Le carbone-suie, ou “black carbon” (BC), contribue au réchauffement climatique avec un forçage positif de l’ordre de +1.1 W m-2 dont l’incertitude reste haute (de l’ordre de 90%). Ce forçage s’effectue à travers l’interaction aérosol-radiation et l’interaction aérosols-nuage. Ces deux mécanismes sont affectés par le degré de mélange des particules du BC avec divers matériaux non-réfractaires et non-absorbants. Cependant, les estimations du forçage radiatif considèrent rarement les effets du mélange interne. Par ailleurs le rôle du BC comme noyau glaçogène qui influence l’interaction aérosol-nuage est largement inconnu. L’objectif de cette thèse est de mieux comprendre les mécanismes par lesquels le degré de mélange interne du BC influence la variabilité des propriétés optiques du BC et les propriétés d’activation des noyaux glaçogènes contenant du BC.Dans le premier chapitre de cette thèse, nous avons exploré la variabilité spatiale et saisonnière du coefficient d’absorption massique -mass absorption cross-section (MAC)- dans l’atmosphère en Europe. Les valeurs de MAC sont déterminées à partir de concentrations de carbone élémentaire et de coefficients d’absorption observée à différentes stations d’observation européenne du réseau ACTRIS (Aerosol, Cloud and Trace gases Research InfraStructure). Les résultats montrent une faible variabilité spatiale du MAC avec une moyenne de 10 ± 2.5 m2 g-1 à 637 nm de longueur d’onde qui peut être considérée comme représentative du BC en Europe. Le cycle saisonnier du MAC est probablement lié à la composition chimique de l’aérosol et son état de mélange, qui provoque une augmentation du MAC.Dans le second chapitre on s’est intéressé au lien entre l’absorption du BC et son état de mélange après transport sur longue-distance. Ce travail se base sur des mesures effectuées dans le cadre du projet CLIMSLIP (CLimate IMpact of Short-Lived Pollutants and methane in the Arctic). Une campagne de mesure a été conduite sur la station de recherche Zeppelin au Svalbard, Norvège en Avril 2012. Les données acquises avec un Single Particle Soot Photometer (SP2) révélaient que le BC est généralement présent en mélange interne dont l’épaisseur moyenne de la couche superficielle de matériel non-absorbant est de 47 nm pour des particules de BC de diamètre compris entre 170 et 280 nm. Ce mélange interne conduit à une augmentation d’absorption de 46%. Elle entraîne cependant une diminution relativement faible de l’albédo de simple diffusion, de l’ordre de 1%.Enfin, la capacité du BC à agir comme noyaux glaçogène pour la formation de cristaux de glace a été étudiée sur le site de haute altitude du Jungfraujoch (Suisse) dans le cadre du “cloud and aerosol characterization experiment” (CLACE) en 2013. Les différents éléments du nuage étaient séparé à partir d’une prise d’entrée type ice-CVI connectée au SP2. Ce dispositif permet de sélectionner uniquement les cristaux de glace et quantifier la fraction de BC activée. Une réduction de la présence de BC dans les résidus de glace a été observée. Des mesures de l’épaisseur de la couche de mélange interne des particules contentant du BC ont montré que les résidus de cristaux de glace présentaient des enrobages bien plus épais comparée à l’aérosol total.Les résultats obtenus au cours de ce travail ont permis de mieux comprendre l’impact du degré de mélange interne sur les propriétés optiques du BC et sur son rôle dans la formation de cristaux de glace. Les propriétés optiques du BC évoluent en fonction de la saison, tandis que la formation d’une couche superficielle amplifie sa capacité d’absorption du rayonnement solaire. De plus, cette étude souligne l’importance du vieillissement atmosphérique du BC sur sa capacité à servir de noyau de nucléation de la glace. Enfin, il fournit une avancée au sujet des propriétés sensibles mesurées dans l’atmosphère avec des techniques innovantes qui permettront la simulation plus précise du forçage radiatif. / Black carbon (BC) induces a warming effect (RFBC = +1.1 W m-2 ± 90%) through two main pathways: aerosol-radiation interaction (RFari) and aerosol-cloud interaction (RFaci). Both BC-radiation and BC-cloud interaction are affected by the mixing of black carbon with other non-refractory and non-absorbing matter present in the atmosphere. An estimation of the global radiative forcing of BC rarely accounts for internal mixing of BC while the net global cloud radiative forcing is sensitive to assumptions in the initiation of cloud glaciation, which is mostly unknown for black carbon particles. Within this thesis we investigated the variability of the light absorbing properties of black carbon, the mixing of black carbon, and the impact on light absorption and ice activation.In the first part of this thesis we investigated the spatial and seasonal variability of the mass absorption cross section (MAC) over Europe. MAC values were determined from ambient observations of elemental carbon mass concentrations (mEC) and absorption coefficients (σap). The data had been acquired during several years at different background ACTRIS supersites spread over Europe. Site specific MAC values were found to be spatially homogeneous, suggesting that the overall MAC average 9.5 ± 1.9 m2 g-1 at a wavelength of 637 nm might be representative of BC at European background locations. The MAC values showed a distinct seasonal cycle at every station. This seasonality might be related to chemical composition and aging. We observed that the MAC value has a linear and positive proportionality with the non-absorbing matter mass fraction.The second part of the work focuses on the coating acquisition of BC and the induced absorption enhancement after long-range transport. Within the CLIMSLIP (climate impact of short-lived pollutants and methane in the Arctic) project field experiments were conducted at the Zeppelin research site in Svalbard, Norway, during the Arctic spring. SP2 data were used to characterize the BC size distribution and mixing. BC containing particles having a core diameter between 170 and 280 nm were found to have a median coating thickness of 47 nm. The relationship between coating thickness and BC absorption was simulated. The observed coating thickness enhanced the mass absorption cross section by 46%, which led to a decrease of less than 1% in the single scattering albedo.In the final part of this work, the role of black carbon as ice nuclei in mixed phase clouds was investigated at the high elevation measuring site Jungfraujoch (Switzerland) during the cloud and aerosol characterization experiment (CLACE) held in 2013. The ice-CVI inlet and a single particle soot photometer were used to select and quantify the ice activated BC particles. According to the observations, BC containing particles were depleted in the ice residuals. The activation efficiency showed a size dependency, with larger BC containing particles being activated more efficiently compared to smaller ones. Activated BC cores having a diameter between 170 and 240 nm showed a larger coating thickness (median = 53 nm) compared to the total aerosol (median = 16 nm).The results obtained in this thesis shed new light on the effect of the mixing state on the optical properties and cloud activation of black carbon particles. Absorbing properties of BC showed a distinct seasonal pattern, while aging was found to consistently increase its absorption behavior. However, black carbon was found not to act as ice nuclei in low tropospheric mixed-phase clouds, where the coating thickness might play a role in the activation efficiency. This work provides freshly determined physical properties derived from ambient observations that will improve the accuracy of future aerosol and cloud radiative forcing estimations.

