Dissolved organic matter (DOM) is the largest pool of organic carbon in aquatic systems and an important component of the global carbon cycle. Large amounts of DOM are decomposed within lakes, resulting in fluxes of CO2 and CH4 to the atmosphere. Therefore, there is a considerable interest in understanding the controls of DOM decomposition in freshwaters. There is evidence that in lakes intrinsic controls related to DOM composition are of primary importance, yet our knowledge about molecular drivers of DOM degradation is limited. This thesis addresses the link between chemical composition and reactivity of lake DOM by applying an experimental approach, molecular-level DOM characterization, and kinetic modeling of DOM decay. The first study shows that photoinduced transformations and partial removal of colored aromatic components of DOM have profound effects on DOM degradation kinetics, mediated by the shifts in the relative share of rapidly and slowly degrading DOM fractions. Two following studies estimate exponential decay coefficients for each individual molecular formula identified within bulk DOM. A continuous distribution of exponential decay coefficients is found within bulk DOM, which directly corroborates the central and previously empirically untested assumption behind the reactivity continuum model of DOM decay. Further, individual decay rates are evaluated in connection to specific molecular properties. On average, highly unsaturated and phenolic compounds appear to be more persistent than compounds with higher aromatic content (plant polyphenols and polycondensed aromatics), and aliphatic compounds demonstrate the highest decay rates. The reactivity of aromatics additionally increases with increasing nominal oxidation state of carbon. Molecular analysis further indicates that increasing reactivity of DOM after UV exposure is caused by disintegration of supramolecular complexes. Study IV shows that changes in relative proportion of terrestrial versus algal DOM control degradability of DOM through seasons. Under ice, when algal-derived DOM is maximally depleted, DOM degradation potential converges to similarly low levels, regardless of lake type (productive or humic), and bacterial respiration primarily relies on terrestrial carbon. This suggests a general pattern of baseline metabolism across boreal lakes. I conclude that DOM is a dynamic reactivity continuum and a tight link exists between DOM behavior and compositional properties.

The most frequent soils in the São Paulo State Coastal Plain are Podzols, characterized by strong to moderate hydromorphic to well-drained podzolization with very well developed podzol-B horizons (Bh or Bhm). Podzolization processes include the effects of hydrology and rooting on profile morphology and the subsequent effects of improved drainage. A Podzol chrono-hydrosequence was described in detail on a cliff at the south coast of Ilha Comprida, a Holocene barrier island, and allowed a subdivision into four distinct groups: poorly-drained profiles, profiles with well-drained B horizons, strongly rooted profiles and superposed profiles. The morphological description and some observations about the exposure cliff were essential for grouping and differentiating the podzol profiles. Some well-drained podzols have OM-depleted mottles that are related to selective decomposition of organic matter (OM) by microorganisms. Such mottles are frequently associated to root channels. Seventeen profiles were studied, thirteen had depletion mottles scattered along the profile. Most of these mottles are whitish and are located preferentially in the horizons of transition between the E and B horizons, particularly in conditions of good drainage. Such mottles have certain morphological differences and may be grouped according to similarities in their morphology and their position in the profile. Distinct groups are: (a) concentric OM-depleted mottles; (b) circular/tubular OM-depleted mottles (burrows); (c) dotted OM-depleted mottles; (d) ghost OM-depleted mottles; (e) irregular OM-depleted mottles and (f) Fe-depleted mottles. The chemical composition of soil organic matter was studied in detail using pyrolysis in combination with gas chromatography/mass spectrometry (Py-GC/MS). Samples of all horizons of the distinct profiles studied were taken, as well as from the center of the mottle (M) and from the direct surroundings (S). The processes involved in the genesis of Podzols in the sandy coastal plain are directly related to drainage, the contribution of dissolved organic matter (DOM), the contribution of organic matter derived from roots, the chemical composition of organic matter and its decomposition by microorganisms, causing a large variation in adjacent Podzols. The well-drained Podzols differ in characteristics from the poorly drained ones in composition and deposition of OM, as well as its decomposition, which is directly related to the activity of groups of microorganisms. They also differ in the relative contribution of OM-derived from roots and DOM. There is a wide variation in the characteristics of decomposition by microorganisms between the profiles of Podzols permanently exposed to air and marine spray (the cliffs) on Ilha Comprida and those inland (pits). There are therefore two main processes that change the morphology of Podzols (OM and composition): (a) change in drainage and rooting, and (b) exposure to air. / Os solos mais frequentes na Planície Costeira do Estado de São Paulo são os podzóis, caracterizados por podzolização com hidromorfismo forte a moderado a bem drenado com horizontes B-podzol muito bem desenvolvidos (Bh ou Bhm). O processo de podzolização inclui os efeitos da hidrologia e do enraizamento no perfil e os efeitos subsequentes da drenagem melhorada. Uma crono-hidrosequencia de podzóis foi descrita em detalhes em um barranco na costa sul da Ilha Comprida, uma ilha barreira do Holoceno, e permitiu uma subdivisão em quatro grupos distintos: perfis mal drenados, perfis com horizonte B bem drenados, perfis fortemente enraizados e perfis superpostos. A descrição morfológica e algumas observações sobre o barranco exposto foram essenciais para o agrupamento e diferenciar os perfis de podzóis. Alguns desses podzóis bem drenados possuem manchas esbranquiçadas que estão relacionadas com a seletiva decomposição da matéria orgânica (MO) por microorganismos. Tais manchas são freqüentemente associadas aos canais radiculares. Foram estudados dezessete perfis, dos quais treze apresentaram manchas de esgotamento espalhadas ao longo do perfil. A maioria destas manchas são esbranquiçadas e estão localizadas preferencialmente nos horizontes de transição entre os horizontes E e B, particularmente em condições de boa drenagem. Tais manchas possuem algumas diferenças morfológicas e puderam ser agrupadas de acordo com semelhanças na sua morfologia e da sua posição no perfil. Os grupos são: (a) manchas concêntricas de depleção da MO; (b) manchas circulares/tubularess de depleção da MO (tocas); (c) manchas pontilhadas de depleção da MO; (d) manchas fantasmas de depleção da MO; (e) manchas irregulares de depleção da MO; e (f) manchas de depleção de Fe. A composição química da matéria orgânica do solo foi estudada em detalhe por pirólise em combinação com cromatografia em fase gasosa/espectrometria de massa (Py-CG/EM). Amostras de todos os horizontes dos perfis estudados foram coletadas, bem como amostras do centro das manchas (M) e do solo adjacente (S). Os processos envolvidos na gênese de podzóis da planície costeira arenosa estão diretamente relacionados com a drenagem, a contribuição de matéria orgânica dissolvida (MOD), a contribuição de matéria orgânica derivada de raízes, a composição química da matéria orgânica e sua decomposição por microorganismos, causando uma grande variação no podzóis. Os podzóis bem drenados diferem em características dos mal drenados em composição e deposição de MO, bem como a sua decomposição, que está directamente relacionada com a actividade dos grupos de microrganismos. Eles também diferem na contribuição relativa da MO derivada de raízes e MOD. Existe uma grande variação nas características da decomposição por microorganismos entre os perfis de podzóis permanentemente expostas ao ar e spray marinho (falésias) na Ilha Comprida e os do interior (trincheiras). Há, portanto, dois processos principais que alteram a morfologia de podzóis (composição da MO): (a) mudança na drenagem e enraizamento, e (b) a exposição ao ar.

