2 και 7,5 – 14,2% για NOx). Επίσης από τα αποτελέσματα φαίνεται ότι τα ποσοστά των ΝΟx που προέρχονται από τα πλοία είναι πολύ μικρά (0,3% - 0,4%), ενώ αντίθετα τα αντίστοιχα ποσοστά του SO2 (6% – 7%) είναι αξιοσημείωτα. Τέλος, άξιο αναφοράς είναι ότι όπως προκύπτει από τις συγκεντρώσεις των ρύπων που προβλέπει το AERMOD, φαίνεται ότι σε μία ζώνη πλάτους 400 m γύρω από το λιμάνι το ποσοστό της συγκέντρωσης του SO2 είναι αυξημένο (8% – 9%). / Air pollution affects public health, natural ecosystem and bring changes in climatic conditions. The problem of air pollution are most marked in urban areas, where the accumulation of human activities should lead to increased greenhouse gases. Under the influence of adverse weather conditions, the concentration levels of pollutants can overcome the limits of the World Health Organization. For the effective address of this problem is necessary to analyze all phenomena and factors that define the relationship source - receptor and atmospheric pollutants. For this purpose are suitable mathematical models simulating weather patterns and phenomena of dispersion and transformation of pollutants. The intense public awareness on issues related to the protection of the environment forces governments to impose the investigation of the effects of projects to the atmosphere. The air pollutant dispersion models are handy tools that can estimate pollutant concentrations, so that they are representative in space and time. The measurements of pollutants with instruments done at specific locations and therefore they are not representative for larger areas. Mean values for pollutants at larger areas easily calculated with models of atmospheric pollution. The aim of this work is the prediction of pollutant concentrations of sulfur dioxide SO2, total nitrogen oxides NOx and the percentage distribution of the contribution of pollution sources in pollutant concentrations recorded at the locations of receptors with the use of the software AERMOD. AERMOD belongs to the Environmental Protection Company (EPA) in the USA. AERMOD uses Gaussian dispersion models. For this purpose collected and used many different types of data, such as meteorological, geographical, automobile traffic and ship emissions, etc. Also it is assumed that the greatest contributions to air pollution of Patras come from the circulation of cars, from the port's ships and from the heating installations. The prediction obtained after processing the above data from the AERMOD program comes in comparison with the available results of measurements of air pollutants from the Laboratory of Environmental Engineering, held in Patras in the period from 13 November 1997 until 23 January 1998 in the morning (8:30 - 9:30) and evening (20:30 - 21:30) in the thesis under the supervision of Mr. P. Giannopoulos. In Chapter 1 reported general information on air pollution, about the significant atmospheric pollutants, and how weather conditions affect the dispersion of pollutants. In the second chapter reported general information about the most important mathematical atmospheric dispersion models, while in the third chapter gives a general description for the theoretical background of the programs AERMOD and AERMET. In Chapter 4 presents the geographical and meteorological data, data on motor vehicle traffic volumes in the city of Patras and information on the movement of ships in the old harbor of Patras. In the fourth chapter presented calculations of emissions of pollutants from cars, ships and central heating of homes. Also in the fourth chapter reported the percentage distribution of emissions from sources of atmospheric pollution and contribution of each in the pollution. Finally in the fourth chapter presented the forecasts for the concentrations of pollutants in the positions of the receptors and compare them with measurements for atmospheric pollutants that were made from November 97 until January 98. In Chapter 5 presented the conclusions of the work. As a conclusion of this study shows that the Gaussian atmospheric dispersion models are useful tools for short-term forecasting of pollution levels, and for the assessment of the contribution of individual sources on air quality. Noted that the simulation models are the unique methodology regarding the possibility of assessing the contribution of individual sources. Also, from the results of this work resulting conclusions about the origin of air pollution in the city of Patras, such that the highest percentage (65 - 76% for SO2 and 85 to 92% for NOx) comes from traffic vehicles, while noteworthy are the percentages of pollutants from central heating (17 - 29% for SO2 and 7.5 to 14.2% for NOx). Also, from the results it appears that rates of NOx from ships are very small (0.3% - 0.4%), while the corresponding percentages of SO2 (6% - 7%) is remarkable. Finally, it is worth mentioning that as indicated by the concentrations of pollutants that AERMOD calculates , it seems that in a zone extending 400 m around the harbor, the percentage of the concentration of SO2 is increased (8% - 9%).