A Terra Preta Antropogênica (TPA) tem essa denominação porque é encontrada em sítios arqueológicos, onde viveram grupos pré-históricos e é considerada um dos solos mais férteis do mundo. Nela é encontrada grande quantidade de material deixado por grupos indígenas como fragmentos cerâmicos, artefatos líticos, e especialmente carvão pirogênico. Estudos realizados com o carvão pirogênico verificaram que ele aumenta a capacidade de trocas catiônicas nesses solos. Por meio de microscopia de fluorencência, foi observada a presença de microrganismos habitando esse carvão, no entanto, não se sabe quais seriam. Devido à falta de informações sobre a diversidade bacteriana nessas estruturas, este trabalho estudou a diversidade bacteriana em amostras de carvão pirogênico de solos TPA coletadas nos sítios Lagoa Balbina (Amazônia Central- Amazonas) e Mina I (Amazônia Oriental - Pará), através de técnicas moleculares independentes de cultivo. O estudo visou também comparar essa diversidade com a encontrada no solo de onde carvão foi isolado. As estruturas de carvão foram separadas fisicamente dos solos e seu DNA genômico total extraído e usado como molde em reação de PCR utilizando oligonucleotídeos do gene 16S rRNA para o Domínio Bacteria. O produto da PCR foi clonado em vetor e os clones foram sequenciados e comparados com o banco de dados de 16S rRNA do RDPX. Com a construção das bibliotecas de clones do gene 16S rRNA a partir das amostras de carvão pirogênico observou-se que existe maior número de bactérias desconhecidas no carvão pirogênico do que no solo onde ele foi isolado. Acidobacteria foi o filo predominante nas bibliotecas de carvão pirogênico das duas localidades de estudo, assim como na biblioteca do solo do sítio Mina I. Já na biblioteca do solo do sítio Lagoa Balbina houve predominância do filo Firmicutes. Por meio do método de rarefação foi possível constatar uma menor riqueza de UTOs nas comunidades bacterianas presentes nas estruturas de carvão pirogênico quando comparado à riqueza de UTOs das comunidades bacterianas cujo habitat é o solo. Mas quando se compara a riqueza de UTOs entre as estruturas de carvão isoladas das duas localidades, observa-se que a riqueza é maior no sítio Mina I. Os valores obtidos com os índices de diversidade revelaram menor diversidade de UTOs nas bibliotecas obtidas para o carvão pirogênico das duas regiões estudadas se comparado dos valores para as bibliotecas obtidas do solo da mesma região. Os valores obtidos com os métodos não paramétricos revelaram maior riqueza de UTOs para as bibliotecas do carvão do sítio Mina I e solo TPA do sítio Balbina. A análise da PCA revelou que as bibliotecas do sítio Balbina mostraram-se altamente similares. Em adição, a análise com S-Libshuff, verificou que todas as bibliotecas comparadas são significativamente diferentes quanto à composição das comunidades bacterianas. O carvão pirogênico não é uma estrutura inerte, pois é capaz de ser habitado por diferentes bactérias e a sua estrutura da comunidade bacteriana é diferente daquela de onde ele foi segregado / Anthropogenic Dark Earth (ADE) has this denomination because it is found at archeological sites, where prehistoric groups lived, and it is considered one of the most fertile soils of the world. In this soil a great amount of material left by indigenous groups was found as ceramic fragments, lithic workmanships, and especially pyrogenic black carbon. Studies accomplished with the pyrogenic black carbon verified that it increases the capacity of cationic changes in soils. Through fluorescence microscopy, the presence of microorganisms was observed inhabiting that black carbon, however, this community is still unknown,due to the lack of information about the bacterial diversity in those structures.This work studied the bacterial diversity in samples of pyrogenic black carbon of ADE soils, collected at the sites Lagoa Balbina (Central Amazon) and Mina I (Oriental Amazon), through molecular techniques independent of cultivation. The study also sought to compare that diversity with the one of the soil where black carbon was isolated. The structures of black carbon were separate physically from the soils and total genomic DNA was extracted and used as template in a PCR reaction, using primers of the 16S rRNA gene for the Bacteria Domain. The PCR product was used for construction of clone libraries and the clones were sequenced and compared with the 16S rRNA of RDPX database. The 16S rRNA gene clone libraries from the samples of pyrogenic black carbon, it shown that is a larger number of unknown bacteria in the black carbon than in the soil where it was isolated. Acidobacteria was the predominant phylum in the pyrogenic black carbon libraries from the both studied places, as well as in the soil library from Mina I site. However in the library Lagoa Balbina site there was predominance of the phylum Firmicutes. Through the rarefaction method it was possible to verify a smaller richness of OTUs in the bacterial communities presents in the pyrogenic black carbon structures when compared to the OTUs richness of the bacterial soil communities.But, when the OTUs richness is compared among the isolated structures of pyrogenic black carbon of the two places, it is observed that the richness is higher in the Mina I site. The values from diversity indexes revealed smaller diversity of OTUs in the pyrogenic black carbon libraries when compared with the soil libraries for the two studied areas. The obtained values with the nonparametric methods revealed larger OTUs richness in the black carbon library of Mina I site and in the ADE soil library of the Balbina site. The PCA analysis showed that the libraries of the site Balbina site were highly similar. In addition, the analysis with S-Libshuff verified that all of the compared libraries were significantly different in bacterial communities composition. The pyrogenic black carbon is not an inert structure, once it is capable of being inhabited by different bacteria, and its bacterial community structure is different from that one where is was segregated