Matéria orgânica natural (MON) é uma complexa matriz de compostos orgânicos originados de fontes naturais que estão presentes nas bacias hidrográficas e dentro dos corpos hídricos. MON é comprovado precursor de subprodutos da desinfecção (SPD), além de afetar processos de tratamento de água tais como coagulação, desinfecção, oxidação, adsorção em carvão ativado e filtração em membranas. Por estas razões, a redução da MON no tratamento de água para consumo humano é importante. Muitos métodos têm sido utilizados para caracterizar e quantificar a MON. Entre os métodos usados se encontram a adsorção em resinas e parâmetros de massa. Carbono orgânico total (COT), carbono orgânico dissolvido (COD), absorção à luz ultravioleta (UV254) e absorbância específica de luz ultravioleta (AEUV) são usualmente utilizados como parâmetros de massa. O fracionamento rápido é uma técnica que usa diferentes resinas para separar frações da MON. Nesse contexto, este trabalho teve como objetivo geral caracterizar a matéria orgânica dissolvida usando o método do fracionamento rápido e os parâmetros COD, UV254 e AEUV em processos de tratamento de água para consumo humano. Também foram analisados turbidez, cor, pH e alcalinidade. Foram avaliados os efeitos dos processos de coagulação, sedimentação, filtração em filtro de areia e adsorção em carvão ativado granular (CAG) nas frações que formam a MON. As amostras de água foram coletadas em estação de tratamento de água da cidade de Porto Alegre, RS. Os valores de turbidez, cor, pH, alcalinidade, UV254 e COD reduziram-se ao longo dos processos de tratamento, enquanto que a AEUV aumentou na sequência dos processos. Os valores de absorção de UV254 decresceram à medida que as amostras passavam através das distintas resinas do fracionamento rápido (DAX-8, XAD-4 e IRA-958). Estas frações tiveram reduções importantes em todas as amostras. Os AMH decresceram de 2,29 mg/L COD na água bruta para 0,25 mg/L COD no efluente da coluna de carvão ativado, enquanto que os ALH reduziram de 1,29 mg/L na água bruta para 0,22 mg/L no efluente do filtro de CAG. As concentrações observadas de matérias hidrofílicas carregadas (MHC) (ex., proteínas) e hidrofílicas neutras (MHN) (ex., carboidratos) foram próximas a zero em todas as amostras. Foi possível concluir que os processos de tratamento afetam a distribuição de frações da MON presente na água. / Natural organic matter (NOM) is a complex matrix of organic compounds originated from natural sources that are present in the watershed and in within water bodies. NOM is a known precursor of disinfection byproducts (DBP) and affects drinking water treatment processes such as coagulation, disinfection, oxidation, carbon adsorption and membrane filtration. For these reasons, the reduction of NOM in water treatment is important. Many methods have been used to characterize and quantify NOM, among them, the resin adsorption and the mass parameters methods. The latter include total organic carbon (TOC), dissolved organic carbon (DOC), ultraviolet absorption at 254 nm (UV254), and specific UV absorption (SUVA). Rapid fractionation is one of the resin adsorption methods. This study has as objective the characterization of dissolved organic matter using rapid fractionation and the parameters DOC, UV254 and SUVA in drinking water treatment processes. Turbidity, color, pH and alkalinity were also analyzed. It was evaluated the effect of coagulation, sedimentation, filtration in sand filter and granular activated carbon (GAC) adsorption in the fractions that form NOM. Samples were collected in a drinking water treatment plant in the city of Porto Alegre, RS. Values of turbidity, color, pH, alkalinity, UV254 and DOC decreased along treatment, while values of SUVA increased. UV254 reduced as the samples passed through the distinct resins used for rapid fractionation (DAX-8, XAD-4 e IRA-958). The main fraction of DOC in samples was very hydrophobic acids (VHA) (as humic acids) followed by slightly hydrophobic acids (SHA) (as fulvic acids). These fractions had major reductions as the samples run through the resins. VHA decreased from 2,29 mg/L COD in raw water to 0,25 mg/L COD in activated carbon column effluent, while SHA decreased from 1,29 mg/L in raw water to 0,22 mg/L in GAC filter effluent. Charged hydrophilic matters (CHA) (as proteins) and hydrophilic neutral (NEU) (as carbohydrates) were observed at concentrations next to zero in most samples. It was possible to conclude that drinking water treatment processes affect the fraction distribution of NOM in water.

O presente trabalho avaliou a variabilidade espacial e temporal de ácidos húmicos (HA) e proteínas (PROT), em uma grande lagoa rasa subtropical. Para tanto, foi usado Cromatógrafo Líquido de Alta Eficiência por Exclusão de Tamanho (HPLC-SEC). Foram incluídas como variáveis explanatórias, carbono orgânico dissolvido (COD), nitrogênio total (NT), nitrogênio total dissolvido (NTD), cor, pH e temperatura. A área de estudo foi a Lagoa Mangueira, uma grande lagoa rasa oligo-mesotrófica inserida ao Sistema Hidrológico do Taim – SHT. As amostras foram coletadas em quatro campanhas, durante o ano de 2010, em dezenove pontos diferentes, compreendendo as zonas litorâneas e pelágica, localizadas no sul, centro e norte da lagoa. Resultados indicaram que a Lagoa Mangueira apresenta heterogeneidade temporal interanual em relação a estas variáveis, ao mesmo tempo que possui um perfil longitudinal homogêneo, não evidenciando um arranjo espacial definido. / The present work evaluated spatial and temporal variability of humic acids (HA) and proteins (PROT) in a large subtropical shallow lake. For this purpose, High Performance Liquid Chromatograph by Size Exclusion (HPLC-SEC) was used. Dissolved organic carbon (DOC), total nitrogen (TN), total dissolved nitrogen (TDN), color, pH and temperature were included as explanatory variables. The study area was Mangueira lake, a large shallow oligo-mesotrophic lake located into the Taim Hydrological System. The samples were collected in four samplings during the year 2010 at nineteen different points, including the littoral and pelagic zones, located in the south, center and north of the lake. Results showed that the Mangueira lake presents interannual temporal heterogeneity in relation to these variables, at the same time that it has a homogeneous longitudinal profile, not evidencing a defined spatial arrangement.