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-10-10T14:25:54Z No. of bitstreams: 1 JOACI DOS SANTOS CERQUEIRA - TESE (PPGRN) 2018.pdf: 25053168 bytes, checksum: f171a30ed512369a6372b1d77a7bb854 (MD5) / Made available in DSpace on 2018-10-10T14:25:54Z (GMT). No. of bitstreams: 1 JOACI DOS SANTOS CERQUEIRA - TESE (PPGRN) 2018.pdf: 25053168 bytes, checksum: f171a30ed512369a6372b1d77a7bb854 (MD5) Previous issue date: 2018-02-23 / CNPq / Os poluentes atmosféricos das usinas termelétricas afetam negativamente a saúde humana, o solo, os corpos hídricos, as edificações, a flora e a fauna. Assim, essa forma de geração de energia elétrica, gera efluentes causadores de danos ao meio ambiente, trazendo impactos ambientais negativos. Neste sentido, o objetivo desse estudo foi avaliar os impactos ambientais causados pelo funcionamento de uma Usina Termelétrica localizada na região metropolitana de Campina Grande-PB. Através de um estudo de campo, de caráter exploratório foi empregado variadas metodologias para identificar as espécies da ornitofauna local, inventariar as espécies arbóreas e avaliar as trocas gasosas vegetais, além de utilizar de sensores ambientais pata determinar os níveis instantâneos dos compostos químicos CO2, CO, SO2, ruídos, temperatura do ar, umidade relativa do ar, temperatura de ponto de orvalho, velocidade do vento e luminescência vegetais, do entorno da Usina Termelétrica Energética Borborema S.A e de uma área amostral; e, através do software Aermod View, simular as concentrações das dispersões das fontes emissoras da Usina Termelétrica. Com isso, registrou-se vinte e nove espécies de aves, pertencentes a 21 famílias; e, para no inventário arbóreo, as principais espécies encontradas foram Combretum glaucocarpum, Croton sonderianus, Aspidosperma pyrifolium e Mimosa tenuiflora; quanto as análises das trocas gasosas realizadas pelo LCpro+, verificou-se que os valores máximos de transpiração foi registrado no ponto (P600), sendo a espécie Ziziphus joazeiro responsável pelo maior valor registrado; em relação ao uso dos sensores ambientais para monitorar a qualidade do ar, atestou-se ser uma ferramenta fundamental para verificar alterações na ambiência do entorno da Termelétrica Borborema S.A.; na modelagem com Aermod View, verificou-se que nas concentrações de NO2, os índices atingiram cerca de cinco vezes maior que o padrão primário estabelecido pelo CONAMA 03/90. Desta maneira, os resultados associados aos procedimentos metodológicos utilizados em conjunto, caracterizam-se como eficazes para avaliação e monitoramento de impactos ambientais para instalação e funcionamento de Termelétricas e demais indústrias poluidoras. / The air pollutants of thermoelectric power plants negatively affect human health, soil, water bodies, buildings, flora and fauna. Thus, this form of electric energy generation, generates effluents that cause damages to the environment, bringing negative environmental impacts. In this sense, the objective of this study was to evaluate the environmental impacts caused by the operation of a Thermoelectric Plant located in the metropolitan region of Campina Grande-PB. Through an exploratory field study, a variety of methodologies were used to identify the species of the local ornitofauna, to inventory the tree species and to evaluate the vegetal gas exchanges, besides using environmental sensors to determine the instantaneous levels of the chemical compounds CO2, CO, SO2, noise, air temperature, relative air humidity, dew point temperature, wind speed and plant luminescence, in the surroundings of Usina Termelétrica Energética Borborema S.A. and a sample area; and, through the Aermod View software, to simulate the dispersion concentrations of the sources emitting the Thermoelectric Plant. Thus, twenty-nine bird species belonging to 21 families were recorded; and, for the tree inventory, the main species found were Combretum glaucocarpum, Croton sonderianus, Aspidosperma pyrifolium and Mimosa tenuiflora; as well as the analyzes of the gas exchanges performed by LCpro +, it was verified that the maximum values of transpiration were recorded at the point (P600), and the Ziziphus joazeiro species was responsible for the highest recorded value; in relation to the use of environmental sensors to monitor air quality, was proved to be a fundamental tool to verify changes in the environment of the Borborema thermoelectric plant S.A.; in the modeling with Aermod View, it was verified that in the concentrations of NO2, the indexes reached about five times greater than the primary standard established by CONAMA 03/90. In this way, the results associated to the methodological procedures used together, are characterized as effective for evaluation and monitoring of environmental impacts for the installation and operation of Thermoelectric and other polluting industries.

