[pt] Se por um lado à privatização do setor de energia, que induz acirrada concorrência, tem estimulado a inovação tecnológica e a adoção de mecanismos de incentivos à eficiência operacional, a regulação do mercado introduz mecanismos de controle requerendo maior responsabilidade no uso consciente da energia de sorte a assegurar a eficiência energética e a proteção ambiental. Pressões de organizações ambientalistas internacionais e a crescente demanda por energia explicam a tendência mundial pelo uso de combustíveis fósseis mais limpos. O baixo nível de emissões e resíduos associados ao processo de combustão de gás natural qualifica esta commodity energética como um elemento estratégico para integrar a matriz energética de organizações e países comprometidos com a sustentabilidade global. O impacto econômico associado à medição de gás natural exige uma otimização do controle do balanço de massa no sistema de entrega. A aplicação da Metodologia de Reconciliação de Dados constitui o objetivo deste trabalho. A técnica provou ser uma ferramenta eficaz para a avaliação do balanço de massa em um gasoduto durante o período de operação associado ao transporte de gás natural. A natureza intrínseca do seu algoritmo de cálculo, que leva em conta a redundância nas medições, qualifica a metodologia para aumentar a confiabilidade da medição assim reduzindo a incerteza individual associada a cada grandeza física capaz de interferir na medição e identificar erros grosseiros. Fundamentado na avaliação metrológica do balanço de massa de um gasoduto brasileiro, os resultados do estudo permitem discutir a adequação da técnica proposta de reconciliação de dados. Dentre as conclusões do trabalho, foi possível mostrar que o uso da técnica de tratamento dos dados do gás não contado (unaccounted for gas) pode atingir valores inferiores a 0,3 porcento, comparando-se, assim, à tolerância preconizada em nível internacional. / [en] If on the one hand, privatization of the energy sector, which induces keen competition, has stimulated technological innovation and the adoption of incentive mechanisms for operational efficiency, regulation of the market introduces control mechanisms requiring greater responsibility in the conscious use of energy so as to ensure energy efficiency and environmental protection. Pressure from international environmental organizations and the growing demand for energy, explain the worldwide tendency for the use of cleaner fossil fuels. The lower levels of emissions and residues associated with the combustion process of natural gas classify this energy commodity as a strategic element to enter into the energy matrix of organizations and countries committed to global sustainability. The economic impact associated with the measurement of natural gas, demands optimization in controlling the mass balance in the delivery system. Application of the Data Reconciliation Methodology constitutes the objective of this work. The technique proved to be an efficient tool for the evaluation of the mass balance in a gas pipeline for the period of operation associated with the transport of natural gas. The intrinsic nature of its calculation algorithm, which takes into account the redundancy of measurements, qualifies the methodology to increase the confidence of measurement, thereby reducing the individual uncertainty associated with each physical volume capable of interfering with the measurement and identify gross errors. Based on the metrological evaluation of the mass balance of a Brazilian pipeline, the results of the study enable discussion on the adequacy of the data reconciliation technique proposed. Among the conclusions of the work, it was possible to demonstrate that the use of the technique in treating the data of unaccounted for gas, could achieve values lower than 0.3 percent, thereby comparable with the tolerances advocated at international level.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-10-31T13:52:01Z No. of bitstreams: 1 Dissertação_AnaMorena.pdf: 8629764 bytes, checksum: 9e0826a52706b5b7aaa97fd329fcac22 (MD5) / Made available in DSpace on 2017-10-31T13:52:01Z (GMT). No. of bitstreams: 1 Dissertação_AnaMorena.pdf: 8629764 bytes, checksum: 9e0826a52706b5b7aaa97fd329fcac22 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / O estudo de parâmetros e processos hidrogeoquímicos, e do uso dos solos permite o balanço de massas/fluxos (BM) de contaminantes entre segmentos fluviais, hierarquizando-os e identificando possíveis atividades-fonte. O incremento de fluxos indica uma depreciação de capital natural (DCN), demandando medidas reparadoras e/ou preventivas, e.g. pagamento por serviços ambientais (PSA). A DCN é o cerne da abordagem proposta, integrando aspectos hidrogeoquímicos e o BM, custos econômicos e mecanismos de gestão. O objetivo geral do trabalho foi estimar a DCN de três bacias afluentes na Bacia Hidrográfica da Baía de Guanabara: Guapi-Macacu (menos impactada), Caceribu (intermediária) e Iguaçu-Sarapuí (altamente impactada). São bacias pequenas com baixo tempo de retenção (5 a 10 horas), de setor montante no geral florestado, com forte declive exportador de materiais, e um jusante tendendo à acumulação e inundação, com verão chuvoso e inverno seco. Foi confeccionado um banco de dados de qualidade de água fluvial (n=678), englobando