Mixtures of chlorinated organic pollutants can be found in the soils at chlorophenol-contaminated sawmill, including (inter alia) polychlorinated phenols (CPs), phenoxyphenols (PCPPs), diphenyl ethers (PCDEs), dibenzofurans (PCDFs) and dioxins (PCDDs). These hydrophobic compounds have low water solubility and hence low mobility as truly dissolved compounds. However, they may migrate through the soil at significant rates via co-transport with dissolved organic matter (DOM) and colloids of fine, waterborne particulate matter. In the work underlying this thesis the distribution of chlorinated hydrophobic pollutants between these two mobile fractions in soil samples from five sawmill sites was studied Soils at five sites at which CPs were formerly used were characterized, and found to have complex profiles of chlorinated hydrophobic pollutants. CPs, PCPPs, PCDEs and PCDD/Fs were present at up to ppm-levels. Furthermore, the relative proportions of the pollutants differed from their relative proportions in the preservatives used at the sites, indicating that they have been transported from, and/or degraded in, the soil at different rates. These organic pollutants have low water solubility and strong affinity for soil organic matter (SOM). The importance of SOM for the fate of CPs, PCPPs, PCDEs, PCDFs and PCDDs in soil was investigated by examining the distribution of compounds between the mobile DOM and the immobile particulate organic matter (POM). The partitioning of CPs between DOM and POM was found to be approximately equal. However, the relative strength of association with POM of groups of chlorinated organic pollutants was positively correlated with their hydrophobicity, and thus increased in the order CP < PCPP < PCDE < PCDF < PCDD. Despite the weak association of PCDD/Fs with DOM our investigations found that considerable concentrations of these pollutants were bound to mobile fractions (DOM and colloids, >0.2 µm) in both a groundwater analysis and a leaching test. CPs and PCPP were present at up to ppm- and ppb-levels, respectively, and PCDEs and PCDD/Fs at up to ppt-levels. The importance of transport in association with the mobile fraction (DOM and colloids) increased with increasing hydrophobicity e.g. PCDDs were almost entirely associated with fine particulate matter, while CPs were largely found in the water phase and only minor proportions were associated with colloids.

The objective of this dissertation is to gain a better understanding of the environmental and climatic effects on the temporal and spatial variability of phytoplankton biomass along the West Florida Shelf. Chapter 1 examines temporal and spatial patterns in chlorophyll concentrations using satellite data collected between 1997 and 2003. Chlorophyll data derived from the SeaWiFS sensor are validated with in-situ data and analyzed. Wind, current, sea surface temperature, river, and rain data are used to better understand the factors responsible for the patterns observed in the satellite data. My question is whether the standard OC4 algorithm is adequate for studying short-term variability of chlorophyll concentrations along the WFS. I will examine temporal and spatial trends using the OC4 and compare them to the Carder semianalytical algorithm which uses remote sensing reflectances at 412nm, 443nm, 490nm,and 555nm to estimate chlorophyll concentrations separately from CDOM estimates. In Chapters 2 and 3 the potential problems due to CDOM and bottom reflectance are examined. In Chapter 2 I analyze the influence of riverine induced CDOM. Water leaving radiances are analyzed in an effort to discriminate true chlorophyll patterns from CDOM contaminated signals. Chapter 3 examines the impact of bottom reflectance on the satellite signal by using the percentage of remote sensing reflectance at a wavelength of 555 to differentiate between optically shallow waters and optically deep waters. Optically shallow waters are defined as those with the percentage of Rrs at 555 due to bottom reflectance greater than or equal to 25 percent, while optically deep waters have percent bottom reflectance less than or equal to 25 percent. These analyses will help assess the validity of the temporal and spatial patterns ofchlorophyll concentration observed with the SeaWiFS data described in Chapter 1.