Devido ao compromisso com a melhoria do meio ambiente, aliado às crescentes exigências dos órgãos ambientais, e a necessidade de identificar a contribuição de cada atividade/processo desenvolvido em institutos de pesquisas, quanto ao impacto destes à qualidade do ar, este trabalho teve a finalidade de desenvolver um modelo de inventário e aplicar uma metodologia de cálculo, que permita estimar a emissão de poluentes atmosféricos, decorrentes das atividades dos centros de pesquisa e desenvolvimento do Instituto de Pesquisas Energéticas e Nucleares (IPEN/CNEN-SP). O estudo foi motivado pela ausência de metodologias de cálculo de emissões atmosféricas específicas para fontes fixas como capelas químicas de exaustão e da necessidade em atender as condicionantes estabelecidas no licenciamento ambiental da instituição. Para a elaboração dos cálculos foram adotados os fatores de emissão e a equação descrita na AP-42 da EPA- Environmental Protection Agency. Foram utilizadas como abordagens de cálculo de emissões: a) Mensuração direta (por meio do inventário de emissões atmosféricas); e b) Estimativa de emissões (utilizando estimativa da taxa de emissão calculada a partir do fator de emissão apropriado). O estudo foi detalhadamente realizado tendo como base inicial o inventário e o modelo de estimativa de emissão atmosférica das fontes fixas aplicado no Centro de Química e Meio Ambiente (CQMA). Cabe ressaltar que o monitoramento online da qualidade do ar no campus é realizado em estação fixa, parceria IPEN CETESB, na estação CETESB Cid. Universitária IPEN - USP. O estudo possibilitou estabelecer, de forma efetiva, o Programa de Monitoramento e Controle de Emissões Atmosféricas (PMEA IPEN), podendo servir de modelo para outras instituições de Pesquisa, Desenvolvimento & Inovação. Como produto final obteve-se um inventário de emissões atmosféricas de fontes fixas da instituição, a taxa de emissão de poluentes, bem como a concentração de poluentes emitidos. A estimativa das emissões não ultrapassou os limites dispostos na legislação em âmbito nacional e estadual. / Atmospheric Emission Factors and Significance Analysis applied to the Air Quality Management in the IPEN / CNEN-SP Campus due to the commitment to improve the environment, combined with the increasing demands of environmental agencies, and the need to identify the contribution of each activity / process developed in research institutes, as well as the impact of these on the air quality, this work aims to develop an inventory model and apply a methodology of calculation for measuring the emission of atmospheric pollutants, arising from the activities of the research and development centers of the Nuclear and Energy Research Institute (IPEN / CNEN-SP). The study was motivated by the absence of atmospheric emission calculation methodologies specific to stationary sources, such as fume hoods. For preparation of the calculations, the emission factors and the equation described in the AP-42 EPA- Environmental Protection Agency were adopted. The emission calculation methods used were: a) Direct measurement (through the inventory of air emissions); and b) Emissions estimate (using the emission rate estimate calculated from the appropriate emission factor). The study was carried out in detail, based on the inventory and model of atmospheric emission of fixed sources applied at the Chemistry and Environment Center (CQMA). It should be noted that online monitoring of air quality on campus is carried out at a fixed station, IPEN CETESB partnership, at CETESB Cid station. University - IPEN - USP. The study has made it possible to establish, in an effective way, the Atmospheric Emission Monitoring and Control Program (PMEA - IPEN), which could serve as a model for other Research, Development and Innovation institutions. The final product was an inventory of atmospheric emissions from fixed sources of the institution, the emission rate of pollutants, as well as the concentration of pollutants emitted. The estimation of the emissions did not exceed the limits established in the national legislation and state level.