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-07-03T17:28:54Z No. of bitstreams: 1 MARTINS, G. S..pdf: 4719726 bytes, checksum: 2256ee6ea720c11998227a048aa70881 (MD5) / Made available in DSpace on 2017-07-03T17:28:54Z (GMT). No. of bitstreams: 1 MARTINS, G. S..pdf: 4719726 bytes, checksum: 2256ee6ea720c11998227a048aa70881 (MD5) / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / O estudo em questão apresenta o uso do Carbono graf ítico (BC) como indicador de queimadas em dois enfoques: ocorrência de paleoincêndios em um r egistro sedimentar do Lago do Saci (PA), com o intuito de evidenciar eventos de distúrbios relacio nados a queima de sistemas florestais associados a ocorrência de paleoclimas secos na parte sudeste da Amazônia ao longo do Holoceno e como indicador de queimadas em registros sedimentares de mudança do u so da terra, no município de Alta Floresta (MT). O perfil da concentração de carbono grafítico (BC) de terminado através do método térmico (CTO-375) refere-se ao testemunho SACI 1, que abrange 9200 an os cal AP e a quatro registros sedimentares de barragens artificiais do norte do Mato Grosso .refe rente aos últimos 100 anos. No registro sedimentar do Lago do Saci foi possível observar quatro fases dis tintas de sedimentação que permite distinguir difer entes fases paleoclimáticas. No Holoceno inferior, observ a-se uma transição de um ambiente úmido para um mais seco, caracterizado por fortes eventos de enxu rradas. No Holoceno Médio estabeleceu-se um ambient e deposicional de baixa energia hidrodinâmica, com al tos valores de carbono grafítico suportando a existência de um clima seco. A transição para o Hol oceno tardio foi marcado por um clima úmido como sugerem o aumento de carbono orgânico total e deriv ados de clorofila assim como reduções nos valores d e concentração de carbono grafítico. Durante o Holoc eno Tardio, o aumento da concentração de BC é observado por volta de 1850 anos cal AP, decorrente s de atividades antrópicas na região ou alteração d e biomassa. Nos registros de mudança do uso da terra, os dados de carbono grafítico auxiliam na determinação da dimensão dos incêndios em escala lo cal ou regional como dado complementar a contagem microscópica de partículas de carvão, bem como proc essos de co-deposição entre o mercúrio e BC, como mostra a correlação significativa e positiva entre os dois parâmetros (p < 0,05; N=59 e r = 0,55). A a nalise das partículas de carvão e Hg sugerem a remobilizaç ão o metal por ação de queimadas, pois os testemunh os LCEN050 e WSW150 apresentaram as maiores concentraç ões de partículas de carvão 10,8x10 6 e 6,96x10 6 partículas/g respectivamente e os menores valores m édios na concentração de Hg (0,06 e 0,07ppm respectivamente). Considerando que em setores mais afastados ao centro municipal e de maior conservaçã o de biomassa, observam-se os maiores valores de acum ulação de carbono grafítico, 0,023% (LCEN050) e 0,078% (WNW150) de BC, sugere-se que o transporte d estas partículas pela circulação atmosférica de longo percurso. Em escala temporal, o processo de o cupação territorial é observado no testemunho WNW150 (única barragem natural entre as quatro estu dadas). O processo de colonização do município, ocorrido na década de 70, é marcado pelo aumento do s fluxos de todos os parâmetros a partir de 1967. O fluxo de partículas de carvão aumenta de 0.028 para 0,500x10 10 partículas/m2/ano e os de Carbono grafítico de 0,405 para 2,28 gBC/m 2 /ano entre 1967 e 1984. / his study presents the use of Black Carbon as indi cator of fire occurrences on two approaches: Occurrences of paleofires in a sediment ary record of Saci lake (PA), to related events of burning forest, associated with the occur rence of dry paleoclimates, in the southeastern part of the Amazon during the Holocene ; and as an indicator of fire records of land change use in Alta Floresta (MT).The concentra tion of Black Carbon (BC)for the core SACI 1, with a basal age of 9200 cal years BP, and four core in the northern Mato Grosso that covers the last 100 years, was determined by the th ermal method (CTO-375).In the sedimentary record of Saci lake was identified four units of sedimentation which correspond to different paleoclimatic phases . In the Early Holocene the transition from humid to a drier climate was observed, characterized by the occurren ce of run-off events. In the Mid-Holocene was established a depositional environment of low h ydrodynamic energy, with high values of BC supporting the existence of a dry climate. The M id-late Holocene transition was marked by a humid climate as suggest the increase in TOC v alues and chlorophyll derivates as well as the reduction in the BC concentration . In the Late Holocene occurs the increase of BC concentrations in 1850 cal yrs BP, due the antropog enic activities in the region or biomass change around the lake. In the land change use reco rds, the BC profile work with a complementary proxy associated with the charcoal pa rticles, could provide the extent of fires in regional or local scale, well as the co-deposition process of mercury and BC , as shown insignificant and positive correlation between the two parameters(p <0.05, N = 59; r = 0.55). The analysis of the coal particles and Hg suggest the r emobilization of the metal by the burning process used for croplands installation, for the cores LCEN 050 and WSW150 had the highest concentrations of carbon particles 10.8x10 6 and 6.96x10 6 particles/g respectively and the lowest average concentration of Hg (0.06and 0.07 ppm respectively) . In the more distant collect point of the town center with larger biomass conservation, there are the highest accumulation of graphitic carbon, 0.023% (LCEN050) and 0.078% (WNW150) BC, it is sugg ested suggest the transport of these particles by the atmospheric circulation. In the te mporal scale, the process of land occupation is observed in the core WNW150. The process of coloniz ation of the city, occurred in the 70's, is marked by increased flows of all parameters since 1967. Th e flow of carbon particles increases from 0.028x10 10 to 0.500x10 10 partícles/m 2 /yr and graphitic carbon of 0.405 to 2.28 gBC/m 2 /yr between 1967 and 1984