The most frequent soils in the São Paulo State Coastal Plain are Podzols, characterized by strong to moderate hydromorphic to well-drained podzolization with very well developed podzol-B horizons (Bh or Bhm). Podzolization processes include the effects of hydrology and rooting on profile morphology and the subsequent effects of improved drainage. A Podzol chrono-hydrosequence was described in detail on a cliff at the south coast of Ilha Comprida, a Holocene barrier island, and allowed a subdivision into four distinct groups: poorly-drained profiles, profiles with well-drained B horizons, strongly rooted profiles and superposed profiles. The morphological description and some observations about the exposure cliff were essential for grouping and differentiating the podzol profiles. Some well-drained podzols have OM-depleted mottles that are related to selective decomposition of organic matter (OM) by microorganisms. Such mottles are frequently associated to root channels. Seventeen profiles were studied, thirteen had depletion mottles scattered along the profile. Most of these mottles are whitish and are located preferentially in the horizons of transition between the E and B horizons, particularly in conditions of good drainage. Such mottles have certain morphological differences and may be grouped according to similarities in their morphology and their position in the profile. Distinct groups are: (a) concentric OM-depleted mottles; (b) circular/tubular OM-depleted mottles (burrows); (c) dotted OM-depleted mottles; (d) ghost OM-depleted mottles; (e) irregular OM-depleted mottles and (f) Fe-depleted mottles. The chemical composition of soil organic matter was studied in detail using pyrolysis in combination with gas chromatography/mass spectrometry (Py-GC/MS). Samples of all horizons of the distinct profiles studied were taken, as well as from the center of the mottle (M) and from the direct surroundings (S). The processes involved in the genesis of Podzols in the sandy coastal plain are directly related to drainage, the contribution of dissolved organic matter (DOM), the contribution of organic matter derived from roots, the chemical composition of organic matter and its decomposition by microorganisms, causing a large variation in adjacent Podzols. The well-drained Podzols differ in characteristics from the poorly drained ones in composition and deposition of OM, as well as its decomposition, which is directly related to the activity of groups of microorganisms. They also differ in the relative contribution of OM-derived from roots and DOM. There is a wide variation in the characteristics of decomposition by microorganisms between the profiles of Podzols permanently exposed to air and marine spray (the cliffs) on Ilha Comprida and those inland (pits). There are therefore two main processes that change the morphology of Podzols (OM and composition): (a) change in drainage and rooting, and (b) exposure to air. / Os solos mais frequentes na Planície Costeira do Estado de São Paulo são os podzóis, caracterizados por podzolização com hidromorfismo forte a moderado a bem drenado com horizontes B-podzol muito bem desenvolvidos (Bh ou Bhm). O processo de podzolização inclui os efeitos da hidrologia e do enraizamento no perfil e os efeitos subsequentes da drenagem melhorada. Uma crono-hidrosequencia de podzóis foi descrita em detalhes em um barranco na costa sul da Ilha Comprida, uma ilha barreira do Holoceno, e permitiu uma subdivisão em quatro grupos distintos: perfis mal drenados, perfis com horizonte B bem drenados, perfis fortemente enraizados e perfis superpostos. A descrição morfológica e algumas observações sobre o barranco exposto foram essenciais para o agrupamento e diferenciar os perfis de podzóis. Alguns desses podzóis bem drenados possuem manchas esbranquiçadas que estão relacionadas com a seletiva decomposição da matéria orgânica (MO) por microorganismos. Tais manchas são freqüentemente associadas aos canais radiculares. Foram estudados dezessete perfis, dos quais treze apresentaram manchas de esgotamento espalhadas ao longo do perfil. A maioria destas manchas são esbranquiçadas e estão localizadas preferencialmente nos horizontes de transição entre os horizontes E e B, particularmente em condições de boa drenagem. Tais manchas possuem algumas diferenças morfológicas e puderam ser agrupadas de acordo com semelhanças na sua morfologia e da sua posição no perfil. Os grupos são: (a) manchas concêntricas de depleção da MO; (b) manchas circulares/tubularess de depleção da MO (tocas); (c) manchas pontilhadas de depleção da MO; (d) manchas fantasmas de depleção da MO; (e) manchas irregulares de depleção da MO; e (f) manchas de depleção de Fe. A composição química da matéria orgânica do solo foi estudada em detalhe por pirólise em combinação com cromatografia em fase gasosa/espectrometria de massa (Py-CG/EM). Amostras de todos os horizontes dos perfis estudados foram coletadas, bem como amostras do centro das manchas (M) e do solo adjacente (S). Os processos envolvidos na gênese de podzóis da planície costeira arenosa estão diretamente relacionados com a drenagem, a contribuição de matéria orgânica dissolvida (MOD), a contribuição de matéria orgânica derivada de raízes, a composição química da matéria orgânica e sua decomposição por microorganismos, causando uma grande variação no podzóis. Os podzóis bem drenados diferem em características dos mal drenados em composição e deposição de MO, bem como a sua decomposição, que está directamente relacionada com a actividade dos grupos de microrganismos. Eles também diferem na contribuição relativa da MO derivada de raízes e MOD. Existe uma grande variação nas características da decomposição por microorganismos entre os perfis de podzóis permanentemente expostas ao ar e spray marinho (falésias) na Ilha Comprida e os do interior (trincheiras). Há, portanto, dois processos principais que alteram a morfologia de podzóis (composição da MO): (a) mudança na drenagem e enraizamento, e (b) a exposição ao ar.