o período 1992-2015. A estatística da composição das águas comparada à legislação mostrou coliformes acima do estabelecido e OD e DBO nos rios Guapi-Macacu e Caceribu com maioria dos dados conformes à legislação, o contrário do encontrado para o Iguaçú-Sarapuí. O Índice de Qualidade de Água (IQA) indicou que setores montante de meia encosta apresentaram qualidade média e os de jusante qualidade ruim a muito ruim, e uma tendência à melhor qualidade no inverno devido à menor ocorrência de enxurradas. Comparando inverno e verão entre os cinco rios, o pH e o nitrato apresentaram diferenças significativas (p < 0,05) e, comparando serra e baixada, OD, turbidez, pH, nitrato e fósforo total apresentaram diferenças significativas. Através de ACP foram identificados dois processos hidrobiogeoquímicos principais: aporte de matéria orgânica de efluentes domésticos e da agropecuária, e aporte de materiais da erosão laminar. Duas coletas (inverno e verão) em 2016 foram realizadas para avaliar a situação atual nas cabeceiras dos rios. Houve uma perda significativa (uma ordem de grandeza) de qualidade nas últimas duas décadas considerando a razão indicadora N-NO3:P-PO4. O BM conseguiu caracterizar e hierarquizar os segmentos medindo os incrementos de fluxo dos contaminantes. O gráfico-síntese proposto para o modelo da DCN considerou “custo de tratamento” de água versus o “parâmetro indicador IQA” - incluindo as classes legais de água doce plotadas em termos de IQA. A curva resultante foi a “curva de oferta de qualidade de água” capaz de expressar o mercado de tratamento da água nas bacias estudadas e medir o custo de recuperação da qualidade perdida (DCN). Aplicado a situações-exemplo observadas no estudo, o modelo mostrou ser capaz de estimar o custo de recuperação da DCN, tendo como referência a potabilidade da água e, com isso, subsidiar negociações entorno do conceito de PSA no contexto imprescindível de um Comitê de Bacia. O PSA mostrou ser mais adequado às áreas na zona de amortecimento das unidades de conservação nas cabeceiras dos rios, pouco povoadas por pequenos produtores, a montante de cidades. A DCN seguiu a ordem de contaminação dos rios e a influência de esgotos urbanos sobretudo. / The study of hydrogeochemical process and parameters and of the soil use allow the contaminants mass/fluxes balance (MB) among fluvial segments, ranking them and the source-activities. The fluxes increment shows a depreciation of natural capital (DNC), demanding remedial and/or preventive measurements, e.g. payments for environmental services (PES). The DNC is the main proposed approach, integrating hydrogeochemical aspects and MB, economic costs and management mechanisms. The aim of this work was to estimate the DNC in three affluent basin of the Guanabara Bay watershed: Guapi-Macacu (less impacted), Caceribu (intermediate) and Iguaçu-Sarapuí (highly impacted). These are small basins with a low retention time (5 to 10 hours), of a forested upstream, with a strong material exporting slope and downstream tending to accumulate and flooding, with a rainy summer and dry winter. A data base of fluvial water quality was created (n=678), corresponding to the period of 1992-2015. The statistics of the water composition compared to the legislation showed coliforms above established, pH in accordance, and DO and BOD in the Guapi-Macacu and Caceribu rivers with most of the data according with the legislation, contrary to Iguaçu-Sarapuí. The water quality index (WQI) showed that half slope’s upstream shows medium quality and the downstream’s bad to too bad quality -, and tending to better quality in the winter, due to less occurrence of floods. Comparing winter and summer among the five rivers, the pH and nitrate levels showed significant differences (p < 0,05) and, comparing ridge and lowland, DO, turbidity, pH, nitrate and phosphorus showed significant differences, too. Through PCA were identified two main hydrobiogeochemical processes: organic matter input of domestic sewage and farming, and material from laminar erosion inputs. In 2016, two data collect (winter and summer) were made to evaluate the current situation in the rivers headboards. There was a significant lost (one order of magnitude) of quality in the last two decades considering the indicator ratio N-NO3:P-PO4. The MB could distinguish and rank the segments measuring the increments of contaminants fluxes. The synthesis-graphic proposed to the model of the DNC considered water “treatments costs” versus “WQI indicator parameter” – including the legal classes of fresh water plotted in terms of WQI. The resulting curve was the “Water Quality Offer Curve” able to express the water treatment market in the studied basins and measure the regeneration cost of quality loss (DNC). Applied to example-situations observed in the study, the model showed to be able to estimate the regeneration cost of the DNC, by having as reference the water potability and, with it, to support negotiations around the PES concept in the essential context of Basin Committee. The PES showed to be more appropriate to the buffer zones of the Conservation Units (CU) in the rivers headboard, sparsely populated by small producers, upstream from the cities. The DNC followed the order of contamination of the rivers and the influence of urban sewage especially.