How great potential effect does the Black carbon emitted from the boreal forest fire region of Alaska have on the retreating glaciers of the St. Elias Mountains? In this study climate and forest fire history data of Alaska was run in the HYSPLIT wind trajectory model to generate trajectories originated from large occurring fires in Alaska from 2005 to 2014. Results show a small percentage of trajectories passing the St. Elias Mountains and an expected pattern of a correlation between passing trajectories and density of amount forest fires. Interdisciplinary climate research is indicating an increase in global temperatures with consequences such as an upswing of forest fires in the Northern Hemisphere. Inner Alaska is fire prone due to a combination of prevailing droughts during the summer season and frequent lightning ignition as a result from homogeneous vegetation and topography. Downwind from Alaska’s forest fire region is the ice field of the St. Elias Mountains, these glaciers are one of the fastest retreating due to increasing global temperatures and possible deposition of soot from Alaskan forest fires. Forest fire emits black carbon, which when deposited on snow or ice surfaces will decrease the albedo and accelerate the melting rate. Previous studies on ice cores from the St. Elias have investigated traces of combustion products from biomass burning. This indicates a possible record of historic forest fires in ice cores. The small percentage of passing trajectories in this study suggests that most large forest fires in Alaska might not be registered in the St. Elias ice cores.

Les aérosols carbonés, qui incluent les aérosols organiques (AO) et le carbone suie (BC), jouent un rôle majeur sur la qualité de l’air et sur le climat. Il est donc primordial de pouvoir quantifier leurs sources, ainsi que celles de leurs précurseurs gazeux, pour la mise en œuvre de plans d’action appropriés. Les études de tendance sur la composition chimique de l’atmosphère sont également nécessaires afin d’améliorer les connaissances de l’impact des particules sur le réchauffement climatique, actuel et à venir. Ce travail de thèse a permis d’exploiter les mesures automatiques et in situ des aérosols carbonés réalisées au SIRTA (Site de Recherche par Télédétection Atmosphérique) depuis plus de 6 ans. Cet observatoire appartient au programme européen ACTRIS (infrastructure de recherche européenne sur les aérosols, nuages, et espèces gazeuses réactives). Il est situé à 25 km au sud-ouest de Paris et est représentatif de la pollution de fond en région Ile de France. Les principales sources d’AO ont été discriminées à l’aide de l’outil Positive Matrix Factorization appliqué aux données issus d’un Aerosol Chemical Speciation Monitor (ACSM). Les propriétés d’absorption de la lumière de BC et du brown carbon (BrC) ont été mesurées à l’aide d’un aethalomètre multi-longueurs d’onde. L’ensemble des résultats obtenus indiquent des cycles saisonniers, hebdomadaires et journaliers spécifiques aux différentes fractions des aérosols primaires et secondaires. Ils ont confirmé que l’AO primaire (AOP), provenant essentiellement de la combustion de biomasse et du transport routier, est prépondérant sur la période froide (de novembre à février), alors que le reste de l’année est dominé par des aérosols organiques oxygénés. Parmi ces derniers, une fraction moins oxydée, provenant probablement de façon majeure de précurseurs biogéniques, est prépondérante en été (60% de l’AO en moyenne estivale). Les études de tendance ont montré une légère diminution des concentrations (de l’ordre de 0.05-0.20 µg/m3 par an) de toutes les fractions d’AO identifiées au cours de la période étudiée, hormis pour cette fraction d’AO moins oxydée qui ne présente pas de tendance significative. Concernant les propriétés optiques, une contribution moyenne globalement équivalente à celle de BC a été observée pour le BrC dans le proche ultraviolet en hiver. Par ailleurs, il a été mis en évidence une augmentation significative des propriétés d’absorption du BC liée à des interactions avec les aérosols secondaires en mélange interne, en particulier en été (avec une valeur moyenne de 1.6 pour le paramètre Eabs). La fraction organique la plus oxydée a pu être identifiée comme principale responsable de ce phénomène, faisant des aérosols organiques secondaires l’une des fractions des particules les plus importants à considérer par les modèles climatiques. / Carbonaceous aerosols, including organic aerosols (OA) and black carbon (BC), are playing important roles on air quality and climate change. Therefore, quantifying contribution of their emission sources, as well as the sources of their gaseous precursors, is needed to implement efficient mitigation measures. Investigating trends in atmospheric composition is also essential to a better knowledge of present and future impacts of airborne particles on global warming. This work aimed at investigating on-line and in situ carbonaceous aerosol measurements performed for more than 6 years at the SIRTA facility (Site Instrumental de Recherche par Télédétection Atmosphérique). This observatory platform is part of the ACTRIS (Aerosols, Clouds, Trace gases Research InfraStructure). It is located 25 km southwest of Paris city center and is representative of background air quality in the Ile de France region. The main sources of submicron OA were discriminated through Positive Matrix Factorization applied to Aerosol Chemical Speciation Monitor (ACSM) data. Light absorption properties of BC and brown carbon (BrC) were obtained from multi-wavelength Aethalometer measurements. Converging results illustrated well-marked seasonal, weekly, and diel cycles of the various primary and secondary carbonaceous aerosol fractions. Primary OA (POA), mainly from wood burning and traffic emissions, were confirmed to dominate submicron OA concentrations during the coldest months (November to February), while Oxygenated OA (OOA) were shown as the major contributors during the rest of the year. Less Oxidized OOA (LO-OOA), possibly with predominant biogenic origins, were found to contribute up to about 60% of total submicron OA on average in summer. Trend analyses indicated slight decreasing features (in the range of 0.05-0.20 µg m-3 yr-1) for every OA fractions over the 6+-year investigated period, except for this LO-OOA factor which showed no significant trend. Regarding absorption properties, BrC - with overwhelming biomass burning origin - was found to have equivalent light absorption impact than BC at near-ultraviolet wavelengths during the winter season. In summer, a mean value of 1.6 was obtained for BC absorption enhancement (Eabs) due to secondary aerosol lensing effect, supporting possible higher BC-related radiative impact than currently expected. Last but not least, More Oxidized OOA (MO-OOA) were shown as the main agent for this Eabs and then appeared as one of the most critical aerosol fraction to be considered within near-future climate models.