Les projections concernant les changements climatiques dans les régions arctiques annoncent une augmentation disproportionnée des températures de surface pouvant influencer le cycle hydrologique et la fonte des pergélisols. Les hautes latitudes sont donc perçu comme des environnements potentiellement très sensibles aux modifications du climat. Ces modifications ont la capacité d’impacter les cycles biogéochimiques, en particulier la mobilisation du carbone vers les milieux aquatiques de la zone arctique. Dans les rivières arctiques, la période la plus importante du cycle hydrologique est la crue de printemps qui peut réaliser la majeure partie des transferts annuels de carbone organique vers l’océan dans un lapse de temps très court. L’objectif de cette thèse vise à suivre la dynamique des MOD en termes de quantité et de qualité au cours du cycle hydrologique du fleuve Ienisei, grâce à diverses techniques de caractérisation des MOD permettant de mettre en évidence les variations saisonniéres de leur composition, sources, âge et état de dégradation. La première étape a été d’examiner la large gamme de techniques de caractérisation des MOD dans les rivières du monde afin d’identifier les plus répendues,pértinentes et fiables. Grâce au développement d’une base de données des mesures des qualités des MOD, nous avons pu évaluer la couverture géographique des études de caractérisation des MOD, donner des estimations et gamme de valeurs des principales variables de caractérisation des MOD et observer des tendances générales des qualités des MOD selon un gradient latitudinal. La seconde étape a porté sur l’étude de la dynamique du COD dans le fleuve Ienisei concernant les variations de concentrations et les liens avec la chimie de l’eau et l’hydrologie. Nous avons mené des campagnes d’échantillonnage durant trois années consécutives (2014 à 2016), en couvrant avec une haute fréquence de prélèvement la période de la crue de printemps afin d’en capturer la dynamique rapide. Nous avons observé des concentrations en COD qui suivent l’hydrogramme avec les concentrations maximales mesurées quelques jours avant le pic de crue. Le COD a aussi répondu aux variations de débit (augmentation, probablement liée à des précipitations plus intenses du début d’automne. Nous avons enregistré un flux de COD moyen, durant les trois années de prélèvement, d’environ 4,53 Tg yr-1, ce qui est dans l’ordre de grandeur rapporté dans la littérature. Nous avons également observe ue variabilité interannuelle relativement importante avec les estimations d’exports annuels variant de 5,45 Tg yr-1 en 2014 à 3,57 Tg yr-1 en 2016, certainement influence par l’amplitude de débit. Nous avons confirmé le rôle prédominant de la crue de printemps dans les exports de COD avec en moyenne plus de 65% des exportations ayant lieu Durant cette période (approximatvement mai/juin). Le troisième point a consisté en l’étude de la qualité des MOD présentent dans les eaux du Ienisei et de son évolution durant le cycle hydrologique en combinant différentes outils de caractérisation. Associer les modes de caractérisation aide à renforcer les observations et à valider les interprétations. La plus part des variables mesurées avec les différentes techniques se sont confirmées les unes les autres. L’utilisation des biomarqueurs de la lignine, des propriétés optiques et de la datation 14C ont permis de tracer les sources prédominantes des MOD comme étant principalement dérivées de matières organiques récemment produites lixiviée depuis les litières forestières boréales et des horizons supèrieures pendant la crue de printemps et de matières organiques plus anciennes provenant des horizons plus profonds durant la période des basses eaux. / Arctic regions are expected to be highly sensitive to climate change regarding the prediction of disproportionately large increases in surface temperatures and their related influence over the hydrological cycle and permafrost thaw. These modifications have the potential to impact biogeochemical cycles in these regions and in particular the mobilization of organic carbon into rivers. The most crucial period in arctic rivers hydrological cycle is the spring freshet that can account for most of the annual organic carbon transfers to the ocean in a very short