Tese(doutorado) - Universidade Federal do Rio Grande, Programa de Pós–Graduação em Oceanografia Biológica, Instituto de Oceanografia, 2012. / Submitted by Cristiane Gomides (cristiane_gomides@hotmail.com) on 2013-12-15T10:09:04Z No. of bitstreams: 1 karina.pdf: 8139075 bytes, checksum: c30bac487b6f4defadafc03c71b60d50 (MD5) / Approved for entry into archive by Sabrina Andrade (sabrinabeatriz@ibest.com.br) on 2013-12-18T17:52:30Z (GMT) No. of bitstreams: 1 karina.pdf: 8139075 bytes, checksum: c30bac487b6f4defadafc03c71b60d50 (MD5) / Made available in DSpace on 2013-12-18T17:52:30Z (GMT). No. of bitstreams: 1 karina.pdf: 8139075 bytes, checksum: c30bac487b6f4defadafc03c71b60d50 (MD5) Previous issue date: 2012 / A alta produtividade na zona costeira e na Plataforma Continental do Sul do Brasil é dada pelo aporte de nutrientes, os quais são determinantes para a produção primária. As regiões de plataforma (Santa Marta-SC 28,60ºS e Albardão-RS 33,20ºS) foram selecionadas por apresentarem características diferenciadas em relação à topografia, sazonalidade e dinâmica das massas de água. Sendo assim, essas possuem diferentes mecanismos de fertilização, além dos aportes continentais. A proximidade à zona de Convergência Subtropical (CST) é determinante para a produtividade dessas regiões, visto que: no inverno, a intrusão da Água Subantártica de Plataforma na região do Albardão aumenta consideravelmente as concentrações de nutrientes na região e; no verão, a Água Central do Atlântico Sul resultado da CST aflora na região de Santa Marta, sendo responsável por 60% da produção nova local. Além disso, aportes subterrâneos foram evidenciados tanto na zona costeira quanto na região de plataforma. No extremo sul do Brasil verificou-se, mediante a variação espaço-temporal de isótopos naturais de rádio e radônio, a ocorrência de advecção de água subterrânea ao longo de toda a costa, desde a desembocadura da Lagoa dos Patos até as proximidades do Uruguai (média: 2,17± 0,2 cm d-1). Com a aplicação de modelos pré-estabelecidos, foi possível calcular os fluxosde nutrientes para a zona costeira (NIT: 21 105 mol d-1) e avaliar o potencial produtivo relacionado a essas descargas (2800 gC m-2 ano-1). Desse modo, entende-se que a parcela de água subterrânea deva ser definitivamente incluída no balanço de massas da região, uma vez que apresenta um potencial produtivo de 7 a 32 vezes maior quando comparado às outras regiões onde a estimativa foi realizada. / High productivity on the coastal region and on the Southern Brazil Continental Shelf is provided by the nutrient input which is fundamental to primary productivity. The regions of Santa Marta, SC (28.60ºS) and Albardão, RS (33.20ºS) were selected due to their special characteristics regarding the topography, seasonality and dynamics of their water mass. Therefore, these areas have different fertilization mechanisms besides the continental input. The proximity to the subtropical convergence zone (SCZ) is determinant in relation to productivity because, in winter, the intrusion of the Subantarctic Shelf Water (SSW) in the Albardão region considerably increases the nutrient concentration whereas, in summer, the South Atlantic Central Water (SACW) that results from the SCZ, moves to the Santa Marta region and is responsible for 60% of the new local production. In addition, subterraneous input was observed both on the coastal areas and on the shelf. In southern Brazil, spatial - time variations of radionuclides (Ra e Rn) show the occurrence of groundwater advection along the coast, from the mouth of Patos Lagoon to Uruguay rates (average: 2.17± 0.2 cm d - 1). Using mathematical models, it was possible to calculate the discharge of nutrients on the coastal zone (TIN: 21105 mol d - 1) and evaluate the productive potential regarding the Submarine Groundwater Discharge (2800 gC m - 2 y - 1). Thus, this study suggests that the portion of ground water should definitely be included in the mass budget of the region, since its productive potential is 7 to 32 times higher by comparison with other regions where this estimate was also carried out.