The German Ultrafine Aerosol Network (GUAN) has been continuously measuring the particle number size distribution (PNSD) and equivalent black carbon (eBC) mass concentration since 2009 at 17 atmospheric observatories in Germany, covering all environments from roadside to high-Alpine environments. GUAN provides us an opportunity to reduce the knowledge gaps about the spatio-temporal variation of sub-micrometer particles in different size ranges and eBC mass. These data are not only highly valuable for air pollution and health studies but also can help to reduce the uncertainties in the climate model predictions. With these long-term multi-site-category measurements, it was investigated for the first time how pollutant parameters interfere with spatial characteristics and site categories. Based on this first investigation, the long-term changes in size-resolved particle number concentrations (PNC) and eBC mass concentration were investigate to evaluate the effectiveness of the emission mitigation policies in Germany. The emission and pollutants near ground can be frequently transported to the free troposphere (FT) in the mountain areas. To identify if the decreased emissions at lower-altitudes have affected the aerosol loading in the aged, well-mixed FT air over Central Europe, the long-term trends in PNC and eBC mass concentration were analyzed for the FT and planetary boundary layer (PBL) conditions separately, at two high-Alpine observation sites. In summary, this dissertation aims to answer the following related scientific questions: Q1: How do the sub-micrometer PNSD, PNC, and eBC mass concentration interfere with spatial characteristics and site categories? (First publication) In the first publication (Sun et al., 2019), the spatio-temporal variability of aerosol parameters including PNSD, PNCs, and eBC mass concentration from the GUAN network were investigated for the period 2009−2014. Significant differences in the pollutant concentration were observed among various site categories. The six-year median value of sub-micrometer PNC (diameter range 20–800 nm) varies between 900 and 9000 cm−3, while median eBC mass concentration varies between 0.1 and 2.3 μg m-3 in 17 observation sites. PNCs in different size ranges were found in different spatial variabilities. A cross-correlation between PNSD and eBC mass concentration was analyzed to detect the influence of anthropogenic sources for different site categories. The size-dependent spatial variability analysis of PNCs extracted three size intervals: a higher spatial variability size range 10–30 nm, a transition size range 30–100 nm and a lower spatial variability size range 100–800 nm. Based on the evaluated spatial variability, the measured parameters at various sites were clustered by a hierarchical clustering approach, which revealed different spatial clusters for “source-driven” and “long-range transport” parameters. This result suggests that the traditional “site category” (i.e. urban, and regional background, etc.) concerning mainly the influence of local sources cannot always catch the variation of aerosol particle mass or number concentrations. The dominant factors for various parameter are different, leading to different variability and spatial distribution. The result of spatial clustering offers a sound scientific base to compare pollutant parameters measured in different locations and environments. By assessing the relationship between the measured parameters and geographical distance between different sites, the spatial variability of the aerosol parameters follows the “First Law of Geography” that everything is related to everything else, but near things are more related than distant things (Tobler, 1970). However, different parameters show different sensitivities on geographical distance. The analysis provides an important reference for setting up an observation network with a specific research purpose and is also useful for the regional scale dispersion models or land-use regression models. Q2: How do the sub-micrometer PNSD, PNC, and eBC mass concentration change at a decadal scale? Have the implementations of emission mitigation policies affected the observed decadal trend? (Second publication) In the second publication (Sun et al., 2020), long-term trends in atmospheric PNCs and eBC mass concentration for a 10 years period (2009–2018) were determined for 16 sites of the GUAN, ranging from roadside to high-Alpine. To ensure the data consistency for the trend detection, a thorough and detailed data quality check and data cleaning for the large GUAN dataset was performed. Statistically significant decreasing trends were found for 85% of the parameters and observation sites indicating an overall decreasing trend in sub-micrometer PNC (except N[10−30]) and eBC mass concentration all over Germany. Comparing the trends of measured parameters with the long-term change in total emission, we proofed that the observed trends of PNCs and eBC mass concentrations were mainly due to the emission reduction. The detailed diurnal and seasonal trends in eBC mass concentration and PNCs further confirmed that the observed decreasing trends were largely owing to the reduced emissions such as traffic emission, residential emission, and industry emission, etc. Moreover, the inter-annual changes of meteorological conditions and long-range transport pattern were found not to be the main reason for the decreases in pollutant parameters. This study suggests that a combination of emission mitigation policies can effectively improve the air quality over large spatial scales such as Germany. Given the relative novelty of the long-term measurements (PNSD, eBC mass