Les méthodes d’évaluation environnementale sont de plus en plus utilisées pour mieux apprécier les impacts environnementaux générés par les activités humaines (produits, services, systèmes). L’analyse de cycle de vie (ACV) est sans doute la méthode d’évaluation la plus répandue. Elle est aussi souvent considérée comme la plus avancée, bien qu’elle comporte de sérieuses limites (elle n’intègre pas de réels indicateurs économiques ou sociaux, par exemple). Dans cette thèse de doctorat, j’examine plus particulièrement la problématique de l’intégration du temps dans les modèles d’inventaire et les calculs d’impact tout au long du cycle de vie. J’y présente une évolution de la méthodologie d’ACV traditionnelle pour le cas du réchauffement climatique, qui incorpore des aspects dynamiques et cumulatifs exprimés directement en équivalent-CO2. Cette perspective orientée vers une meilleure prise en compte dans les pratiques de reporting et/ou les politiques publiques est ensuite déclinée sur trois cas d’application de complexité croissante pour l’analyse. L’hypothèse centrale de ce travail est que le passage d’une ACV traditionnelle à une ACV dite « dynamique » permettrait d’obtenir des résultats d’évaluation d’impacts plus proches de la réalité des phénomènes environnementaux / Environmental impact assessment methods are now widely used in order to measure environmental impacts associated with human activities (for products, services, and systems). Life-cycle assessment (LCA) is without doubt the foremost assessment method. LCA is also often thought of as the more advanced one, despite serious limitations (e.g. LCA does not include properly economical or social dimensions). In this PhD report, I explore more specifically the issue of integrating time in both inventory models and impact assessments along the life-cycle. In the case of climate change, I offer an evolution of traditional LCA towards a framework that includes dynamic and cumulative aspects as expressed directly in CO2-equivalent. This approach, which is oriented towards reporting practices and/or public policies, is afterwards applied to three different case studies of growing complexity. The central hypothesis of this work is that switching from traditional to so-called “dynamic” LCA would allow for better results with regards to one reality of environmental processes

Devido ao compromisso com a melhoria do meio ambiente, aliado às crescentes exigências dos órgãos ambientais, e a necessidade de identificar a contribuição de cada atividade/processo desenvolvido em institutos de pesquisas, quanto ao impacto destes à qualidade do ar, este trabalho teve a finalidade de desenvolver um modelo de inventário e aplicar uma metodologia de cálculo, que permita estimar a emissão de poluentes atmosféricos, decorrentes das atividades dos centros de pesquisa e desenvolvimento do Instituto de Pesquisas Energéticas e Nucleares (IPEN/CNEN-SP). O estudo foi motivado pela ausência de metodologias de cálculo de emissões atmosféricas específicas para fontes fixas como capelas químicas de exaustão e da necessidade em atender as condicionantes estabelecidas no licenciamento ambiental da instituição. Para a elaboração dos cálculos foram adotados os fatores de emissão e a equação descrita na AP-42 da EPA- Environmental Protection Agency. Foram utilizadas como abordagens de cálculo de emissões: a) Mensuração direta (por meio do inventário de emissões atmosféricas); e b) Estimativa de emissões (utilizando estimativa da taxa de emissão calculada a partir do fator de emissão apropriado). O estudo foi detalhadamente realizado tendo como base inicial o inventário e o modelo de estimativa de emissão atmosférica das fontes fixas aplicado no Centro de Química e Meio Ambiente (CQMA). Cabe ressaltar que o monitoramento online da qualidade do ar no campus é realizado em estação fixa, parceria IPEN CETESB, na estação CETESB Cid. Universitária IPEN - USP. O estudo possibilitou estabelecer, de forma efetiva, o Programa de Monitoramento e Controle de Emissões Atmosféricas (PMEA IPEN), podendo servir de modelo para outras instituições de Pesquisa, Desenvolvimento & Inovação. Como produto final obteve-se um inventário de emissões atmosféricas de fontes fixas da instituição, a taxa de emissão de poluentes, bem como a concentração de poluentes emitidos. A estimativa das emissões não ultrapassou os limites dispostos na legislação em âmbito nacional e estadual. / Atmospheric Emission Factors and Significance Analysis applied to the Air Quality Management in the IPEN / CNEN-SP Campus due to the commitment to improve the environment, combined with the increasing demands of environmental agencies, and the need to identify the contribution of each activity / process developed in research institutes, as well as the impact of these on the air quality, this work aims to develop an inventory model and apply a methodology of calculation for measuring the emission of atmospheric pollutants, arising from the activities of the research and development centers of the Nuclear and Energy Research Institute (IPEN / CNEN-SP). The study was motivated by the absence of atmospheric emission calculation methodologies specific to stationary sources, such as fume hoods. For preparation of the calculations, the emission factors and the equation described in the AP-42 EPA- Environmental Protection Agency were adopted. The emission calculation methods used were: a) Direct measurement (through the inventory of air emissions); and b) Emissions estimate (using the emission rate estimate calculated from the appropriate emission factor). The study was carried out in detail, based on the inventory and model of atmospheric emission of fixed sources applied at the Chemistry and Environment Center (CQMA). It should be noted that online monitoring of air quality on campus is carried out at a fixed station, IPEN CETESB partnership, at CETESB Cid station. University - IPEN - USP. The study has made it possible to establish, in an effective way, the Atmospheric Emission Monitoring and Control Program (PMEA - IPEN), which could serve as a model for other Research, Development and Innovation institutions. The final product was an inventory of atmospheric emissions from fixed sources of the institution, the emission rate of pollutants, as well as the concentration of pollutants emitted. The estimation of the emissions did not exceed the limits established in the national legislation and state level.