La qualité des eaux des lacs et le risque d’eutrophisation peuvent être évalués par une étude des composés biogènes. Les sources et les puits de nutriments qui déterminent les processus biogéochimiques peuvent être quantifiés avec un bilan de masse de matière. L’objectif de la thèse était de réaliser ce bilan de masse pour les nutriments dans les deux grands lacs côtiers médocains, Lacanau et Carcans-Hourtin (SW France). Pour cela, j'ai réalisé un suivi de la concentration en nutriments et des paramètres associés des eaux de pluie, des rivières, des canaux, des eaux des lacs et des eaux souterraines au cours de deux cycles hydrologiques en 2014 et 2015. Les processus biogéochimiques à l’interface eau-sédiment et les flux benthiques ont été déterminés à partir de carottes sédimentaires prélevées saisonnièrement et la construction d’une carte sédimentaire des deux lacs. Le bilan hydrologique a pu être réalisé à partir des données de débit et de hauteur d'eau, des mesures géophysiques et des mesures de 222Rn. Nos résultats ont permis de faire un bilan de masse complet de l'azote, du phosphore, de la silice, du fer et de l'alcalinité. Nous avons déterminé les principales sources et les puits de matière et leur évolution au cours de l’année. Les principaux résultats de la thèse sont avant tout la création d’un jeu de données original et riche qui permet pour la première fois d’avoir une vue d’ensemble de la biogéochimique des lacs aquitains. Nous montrons que l’impact des flux souterrains est faible. Les flux benthiques jouent un rôle majeur pour l’azote. L’export de composés biogènes à la sortie des lacs vers le milieu côtier a été quantifié et comparé aux apports par le bassin versant, ce qui a permis d’évaluer la capacité de séquestration des nutriments dans les sédiments. Nous montrons que ces lacs sont pauvres en phosphore, ce qui limite la productivité biologique. Nous avons aussi défini les conditions et les conséquences de la stratification transitoire des eaux des lacs en été. Cet ensemble de données a également permis d'apporter des connaissances supplémentaires sur la dynamique du mercure dans les lacs aquitains. Nous montrons le rôle que jouent les apports en sulfate du bassin versant sur la production de méthylmercure dans les sédiments. / To evaluate water quality and the risk of eutrophication of lakes, the dynamics of biogenic compounds must be studied. Sources and sinks of nutrients that define lake biogeochemical processes can be assessed from a mass balance approach and the study of internal reactions. The objective of the thesis was to realize a mass balance for nutrients in two coastal lakes: Lacanau and Carcans-Hourtin (SW France). For this purpose, I conducted a monitoring of rainwater, rivers, canals, lakes and groundwater concentration of nutrients and associate parameters during the two hydrological cycles of 2014 and 2015. Biogeochemical processes at the sediment water interface and benthic fluxes were determined from sediment cores collected at each season, and from the drafting of a new sediment map. The water balance was obtained from water level and discharge measurements, geophysical prospection and 222Rn measurements. Our results allowed us to make a full mass balance of nitrogen, phosphorus, silica, iron and alkalinity. We have identified the main sources and sinks of nutrients and their evolution along the year. The main results of the thesis is that groundwater discharge is not a significant contribution of nutrients; benthic fluxes supply high amount of dissolved nitrogen and most of the nutrient are sequester in the lake sediments. Total export of nutrient at the outlet of lakes has been quantified and compared to inputs from the watershed. We point out that phosphorus limits lake productivity. We also show the dynamics of transient lake stratification in summer and its impact on biogeochemical processes. This set of data has also provided additional insight into the dynamics of mercury in Aquitaine lakes. We show the role of sulphate inputs from the watershed in the production of methylmercury in lake sediments. All these results give for the first time an overall view of Aquitaine lake biogeochemistry.