concentration) in a network such as GUAN, the results proved to be quite robust and comprehensive. Q3: Have the decreased PNC and eBC mass concentration due to emission mitigation policies at the lower-altitudes affected the background air in lower FT over Central Europe? (Third publication) In the third publication (Sun et al., 2021), the long-term change of the eBC mass concentration and size-resolved PNCs were determined and analyzed at two high Alpine stations for the period 2009-2018: Schneefernerhaus at mountain Zugspitze in Germany (ZSF, 2671 m a.s.l.) and Jungfraujoch in Switzerland (JFJ, 3580 m a.s.l.). The trend analysis was performed for the FT and PBL-influenced conditions separately, aiming to assess whether the reduced emissions at lower-altitudes over Central Europe can affect the background air in the lower FT on a large spatial scale. The FT and PBL conditions at the two stations were segregated using the adaptive diurnal minimum variation selection (ADVS) method. The result showed that the FT condition in cold months is more prevalent than in warm months. Overall, the FT conditions frequency was ~25% and 6% in the cold and warm seasons at ZSF, respectively. At JFJ, the frequency of FT was ~45% and 10% in these two seasons, respectively. The PNC and eBC mass concentration showed a statistically significant decrease during PBL time. The observed decreasing trends in eBC mass concentration in the PBL-influenced condition are well consistent with the reported trends in total BC emission in Germany and Switzerland. For the FT conditions, decreases in PNC and eBC mass concentration over the years was detected at both sites, suggesting the background PNC and eBC mass in the lower FT over Central Europe has decreased as well. The implementation of emission mitigation policies is the most decisive factor but the weather pattern change over Central Europe also has contributed to the decreasing trends in FT condition.:List of Figures ……………………………………………………………………………………………..I List of Tables ..……………………………………………………………………………………………..I Abbreviations .……………………………………………………………………………………………II 1. Introduction …………………………………………………………………………………………….1 1.1 Role of atmospheric sub-micrometer aerosol particles…...………………………………………...1 1.2 Measurement of sub-micrometer particle number size distribution, particle number concentration, and eBC mass concentration…..……………………………………………….………………………….2 1.3 Previous long-term observations of PNSD, PNC, and eBC mass concentration…………………...4 1.4 Objectives...………………………………………………………………………………………….6 2. Data and Method…..……………………………………………………………………………………9 2.1 The German Ultrafine Aerosol Network (GUAN) …………………………………………………9 2.1.1 Measurement sites in GUAN…………………………………………………………………..10 2.1.2 Instrumental set-up.……….………………………………………………………….…………14 2.1.3 Quality assurance.………………………………………………………………………….……16 2.1.4 Data coverage…..………………………………………………………………………………..17 2.2. High-Alpine observatory Jungfraujoch (JFJ)……………………………………………………..18 2.2.1 Measurement site……….……………………………………………………………………….18 2.2.2 Instrumentation ..………………………………………………………………………………..19 2.3 Data analysis methods……………………………………………………………………………….19 2.3.1 Agglomerative hierarchical clustering….……………………………………………………...19 2.3.2 Customized Sen’s slope estimator…………………..…………………………………………...21 2.3.3 Generalized least-square regression and autoregressive bootstrap confidence intervals (GLS- ARB)…………………………………………………………………………………………………21 2.3.4 Seasonal Mann-Kendal test…..………………….………………………………………………22 2.3.5 Back-trajectory classification method….……………………………………………………...24 3. Results and Discussion…..………………………………………………………………………….27 3.1 First publication….…………………………………………………………………………………..27 3.1.1 Variability of black carbon mass concentrations, sub-micrometer particle number concentrations and size distributions: results of the German Ultrafine Aerosol Network ranging from city street to High Alpine locations……………………………………...………………………………………...27 3.1.2 Supporting information..……………………………………………………………………….41 3.2 Second publication…………………………………………………………………………………..45 3.2.1 Decreasing trends of particle number and black carbon mass concentrations at 16 observational sites in Germany from 2009 to 2018…..…………………………………………………………..45 3.2.2 Supporting information...……………………………………………………………………….66 3.3 Third publication……………………………...……………………………………………………..75 3.3.1 Long-term trends of black carbon and particle number concentration in the lower free troposphere in Central Europe…………………………………………………………………………75 3.3.2 Supporting information..…….……………………………………………………………….92 4. Summary and Conclusions..………………………………………………………………………… 95 5. Outlook….…………………………………………………………………………………………...99 Appendix A….………………………………………………………………………………………...100 Bibliography…………………………………………………………………………………………...101 Acknowledgements….…………………………………………………………………………………115

Die Modifizierung von Carbon Black Partikeln und multi-walled Carbon Nanotubes mit Poly(vinylformamid-co-vinylamin) wurde in Abhängigkeit vom pH-Wert untersucht, um primäre Aminogruppen auf die Oberfläche der Kohlenstoffspezies einzuführen. Mit einer anschließenden Pfropfreaktion der Aminogruppen tragenden Nanotubes mit Maleinsäureanhydrid-Copolymeren sind eine Vereinzelung und ein Stabilisieren der der Carbon Nanotubes möglich. Durch eine Auswahl an Maleinsäureanhydrid-Copolymeren war nach einer Funktionalisierung der mit PVFA-co-PVAm beschichteten Carbon Nanotubes die Änderung der Oberflächeneigenschatften von hydrophil bis hin zu ultrahydrophob möglich. Die Charakterisierung der Partikel und Nanotubes erfolgte mit Hilfe der Elementaranalyse, BET-Untersuchungen, XPS, Kontaktwinkelmessungen, TGA-Untersuchungen, elektrokinetischer Messungen und REM-Aufnahmen.