A geração de resíduos sólidos é inerente ao desenvolvimento humano. O concreto armado é um dos materiais mais utilizados pelo homem e tem o cimento Portland como seu principal constituinte, o qual é produzido pela moagem de clínquer e gesso. O clínquer pode ser definido como um mineral artificial, obtido a partir das reações físico-químicas de calcário, argila e corretivos a altas temperaturas, em forno rotativo industrial, mediante a queima de combustíveis fósseis. No início da década de 70 foram realizadas as primeiras experiências de substituição de combustíveis fósseis por resíduos industriais nos Estados Unidos e países europeus, através da técnica denominada co-processamento, resultando na manufatura de um produto ao mesmo tempo em que os resíduos eram eliminados. O co-processamento se baseia na recuperação da energia disponível nos resíduos, substituindo parte daquela fornecida pelos combustíveis tradicionais ou na substituição de matérias-primas por resíduos com características químicas semelhantes àquelas normalmente empregadas na produção do clínquer. No estado de São Paulo as primeiras iniciativas para a utilização de resíduos industriais em fornos de clínquer ocorreram no início da década de 90. A partir de 1997 os órgãos ambientais de alguns estados brasileiros normatizaram procedimentos de licenciamento da atividade que foi, posteriormente, uniformizada por norma em âmbito federal. No ano de 1995 a Companhia de Cimento Ribeirão Grande/SP, Brasil, iniciou os procedimentos visando a substituição parcial dos combustíveis utilizados nos fornos rotativos por uma mistura de resíduos industriais. No período de 1995 a 2002 foram realizadas campanhas de amostragens em chaminés para avaliação das emissões atmosféricas dos dois fornos de produção de clínquer. A análise dos resultados obtidos associada às demais informações disponíveis de monitoramento das características das matérias-primas e combustíveis utilizados, bem como dos produtos finais, clínquer e cimento, não evidenciou alterações significativas nos níveis de emissões atmosféricas, sobretudo de material particulado e óxidos de enxofre, que pudessem ser associadas à utilização dos resíduos. Foram confirmadas as baixas emissões de inorgânicos e evidenciado o papel representado pelos resíduos no aporte dessas substâncias no sistema-forno, concluindo-se que esse aporte pode ser tão ou mais importante pela via da alimentação da farinha, cujos teores estão associados às características das jazidas minerais utilizadas. Foi também confirmada a alta eficiência do sistema-forno na destruição e remoção dos compostos orgânicos perigosos alimentados durante os testes de queima. / The production of industrial residues in inherent to the human development. The cement concrete is one of the most used material, manly the type portland cement, which is constituted by grinding clinker and gypsum together. Clinker can be defined as an artificial mineral obtained by applying physico-chemical reactions, at very high temperatures, to an appropriated mixture of limestone, clay, and some other materials in a rotating industrial kiln wich burns fossil fuels. In the early 1970 decade occurred the first experiences substituting fossil fuels by organic residues in USA and Europe through a technique named co-processing that results the production of certain manufacture while eliminates residues. Co-processing is based in the recovery of thermal energy and/or the mass of some constituents from some residues, with the same chemical characteristics of normal sources of energy, then economizing fuels and mass constituents and making better use of residues, otherwise useless and environmentally polluters. In the state of São Paulo this practice began in early 1990 decade and by 1997 it was started the standardization of the rules for its use in some units of the federation. Later this activity was regulated by nationally approved standard rules. In 1995 the industry Companhia de Cimento Ribeirão Grande (CCRG), a cement plant located in the city of Ribeirão Grande, São Paulo state, Brazil, started procedures searching the partial substitution of the normal fuels by a mixture of industrial residues in its two rotating kilns. The gaseous emissions from the chimneys of these two clinker kilns were studied from 1995 to 2002 about the use of residues as part of the fuel. Analyses of the final results associated with other informations concerning to the quality of raw minerals, fuels and products did not show significant alterations in atmospheric emissions, mainly for particulate material and sulfur oxides, related with the use of residues. The emissions of inorganic continued to be low and not significantly altered by the presence of residues. It was possible to conclude that the alterations in inorganic emissions depend more from the quality of the raw minerals feed in the kilns, which is more difficult to control, than from the presence of residues being burn with the fuel. It was shown a high efficiency in the destruction of dangerous organic compounds feed in the cement kilns, under test conditions.