La réduction du volume des glaciers et la fusion printanière plus précoce de la neige causée par le réchauffement climatique provoquent des variations du cycle hydrologique à la fois pour les têtes de bassin versant, mais aussi pour les zones situées plus à l’aval. Afin de prédire correctement l’amplitude des changements possibles futurs et d’envisager une gestion adaptée, une bonne connaissance de l’interaction entre les glaciers, le climat et les écoulements hydriques est nécessaire. L’objectif de cette étude est d’évaluer l’effet de la variabilité climatique sur le fonctionnement hydro-glaciologique et ses conséquences sur la disponibilité de l’eau du bassin versant de l’Arve (Alpes françaises) depuis 1960. Ce bassin s’étend sur une surface de 1958 km2 et est composé de cinq bassins versants emboités (Arveyron d’Argentière, Arveyron de la Mer de Glace, Arve au Pont des Favrands, à Sallanches and au Bout du Monde), tous influencés par la fusion glaciaire et nivale mais dans différentes proportions étant donnée la large gamme d’extension de couverture glaciaire s’étalant de 5 á 53%. Ce travail est basé sur des longs jeux de données glaciologiques, météorologiques, hydrologiques et de couverture de neige qui sont issues soit de mesures ponctuelles dans l’espace soit de données obtenues par télédétection.L’analyse des tendances a été réalisée sur des données hydrologiques et météorologiques des cinq bassins versants emboités. Pour cela, le cycle saisonnier du débit est ajusté en utilisant une fonction mathématique de type “modèle à pic asymétrique”. Les changements observés des débits ont été reliés aux variables météorologiques ainsi que à l’évolution de la couverture glaciaire. Les résultats indiquent un comportement contrasté entre les bassins versants selon les taux d’englacements, avec une tendance croissante des valeurs de débit dans les bassins versants fortement englacés (couverture de glacier >30%) et une décroissante pour les moins englacés. La sensibilité du cycle hydrologique au changement climatique futur a été évaluée. Pour le milieu du 21e siècle, on prévoit que le volume annuel écoulé serait réduit de 16% pour l’Arveyron d’Argentière et de 31% pour l’Arveyron de la Mer de Glace. Pour la période estivale, la quantification détaillée de chaque terme de l’équation du bilan hydrologique, ainsi que leurs incertitudes, sur les bassins versants de l’Arveyron d’Argentière et de l’Arveyron de la Mer de Glace-Leschaux a permis de souligner l’importance des transferts d’eau souterraine pour représenter et prédire le comportement hydro-glaciologique d’un bassin versant donné. Deux model d’écoulement distribués de type degré-jour couples à un modèle de routage hydrologique à réservoir linéaire ont était utilisé sur le bassin versant de l’Arveyron d’Argentière sur la période 1960–2009. La calibration est effectuée autant sur la base des données de débit qu’avec une approche multicritère avec les données de débit, de couverture neigeuse et du bilan de masse annuel, à pas de temps journalier. Les résultats montrent l’aptitude d’utiliser un modèle classique degré-jour pour simuler le comportement hydro-glaciologique et la production d’eau sous-glaciaire d’un bassin versant fortement glaciaire. Pour la période 1960–2004, une valeur de Kling Gupta Efficiency de 0.85 entre le débit simulé et observe à était obtenu. La calibration multicritère semble réduire les incertitudes des simulations. / Glacier recession and the anticipation of spring snow melt driven by a warming climate could lead to changes in the hydrological cycle affecting not only the headwater catchments but also the areas downstream. In order to correctly predict the magnitude of future possible changes and to consider appropriate strategies of water management, a good understanding of the interaction between glaciers, climate and hydrology is needed. The aim of this study is to assess the effect of climate variability on the hydro-glaciological behaviour and its consequence on water availability in the Arve River catchment (French Alps) since 1960. It covers 1958 km2 and is composed by five nested catchments (Arveyron d’Argentière, Arveyron de la Mer de Glace, Arve at Pont des Favrands, Arve at Sallanches and Arve at Bout du Monde), all influenced by glacier and snow melt but characterized by various percentages of glacier cover ranging from 5 to 53%. This research is based on a long dataset of in situ or remote sensing glaciological, meteorological, hydrological and snow cover area data.Trend analyses are performed on the hydrological and meteorological data at all the considered sites. The seasonal cycle of each catchment is fitted using a mathematical function, namely the asymmetric peak model, and changes in the discharge are related to observed changes in the meteorological variables and the glaciers’ evolution. Results point out a contrasting behaviour among the catchments characterized by different glacier covers, showing an increasing trend