window of time. The focus of this thesis was to monitor the dynamic of DOM in terms of quantity and quality along the hydrological cycle of the Yenisei river, through DOM characterization approaches to reveal seasonal variations in its composition, sources, age and degradation state. The first step was to make a review of the full range of existing DOM characterization approaches in worldwide river systems to identify the most widely used, the most relevant and reliable ones. Through the development of a DOM quality measurements database, we have been able to evaluate the geographical coverage of DOM characterization studies, to give estimates and ranges of values of the main reported DOM characterization variables and to observe global trends of DOM quality across latitudinal gradient. Second stage was to investigate DOC dynamic in the Yenisei river with regard to quantity and links with water chemistry and hydrology. We conducted sampling campaigns during three consecutive years (2014 to 2016), covering with a high sampling frequency the spring flood period to capture its very dynamic evolution. We reported DOC concentrations that followed the hydrograph with highest concentrations observed a few days before peak discharge. DOC concentration also responded to discharge variation (increase, likely due to higher precipitation) in early autumn. We reported average DOC flux over the three sampling years of about 4.53 Tg yr-1 which is within the range of values reported in the literature. We observed interannual variability with annual export estimates ranging from 5.45 Tg yr-1 in 2014 to 3.57 Tg yr-1 in 2016, likely driven by discharge amplitude. We confirmed the important role of spring freshet in DOC export with on average more than 65% occurring during this period (roughly May/June). Third point was to determine DOM quality combining characterization techniques. Combination of approaches helped to strengthen observations and cross validate interpretations. Most of the variables reported from the different characterization techniques confirmed one each other. The use of lignin biomarkers, optical properties and radiocarbon age of DOM allowed us to trace DOM main sources has primarily deriving from recently produced organic matter leached from boreal forest litter and top soil horizon during the spring flood and older organic matter derived from deeper soil horizons during low flow period.

O presente trabalho avaliou a variabilidade espacial e temporal de ácidos húmicos (HA) e proteínas (PROT), em uma grande lagoa rasa subtropical. Para tanto, foi usado Cromatógrafo Líquido de Alta Eficiência por Exclusão de Tamanho (HPLC-SEC). Foram incluídas como variáveis explanatórias, carbono orgânico dissolvido (COD), nitrogênio total (NT), nitrogênio total dissolvido (NTD), cor, pH e temperatura. A área de estudo foi a Lagoa Mangueira, uma grande lagoa rasa oligo-mesotrófica inserida ao Sistema Hidrológico do Taim – SHT. As amostras foram coletadas em quatro campanhas, durante o ano de 2010, em dezenove pontos diferentes, compreendendo as zonas litorâneas e pelágica, localizadas no sul, centro e norte da lagoa. Resultados indicaram que a Lagoa Mangueira apresenta heterogeneidade temporal interanual em relação a estas variáveis, ao mesmo tempo que possui um perfil longitudinal homogêneo, não evidenciando um arranjo espacial definido. / The present work evaluated spatial and temporal variability of humic acids (HA) and proteins (PROT) in a large subtropical shallow lake. For this purpose, High Performance Liquid Chromatograph by Size Exclusion (HPLC-SEC) was used. Dissolved organic carbon (DOC), total nitrogen (TN), total dissolved nitrogen (TDN), color, pH and temperature were included as explanatory variables. The study area was Mangueira lake, a large shallow oligo-mesotrophic lake located into the Taim Hydrological System. The samples were collected in four samplings during the year 2010 at nineteen different points, including the littoral and pelagic zones, located in the south, center and north of the lake. Results showed that the Mangueira lake presents interannual temporal heterogeneity in relation to these variables, at the same time that it has a homogeneous longitudinal profile, not evidencing a defined spatial arrangement.