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The estimates of global black carbon direct radiative forcing are still subject to substantial uncertainties ranging between 0.20 and 0.42 Wm-2 . In order to reduce these uncertainties, we must improve the representation of complex black carbon mixing state when simulating their optical properties and applying in global models. The main motivation behind this thesis is to gain a better understanding of the current state of the art when it comes to accurately modeling the radiative properties of BC-containing aerosols. We investigated how the optical properties of BC fractal aggregates are affected by the physiochemical properties that change during their ageing cycle, such as the fractal dimension, organic fraction, and particle size. Findings from the numerical study showed that the radiative forcings of black carbon particles can vary by as much as 61% depending on the particle's morphology and chemical composition. This influence of morphology and composition is particularly relevant to polluted urban environments with high mass concentrations of BC. Starting with soot from laboratory-based soot generators, representative for freshly emitted soot in the atmosphere, different morphological representations of BC and their modelling techniques were extensively tested. For BC particles with mobility diameters ³ 70nm and coating fractions £ 60%, the morphological representation as fractal aggregates performed well for modeling their optical properties. Our findings indicate that the use of the volume mean diameter of BC-containing particles, rather than the number mean diameter, is beneficial for calculating their optical properties. In addition, considering the particles to be fractal aggregates for the entire size distribution significantly reduced the uncertainty in optical simulations to nearly ten percent. Investigations conducted in Delhi, a polluted Asian urban environment, confirmed that fractal morphology plays a critical role in reducing the overestimation of aerosol light absorption simulations. When anthropogenic BC emissions are high, the particle light absorption can be overestimated by 50 to 200% by using assumptions of both external mixing and internal core-shell mixing. To address the computationally expensive nature of fractal simulations, we propose a metric known as the morphology index (MI). In order to obtain an accurate particle light absorption, this index distributes weightage between two extreme cases, the core-shell model and the fractal aggregate model. The measurements in Delhi showed that the aerosols transported over long distances had an MI of 0.78 ± 0.20, while the locally emitted aerosols had an MI of 0.48 ± 0.18. In order to identify the most relevant particle size mode for light absorption, a BC-based aerosol classification approach was developed. The method is based on correlations between BC mass concentrations and aerosol number concentrations at different particle sizes (BC-size correlation spectra). We introduce the concept of BC-size correlation spectra as a method for understanding the heterogeneous size-dependent distribution of aerosol light absorption as well as using it in conjunction with MI to better represent the optical properties of aerosols in different BC regimes. As a means of reducing the computational burden associated with optical simulations of fractal BC particles, a machine learning-based application was developed. In order to train the model, a comprehensive dataset was derived from the commonly used but computationally expensive multi- sphere T-matrix method (MTSM). This fast machine learning algorithm can predict the optical properties of coated BC fractal aggregates at different stages of atmospheric ageing in a fraction of the time compared to time-consuming numerical scattering calculations, with an average deviation of less than one per cent.:Bibliographische Beschreibung 1 Bibliographic Description 2 List of Figures 4 List of Symbols and Abbreviations 5 1. Introduction 7 2. Theoretical background 10 2.1 Aerosol properties 10 2.1.1 Physiochemical properties of aerosols 10 2.1.2 Optical properties of aerosols 12 2.2 Black carbon fractal aggregates 13 3. Methodology 14 3.1 Overview of the methods 14 3.1.1 Simulating BC fractal aggregates 14 3.1.2 Particle light scattering calculations 15 3.1.3 Radiative forcing model 16 3.1.4 BC size-correlation spectrum 17 3.1.5 Morphology Index 17 3.1.6 Machine learning methods 18 3.2 Summary of Methodology for each Paper 19 4. Motivation and Main Conclusions for Paper I-IV 21 4.1 Paper I 21 4.2 Paper II 22 4.3 Paper III 23 4.4 Paper IV 24 5. Summary 25 6. Future Work 27 Bibliography 28 Appended Papers 33 List of Publications included in this dissertation 162 Author’s Contribution to the Papers 163 Publications not included in this dissertation 164 Acknowledgements 165 / Die Abschätzungen des Strahlungsantriebs von Schwarzem Kohlenstoff (engl. Black Carbon, BC) sind immer noch mit erheblichen Unsicherheiten behaftet, die zwischen 0.20 und 0.42 Wm-2 liegen. Um diese Unsicherheiten zu verringern, müssen wir die Darstellung des komplexen Mischungszustands von schwarzem Kohlenstoff bei der Simulation seiner optischen Eigenschaften in globalen Modellen verbessern. Die Hauptmotivation für diese Arbeit ist es, ein besseres Verständnis des aktuellen Stands des Wissens zu erlangen, wenn es um die genaue Modellierung der Strahlungseigenschaften von BC-haltigen Aerosolen geht. Es wurde ein grundlegendes Verständnis dafür geschaffen, wie die optischen Eigenschaften fraktaler BC-Aggregate durch die physiochemischen Eigenschaften beeinflusst werden, die sich während ihres Alterungszyklus ändern, wie die fraktale Dimension, der organische Anteil und der Partikelgröße. Die Ergebnisse der numerischen Studie zeigen, dass die Strahlungsantriebe von schwarzem Kohlenstoff je nach Morphologie und chemischer