on the discharge values in highly glacierized catchments (with a glacier cover >30%) and a decrease in the low glacierized ones. The sensitivity of the seasonal cycle to the future climate is evaluated. In the mid-21st century the annual runoff would be reduced by 16% for Arveyron d’Argentière and 31% for Arveyron de la Mer de Glace. Over the summer season, a detailed quantification of each term of the hydrological balance equation, as well as their uncertainties, on the Argentière and Mer de Glace-Leschaux drainage basins allows to underline the importance of considering the groundwater transfers to represent and predict the hydro-glaciological behaviour of a considered catchment. Two different distributed temperature index melt models coupled with a linear reservoir discharge model are used on the Arveron d’Argentière catchment over the 1960–2009 period. The calibration is carried out against discharge only and with a multi- criteria approach considering the discharge, the snow cover area and the glacier-wide annual mass balance values at daily time step. Results demonstrate the suitability of the use of a classical degree day model in simulating the hydro-glaciological behaviour and the subglacial water production of a highly glacierized catchment. A KGE of 0.85 is obtained between the observed and simulate discharge values over the 1960–2004 period. The use of a multi-criteria approach seems to reduce the simulation uncertainties.

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No description available.

<p>The Earth–atmosphere energy balance is dictated by incoming solar radiation and outgoing thermal radiation with greenhouse gases (GHG) and aerosols playing a major role in this effect. The atmospheric abundance and properties of airborne particles and gases lead to the redistribution of radiative energy, resulting in a warming or cooling effect. However, the extent of this effect remains to be insufficiently constrained. Improved quantification and characterization of GHG and aerosols are important requirements to inform current climate models. High-precision instrumentation and thoughtful experimental strategies are necessary to yield various analytical measurement datasets, despite complex meteorological and environmental conditions. This dissertation focuses on the assessment of CO₂and atmospheric particles from aircraft-based measurements enabling representative and spatially sampling of local regions of interest.</p> <p>Chapter 1 provides introductory discussion on the atmospheric implication of GHG and aerosols on the climate and related uncertainties. Chapter 2 summarizes the employed experimental techniques for quantification of GHG and characterization of atmospheric particles. We relied on an aircraft platform equipped with an air turbulence probe for 3D wind vector calculation and a high-precision cavity ring-down spectrometer for the quantification of ambient CO₂, CH₄, and H2O_<em>v</em>. Furthermore, the simultaneous composition and morphological information of aerosol samples were assessed using complementary chemical imaging techniques. Chemical composition of elements with Z > 23 was determined using computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM/EDX). Scanning transmission X-ray microscopy coupled with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) was used to determined spatially resolved elemental specific molecular information present in atmospheric particles.</p> <p>Chapter 3 presents our study focused on the characterization of mixed mineral dust and biomass burning (BB) aerosols during an intensive burning event. We identified distinct particle types based on individual elemental contribution pre-, syn-, and post-burning event including highly carbonaceous (54–83%) particles, aged mineral dust (1–6%), and sulfur-containing particles (17–41%). X-ray spectromicroscopy techniques were used to characterize the internal chemical heterogeneity of individual BB particles and the morphology of soot inclusions, as well as changes in the particle organic volume fraction (OVF). An estimation method for particle component masses (i.e., organics, elemental carbon, and inorganics) inferred from STXM measurements was used to determine quantitative mixing state metrics based on entropy-derived diversity measures for particles acquired at different periods of the BB event. In general, there was a small difference in the particle-specific diversity among the samples (<em>D</em>_<em>α</em> = 1.3–1.8). However, the disparity from the bulk population diversity observed during the intense periods was found to have high values of <em>D</em>_<em>γ</em> = 2.5–2.9, while particles collected outside of the burning event displayed lower bulk diversity of <em>D</em>_<em>γ</em> = 1.5–2.0. Quantitative methods obtained from chemical imaging measurements presented here will serve to accurately characterize the evolution of mixed BB aerosols within urban environments.