Matéria orgânica natural (MON) é uma complexa matriz de compostos orgânicos originados de fontes naturais que estão presentes nas bacias hidrográficas e dentro dos corpos hídricos. MON é comprovado precursor de subprodutos da desinfecção (SPD), além de afetar processos de tratamento de água tais como coagulação, desinfecção, oxidação, adsorção em carvão ativado e filtração em membranas. Por estas razões, a redução da MON no tratamento de água para consumo humano é importante. Muitos métodos têm sido utilizados para caracterizar e quantificar a MON. Entre os métodos usados se encontram a adsorção em resinas e parâmetros de massa. Carbono orgânico total (COT), carbono orgânico dissolvido (COD), absorção à luz ultravioleta (UV254) e absorbância específica de luz ultravioleta (AEUV) são usualmente utilizados como parâmetros de massa. O fracionamento rápido é uma técnica que usa diferentes resinas para separar frações da MON. Nesse contexto, este trabalho teve como objetivo geral caracterizar a matéria orgânica dissolvida usando o método do fracionamento rápido e os parâmetros COD, UV254 e AEUV em processos de tratamento de água para consumo humano. Também foram analisados turbidez, cor, pH e alcalinidade. Foram avaliados os efeitos dos processos de coagulação, sedimentação, filtração em filtro de areia e adsorção em carvão ativado granular (CAG) nas frações que formam a MON. As amostras de água foram coletadas em estação de tratamento de água da cidade de Porto Alegre, RS. Os valores de turbidez, cor, pH, alcalinidade, UV254 e COD reduziram-se ao longo dos processos de tratamento, enquanto que a AEUV aumentou na sequência dos processos. Os valores de absorção de UV254 decresceram à medida que as amostras passavam através das distintas resinas do fracionamento rápido (DAX-8, XAD-4 e IRA-958). Estas frações tiveram reduções importantes em todas as amostras. Os AMH decresceram de 2,29 mg/L COD na água bruta para 0,25 mg/L COD no efluente da coluna de carvão ativado, enquanto que os ALH reduziram de 1,29 mg/L na água bruta para 0,22 mg/L no efluente do filtro de CAG. As concentrações observadas de matérias hidrofílicas carregadas (MHC) (ex., proteínas) e hidrofílicas neutras (MHN) (ex., carboidratos) foram próximas a zero em todas as amostras. Foi possível concluir que os processos de tratamento afetam a distribuição de frações da MON presente na água. / Natural organic matter (NOM) is a complex matrix of organic compounds originated from natural sources that are present in the watershed and in within water bodies. NOM is a known precursor of disinfection byproducts (DBP) and affects drinking water treatment processes such as coagulation, disinfection, oxidation, carbon adsorption and membrane filtration. For these reasons, the reduction of NOM in water treatment is important. Many methods have been used to characterize and quantify NOM, among them, the resin adsorption and the mass parameters methods. The latter include total organic carbon (TOC), dissolved organic carbon (DOC), ultraviolet absorption at 254 nm (UV254), and specific UV absorption (SUVA). Rapid fractionation is one of the resin adsorption methods. This study has as objective the characterization of dissolved organic matter using rapid fractionation and the parameters DOC, UV254 and SUVA in drinking water treatment processes. Turbidity, color, pH and alkalinity were also analyzed. It was evaluated the effect of coagulation, sedimentation, filtration in sand filter and granular activated carbon (GAC) adsorption in the fractions that form NOM. Samples were collected in a drinking water treatment plant in the city of Porto Alegre, RS. Values of turbidity, color, pH, alkalinity, UV254 and DOC decreased along treatment, while values of SUVA increased. UV254 reduced as the samples passed through the distinct resins used for rapid fractionation (DAX-8, XAD-4 e IRA-958). The main fraction of DOC in samples was very hydrophobic acids (VHA) (as humic acids) followed by slightly hydrophobic acids (SHA) (as fulvic acids). These fractions had major reductions as the samples run through the resins. VHA decreased from 2,29 mg/L COD in raw water to 0,25 mg/L COD in activated carbon column effluent, while SHA decreased from 1,29 mg/L in raw water to 0,22 mg/L in GAC filter effluent. Charged hydrophilic matters (CHA) (as proteins) and hydrophilic neutral (NEU) (as carbohydrates) were observed at concentrations next to zero in most samples. It was possible to conclude that drinking water treatment processes affect the fraction distribution of NOM in water.