A tese enfatiza o desenvolvimento e aplicação de amostradores difusionais para pré-concentração de traços de poluentes gasosos e sua conjugação com técnicas de separação e determinação, especialmente, a eletroforese capilar. Foram implementadas novas aplicações para um amostrador com múltiplos filamentos microporosos de polipropileno, previamente desenvolvido pelo grupo de pesquisa, e para o novo dispositivo de coleta de dimensões reduzidas, composto por monofilamento microporoso de polipropileno (CMDS) com volume interno de 30 µL. Para o estabelecimento da vazão estável em 1,0 µL min-1 de fase aceptora pelo capilar poroso, recorreu-se à pressurização do reservatório com uma bomba pneumática de aquário e regulagem de vazão por um capilar de sílica fundida e uma válvula de agulha. Outra bomba pneumática foi utilizada para aspirar o fluxo de ar amostrado. As amostras foram coletadas seqüencialmente em frascos de 200 µL, mantidos sob temperatura reduzida em unidade de refrigeração do tipo Peltier acoplado ao amostrador. O CMDS monofilamentar, mais compacto e robusto, apresentou alta eficiência de coleta para a pré-concentração de formaldeído (CH2O), ácidos fórmico e acético e amônia da fase gasosa da atmosfera. Para as espécies com elevada constante de Henry, água deionizada serviu como fase aceptora, enquanto que para amônia, recorreu-se ao deslocamento do equilíbrio por um aceptor ácido, de modo a reter o analito na forma de NH4 +. A concentração das espécies em fase líquida foi determinada posteriormente por eletroforese capilar com detecção condutométrica sem contato (CE-C4D). Os limites de detecção, em fase líquida, para formiato, acetato, formaldeído (determinado na forma do aduto hidroximetanosulfonato HMS) e amônio foram estimados em 1,0, 1,5, 1,2 e 1,2 µmol L-1, respectivamente (equivalentes à 0,9, 3,0, 1,0 e 0,7 µg m-3 dessas espécies na atmosfera, respectivamente). Para a determinação de CH2O por injeção em fluxo (FIA) acoplada à detecção amperométrica em eletrodo de ouro platinizado, fez-se uso do coletor multifilamentar, por atender melhor à necessidade de volume de amostra. A interferência de espécies comumente presentes na atmosfera, como H2O2 e SO2, pôde ser contornada realizando coletas em presença de peróxido de hidrogênio para promover a oxidação do S(IV) à S(VI) e, posteriormente, destruindo o oxidante em reator contendo enzima catalase imobilizada. A determinação de CH2O foi implementada com sucesso por FIA com detecção por amperometria em eletrodo de ouro platinizado. Um CMDS portátil que funciona à pilha, próprio para amostragens em campo, foi desenvolvido utilizando, para o deslocamento do ar amostrado, uma bomba de pistão retirada de aparelho automático para medida de pressão arterial. O amostrador foi empregado na coleta de H2S, SO2 e alquil-mercaptanas em fase gasosa da atmosfera, utilizando fase aceptora alcalina para promover a desprotonação e conseqüente fixação das espécies em meio líquido. Os analitos foram determinados por CE-C4D ou por microextração em fase sólida (SPME) seguida de determinação por GC. O uso conjunto do antioxidante ascorbato para conservação das amostras e de etanol para fixação dos compostos voláteis em meio aquoso permitiu o estabelecimento de um protocolo completo para coleta e detecção dessas espécies reduzidas de enxofre, com sensibilidade suficiente para monitorar emissões de origem biogênica, o que foi exemplificado na prática coletando amostras próximo a um córrego contaminado com esgoto. A perfeita combinação do diminuto volume de fase aceptora do CMDS com a demanda de nanolitros de amostra da CE-C4D culminou com o desenvolvimento de um sistema de análise total (TAS) com gerenciamento de fluidos baseado em propulsão por bombas de aquário (de baixo custo e alta durabilidade) e válvulas solenóide de estrangulamento, controladas por computador. Como exemplo de aplicação inovador e bem sucedido do TAS desenvolveu-se a análise concomitante e em tempo quase real de ácidos fórmico e acético no ar, com freqüência de 10 pares de dados por hora. As vantagens do sistema CMDS-CE-C4D incluem simplicidade, versatilidade, consumo de reagentes e amostra e geração de resíduos minimizada, robustez e rapidez