</p> <p>Chapter 4 follows the investigation of the physicochemical properties of atmospheric particles collected onboard a research aircraft flown over the Azores using offline spectromicroscopy techniques. Particles were collected within the marine boundary layer (MBL) and free troposphere (FT) comparing samples after long-range atmospheric transport episodes facilitated by dry intrusion (DI) events. The quantification of the OVF of individual particles derived from X-ray spectromicroscopy, which relates to the multi-component internal composition of individual particles, showed a factor of 2.06±0.16 and 1.11±0.04 increase in the MBL and FT, respectively, among DI samples. We show that supplying particle OVF into the <em>κ</em>-Köhler equation can be used as a good approximation of field-measured <em>in situ</em> CCN concentrations. We also report changes in the <em>κ</em> values in the MBL from <em>κ</em>_{MBL, non-DI} = 0.48 to <em>κ</em>_{MBL, DI} = 0.41, while changes in the FT result in <em>κ</em>_{FT, non-D}_I = 0.36 to <em>κ</em>_{FT, DI} = 0.33, which is consistent with enhancements in OVF followed by the DI episodes. Our observations suggest that the entrainment of particles from long-range continental sources alters the mixing state population and CCN properties of aerosol in the region.</p> <p>Chapter 5 discusses the identification and characterization of fine-mode primary biogenic atmospheric particles (PBAP) from the harvesting of crops. Particle samples were analyzed using complementary chemical imaging techniques to apportion the particle-type population based on their size, morphology, and composition. The contribution of PBAP in the size range of 0.15−1.25 μm is estimated to be 10−12% of ∼39,000 analyzed particles. In addition, particle viscosity and phase state were inferred with X-ray spectromicroscopic analysis has shown that the fine-mode organic particles collected are viscous/semisolid (10²−10¹² Pa s) while the majority of PBAP fragments are solid (>10¹²Pa s). The observation of submicrometer, solid carbonaceous fragments of biogenic origin have implications for the regional CCN and ice nuclei budget. Therefore, the seasonal harvesting of crops may play an important, yet unrecognized, role in regional cloud formation and climate.</p> <p>Chapter 6  explores the measurements and quantification of latent heat, sensible heat, and CO₂ fluxes among different land covers in the surrounding area of urban regions using airborne flux techniques. Cities account for the majority of the global CO₂ emissions due to the consumption of energy, resources, infrastructure, and transportation demands. Accordingly, the accurate quantification of these emissions, with exceptional precision, is necessary so that progress towards emission reduction can be monitored. However, a major challenge in quantifying urban emission estimates arises from accurate background emission definitions and apportionment of emission sources in complex urban environments. Airborne eddy covariance measurements were performed to quantify the bidirectional exchange of latent heat, sensible heat, and CO₂ fluxes in the upwind region of Indianapolis within an active biosphere. Here, we observed differences in fluxes across different days and land covers (e.g., corn, soybean, and forests) allowing us to understand the impact of seasonal variability in urban emissions during the full growing season. These experiments illustrate the capability of a research aircraft to perform technically challenging near-direct measurements of atmosphere–surface exchange over local and regional scales.</p> <p>Chapter 7 presents a new method to spatially allocate airborne mass balance CO₂ emissions. We performed seven aircraft measurements downwind of New York City (NYC) quantifying CO₂ emissions during the non-growing seasons of 2018–2020. A series of prior inventories and footprint transport models were used to account for flux contribution outside the area of interest and attribute emission sources within policy-relevant boundaries of the five boroughs encompassing NYC and then employ the modeled enhancement fraction (Φ) to the bulk emission observations from the mass balance approach. Here, we calculated a campaign-averaged source apportioned mass balance CO₂ emission rate of 56±24 kmol/s. The performance and accuracy of this approach were evaluated against other published works including inventory scaling and inverse modeling, yielding a difference of 5.1% with respect to the average emission rate reported by the two complementary approaches. Utilizing the ensemble of emissions inventories and transport models, we also evaluated the overall sources of variability induced by the prior (1.7%), the transport (4.2%), and the daily variability (42.0%). This approach provides a solution to interpreting aircraft-based mass balance results in complex emission environments.