Zusammensetzung der Partikel um bis zu 61 % variieren können. Dieser Einfluss von Morphologie und Zusammensetzung ist besonders relevant für verschmutzte städtische Umgebungen mit hohen Massenkonzentrationen von BC. Ausgehend von Labormessungen mit Ruß-Generatoren, deren Emissionen frisch emittierten Ruß in der Atmosphäre entsprechen, wurden verschiedene morphologische Darstellungen von BC und deren Modellierungstechniken in umfassend getestet. Für BC-Partikel mit Mobilitätsdurchmessern ³ 70 nm und Beschichtungsanteilen £ 60% erwies sich die morphologische Darstellung durch fraktale Aggregate für die Modellierung ihrer optischen Eigenschaften als gut geeignet. Unsere Ergebnisse deuten darauf hin, dass die Verwendung des mittleren Volumendurchmessers von BC- haltigen Partikeln anstelle des mittleren Größendurchmessers für die Berechnung optischer Eigenschaften von Vorteil ist. Wenn die Partikel für die gesamte Größenverteilung als fraktale Aggregate betrachtet werden, reduziert sich die Unsicherheit in den optischen Simulationen auf fast zehn Prozent. Untersuchungen in Delhi, einer verschmutzten asiatischen städtischen Umgebung, bestätigten, dass die fraktale Morphologie eine entscheidende Rolle bei der Verringerung der Überschätzung von Simulationen zur Lichtabsorption von Aerosolen spielt. Wenn die anthropogenen BC- Emissionen in Delhi hoch sind, kann die Lichtabsorption der Partikel um 50 bis 200 % überschätzt werden, wenn sowohl eine externe als auch eine interne Kern-Schale-Mischung angenommen wird. Um dem hohen Rechenaufwand fraktaler Simulationen zu begegnen, schlagen wir eine Metrik vor, die wir als Morphologieindex (MI) bezeichnen. Um eine genaue Lichtabsorption der Partikel zu erhalten, verteilt dieser Index die Wichtung zwischen zwei Extremfällen, dem Kern-Schale Modell und dem Modell der fraktalen Aggregate. Die Messungen in Delhi ergaben, dass die über weite Strecken transportierten Aerosole einen MI von 0.78 ± 0.20 aufwiesen, während die lokal emittierten Aerosole einen MI von 0.48 ± 0.18 hatten. Um den für die Lichtabsorption wichtigsten Partikelgrößenbereich zu ermitteln, wurde ein BC- basierter Aerosolklassifizierungsansatz entwickelt. Die Methode basiert auf Korrelationen zwischen BC-Massekonzentrationen und Aerosolanzahlkonzentrationen bei verschiedenen Partikelgrößen (BC-Größen-Korrelationsspektren). Wir führen das Konzept der BC-Größenkorrelationsspektren als Methode zum Verständnis der heterogenen größenabhängigen Verteilung der Lichtabsorption von Aerosolen ein und nutzen es in Verbindung mit MI zur verbesserten Darstellung der optischen Eigenschaften von Aerosolen in verschiedenen BC-Regimen. Um den mit optischen Simulationen fraktaler BC-Partikel verbundenen Rechenaufwand zu verringern, wurde ein auf maschinellem Lernen basierende Anwendung entwickelt. Dieser schnelle Algorithmus für maschinelles Lernen kann die optischen Eigenschaften beschichteter fraktaler BC- Aggregate in verschiedenen Stadien der atmosphärischen Alterung in einem Bruchteil der Zeit berechnen, die im Vergleich zu zeitaufwändigen numerischen Streuungsberechnungen erforderlich ist, und das mit einer durchschnittlichen Abweichung von weniger als einem Prozent.:Bibliographische Beschreibung 1 Bibliographic Description 2 List of Figures 4 List of Symbols and Abbreviations 5 1. Introduction 7 2. Theoretical background 10 2.1 Aerosol properties 10 2.1.1 Physiochemical properties of aerosols 10 2.1.2 Optical properties of aerosols 12 2.2 Black carbon fractal aggregates 13 3. Methodology 14 3.1 Overview of the methods 14 3.1.1 Simulating BC fractal aggregates 14 3.1.2 Particle light scattering calculations 15 3.1.3 Radiative forcing model 16 3.1.4 BC size-correlation spectrum 17 3.1.5 Morphology Index 17 3.1.6 Machine learning methods 18 3.2 Summary of Methodology for each Paper 19 4. Motivation and Main Conclusions for Paper I-IV 21 4.1 Paper I 21 4.2 Paper II 22 4.3 Paper III 23 4.4 Paper IV 24 5. Summary 25 6. Future Work 27 Bibliography 28 Appended Papers 33 List of Publications included in this dissertation 162 Author’s Contribution to the Papers 163 Publications not included in this dissertation 164 Acknowledgements 165

Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are two atmospheric pollutants produced by motor vehicles using carbonaceous fuels. As a part of the Mexico City Project, measurements of BC, PPAHs and many other gas- and particle-phase emissions were measured in Mexico City using a mobile laboratory during the Mexico City Metropolitan Area field campaign in April 2003 (MCMA-2003). The main goal of this research is to estimate emissions of BC and particulate PAHs (PPAHs) for Mexico City's vehicle fleet. The emissions of gas-phase pollutants such as carbon monoxide (CO), total nitrogen oxides (NOy) and volatile organic compounds (VOC) are also estimated. The mobile lab has previously been used to chase vehicles and measure their emissions, but analysis has traditionally focused on determining emission factors of individual vehicles associated with specific chasing events. The laboratory continuously samples ambient air from an inlet at the front of the van, and it is always "seeing" exhaust plumes from the vehicles around it while driving through traffic. We have developed an algorithm that automatically identifies the exhaust plume measurement points, which are then used as the basis for calculation of emission factors. In the nearly 90 hours of on-road sampling during the field campaign, we have identified ~30,000 exhaust measurement points. The large sample size enables us to estimate fleet-average emission factors and thus the emission inventory. Motor vehicles are estimated to emit annually 1,960 tons of BC, 56.2 tons of PPAHs, 1,320,000 tons of CO, 125,000 tons of NOy and 2440 tons of VOCs. The spatial and temporal patterns of BC and PPAHs in different locations with in MCMA are also studied. / Master of Science