enquanto uma amostra é coletada, o eletroferograma da anterior é adquirido sem necessidade de bombas de alta pressão ou colunas dispendiosas como as requeridas para HPLC / The development and application of porous membrane diffusion samplers for fast and efficient pre-concentration of an array of trace air pollutants was emphasized in this thesis, in conjunction with compatible separation and determination techniques, especially capillary electrophoresis. New applications were found for a formerly developed diffusion scrubber based on a bundle of microporous hollow polypropylene capillary membranes and for a scaled down version with a single core capillary membrane diffusion scrubber (CMDS) comprising an internal volume of 30 µL, were used for sampling of the trace level pollutants to an adequate liquid acceptor. The low-flow of acceptor solution, 1.0 µL min-1, required by the CMDS was satisfied by pressurization of the reservoir with an aquarium pump combined with flow regulation by a silica capillary as hydrodynamic resistor and a needle valve. Another aquarium pump was used for the aspiration of the sampled air through the sampler. The low volumes collected in the CMDS were stored in 200 µL vials inserted in a cooling plate of a Peltier device. The robust and compact system was used for sampling of formaldehyde (CH2O), formic acid, acetic acid and ammonia in the gaseous phase of the atmosphere. For chemical species with high Henry´s constant, deionized water suffices as acceptor phase. Otherwise, equilibria displacement to a non-volatile ion, like NH4 + for NH3 sampling, promoted quantitative retention in the acceptor phase. The concentrations of the analytes in the liquid phase were determined by capillary electrophoresis with capacitively coupled contactless conductometric detection (CEC4D). The detection limits obtained in the liquid phase for formate, acetate, formaldehyde (in the form of the adduct hydroxymethanesulfonate HMS) and ammonium were 1,0, 1,5, 1,2 e 1,2 µmol L-1 respectively (what corresponds to 0,9, 3,0, 1,0 e 0,7 µg m-3 of the respective gaseous species in the air). The higher volume of acceptor phase provided by the sampler with a bundle of microporous membrane capillaries (~600 µL) are in tune with the needs of flow injection analysis (FIA), as demonstrated for amperometric detection of CH2O on a platinized gold electrode. The interferences from SO2 and H2O2 were overcome by adding H2O2 to the acceptor solution to promote the oxidation of S(IV) to S(VI) and destruction of the oxidant afterwards in a column with immobilized catalase enzyme. The aquarium pump used for gas aspiration was substituted to a piston pump, taken from arterial blood pressure meter fed with 8 V D.C., to turn possible field collections with the CMDS device. The system was used for the sampling of H2S, SO2 e alkyl-mercaptans in the gaseous phase of the atmosphere. To succeed on that, the samplings were performed in alkaline media to promote deprotonation of the species (and stabilization in non-volatile forms). The collected analytes were determined by CE-C4D or by solid phase microextraction (SPME) followed by GC analysis. The joint use of the antioxidant ascorbate for sample preservation and ethanol for fixation of the volatile compounds allowed the establishment of a complete protocol for sampling, storage and detection of the sulfur reduced species with enough sensitivity for monitoring biogenic emissions from waste discharge. Perfect matching of the low-volume characteristics of the CMDS device and the CE-C4D equipment led to the conception of a low-cost automatic CMDS-CE-C4D total analysis system (TAS) and its innovative and successful application to near-realtime simultaneous analysis of formic acid and acetic acid in air. During the evaluation of one sample, the TAS collects a new one, with valves, pumps and high voltage delivery under software control. Advantages include rapidity (10 data points per hour for each analyte), high preconcentration efficiency, simplicity and versatility, minimum sample and reagent consumption and residue generation (green analytical method), no need of costly high pressure pumps and separation columns like those used in HPLC