</p> <p>Chapter 8 concludes with a brief discussion of technological advances and research outlooks for X-ray spectromicroscopy analysis on atmospheric particles and the quantification of GHG. Opportunities for future applications and novel development of CCSEM/EDX and STXM/NEXAFS to substantially extend the instrument capabilities and improve our understanding of the physicochemical properties of individual atmospheric particles. Chapter 8 also discusses recent developments in satellite-based CO₂ monitoring to complement direct airborne observations. In recent years, significant progress has been made in satellite-based measurements of CO₂ to reveal the spatio-temporal variation in atmospheric CO₂ concentration. The column-averaged dry air CO₂ mole have reached an accuracy of ~1 ppm with a spatial resolution of less than 4 km. Furthermore, column-averaged retrievals can be used to detect and estimate the surface CO₂ fluxes in an active biosphere, quantify anthropogenic emissions over megacities, and monitor the transport of fossil fuel plumes across different continents and seasons.</p>

Die Gletscher Hochasiens beeinflussen durch ihr Schmelzwasser die Wasserverfügbarkeit eines der gefährdetsten ‚globalen Wassertürme‘. Des Weiteren stellen diese Gletscher und die Gletscherseen eine Gefahr durch Überschwemmungen, Lawinen und Erdrutsche dar. Die Sensitivität und Variabilität von Gletschermassenbilanzen in Hochasien werden in dieser Dissertation untersucht. Das Energie- und Massenbilanzmodell „COupled Snowpack and Ice surface energy and mass balance model in PYthon (COSIPY)“ ist dabei das Hauptwerkzeug. Neun verschiedene gegitterte Niederschlagsdatensätze wurden verglichen, um Aussagen über deren Anwendungsmöglichkeiten zu treffen. Es wurden Verfahren für die Vorverarbeitung von Reanalyse-Datensätzen entwickelt, um diese als klimatische Antriebsdaten für COSIPY zu verwenden. Dazu standen Daten von drei automatischen Wetterstationen an verschiedenen Gletschern zur Verfügung. Die Modellevaluation auf der Basis von Beobachtungsdaten bildete den Ausgangspunkt, um die klimatische Massenbilanz von 14 Gletschern in allen großen Gebirgszügen Hochasiens mit einem konsistenten Ansatz zu modellieren. Die räumlich aufgelösten klimatischen Massenbilanzen von 2000 bis 2018 wurden mithilfe geodätischer Massenbilanzen aus Fernerkundungsdaten kalibriert. Generell haben mehr südöstlich gelegene Gletscher höhere Massenumsätze und diese sind sensitiver gegenüber Schwankungen von Temperatur und Niederschlag. Alle Gletschermassenbilanzen sind am sensitivsten gegenüber Temperaturänderungen im Sommer und gegenüber Niederschlagsänderungen im Sommer oder Frühling. Die Resultate unterstreichen die Notwendigkeit zukünftiger Forschung zu räumlich aufgelösten Reaktionen von Gletschern auf Klimaantrieb und daraus resultierender Variabilität von Schmelzwasser unter Verwendung interdisziplinärer Methoden in Hochasien. Aufgrund der Heterogenität der Gletscher in Hochasien ist diese Forschung essentiell für die künftige Anpassung an Klimavariabilität und Klimawandel in der Region. / The meltwater from the glaciers of High Mountain Asia (HMA) impacts water availability of one of the most vulnerable ‘water towers’ of the globe. Furthermore, glaciers and glacial lakes represent a danger through floods, avalanches and landslides. The climatic sensitivity and variability of the glacier mass balances are investigated within this thesis. The COupled Snowpack and Ice surface energy and mass balance model in PYthon (COSIPY) is thereby the main tool. Nine gridded precipitation datasets have been compared to evaluate possible applications in HMA. The variability and timing of precipitation between May and September 2017 are consistent between the datasets, whereas great differences in precipitation amount were found. A preprocessing toolbox has been developed to use reanalysis datasets as climate forcing for COSIPY within the thesis. Measurements of three automatic weather stations at different glaciers were available for bias correction. Based on these model validations with observed data, climatic mass balances of 14 glaciers in all major mountain ranges in HMA were simulated using a consistent approach. The distributed climatic mass balances for the period from October 2000 to September 2018 were calibrated with remote-sensing-based geodetic mass balances. In general, glaciers with higher mass turnover are located in the southeast of HMA. They are more sensitive to perturbations of temperature and precipitation. All glaciers are most sensitive to monthly temperature perturbations in summer and to precipitation perturbations in summer, spring or spring and summer. The results emphasise the need for future research on spatially resolved responses of glaciers to climate forcing and resulting variability of meltwater using coherent interdisciplinary methods in HMA. Due to the heterogeneity of glaciers in HMA, such research is essential for adaptation to future climate variability and climate change in the region.

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