A l'heure actuelle le rôle des zones côtières dans le cycle global du carbone est encore relativement mal documenté. Ceci est lié à la forte hétérogénéité et au fort dynamisme de ces zones au sein desquelles de nombreux processus physiques et biologiques interagissent sur les stocks et les flux de carbone. Le carbone organique dissous (DOC) est un élément essentiel à la compréhension du cycle du carbone océanique, notamment dans les zones côtières où il peut représenter jusqu'à 90% du carbone organique total. Compte tenu des nombreuses incertitudes qui résident encore sur la dynamique de cette matière carbonée, l'objectif général de cette thèse visait à améliorer les connaissances sur la distribution du DOC au niveau de ces interfaces "continent/océan" en s'appuyant sur les propriétés optiques de la fraction colorée de ce DOC, la matière organique dissoute (CDOM). Pour cela, des échantillonnages ont été réalisés entre 2010 et 2015 dans trois sites côtiers fortement contrastés (Manche orientale, Guyane Française, Vietnam) et ont permis de : (i) caractériser la dynamique de la CDOM et du DOC et d'identifier une forte hétérogénéité de la relation entre ces deux paramètres au sein de ces sites côtiers aux caractéristiques contrastés, (ii) de proposer une relation novatrice applicable à la télédétection "couleur de l'eau" permettant de dériver les concentrations en DOC à partir des propriétés optiques de la CDOM potentiellement généralisable dans des sites côtiers dominés par les apports terrigènes. Dans un second temps, des études en milieu contrôle (45 jours) couplées à un suivi de terrain (2012-2014) ont été effectuées afin de caractériser spécifiquement la cinétique et l'impact d'une production biologique de matière organique dissoute sur les relations entre CDOM et DOC. Elles ont permis d'identifier un marquage optique (i.e. S320-412) de cette production autochtone de MOD lors de l'efflorescence printanière de Phaeocystis.globosa caractéristique des eaux côtières de la Manche et de proposer une approche pour estimer les contenus en DOC depuis les propriétés optiques du CDOM dans de telles situations de production marine de matière organique dissoute. / The coastal ocean represents an important component of the global carbon cycle however its participation to the overall carbon flux is currently not well constrained. Information on DOC stock and its variability in the coastel ocean is however still very scarce and its represents a strong limitation to our current understanding of the exact role of these ecosystems in the oceanic carbon cycle. In this context, the general aims of this study was to get more insights on dissolved organic carbon dynamics in the coastal ocean through the optical properties of dissolved organic matter (CDOM) that present the advantage to be easily measured from in situ or satellite observations. In practice, in situ data gathered during several sampling cruises conducted in three constrasted continental margins (Eastern Channel, French Guiana, Vietnam) have allowed : (i) the characterization of the strong regional discrepancies in the CDOM-DOC relationships between the three coastal sites investigated, (ii) the possible use of a generalized parameterization to retrieve DOC concentrations from CDOM optical properties (estimated in situ or from ocean color remote sensing)over a large range of coastal sites dominated by terrestrial imput of DOM. A further objective of this work was to investigate the impact on DOM dynamics of the phytoplankton bloom event of Phaeocystis.globosa known to affect the coastal waters of the eastern English Channel during the spring period. In practice, this DOM production was investigated during a 45 days mesocom experiment coupled to field survey data (2012-1014) leading to the identification of an optical marker of this marine CDOM production (i.e. S320-412). We further demonstrated that this optical parameter provides useful information to enhance our ability to retrieve DIC 1 from CDOM optical properties in a context of an algal bloom event.

A Ilha Comprida formou-se no Quaternário tardio e é uma ilha barreira arenosa composta de um conjunto de superfícies de rugosidade moderada à plana, nas quais se formaram Espodossolos com padrões variados de desenvolvimento e morfologia. Essa pesquisa utilizou a abordagem multiescalar, com observações e descrições através de sensoriamento remoto, topocronossequências, perfis, horizontes e seções delgadas de solo. O levantamento cartográfico com o auxílio de fotografias aéreas 1:16.000 do setor sul da Ilha Comprida permitiu mapear as feições geomorfológicas de cordões praiais, áreas planas, reentrâncias de manguezais, dunas frontais (cordões eólicos), rupturas de deflação (blow-outs) e bordas de terraços. O estudo baseou-se em dois perfis transversais (leste-oeste) com 3 km de extensão, onde foi possível identificar diversas unidades de crescimento sedimentar. As transeções A-B e C-D estão situadas no interior e na falésia sul da ilha, respectivamente. Comparando-se os solos dessas transeções é possível constatar o papel desempenhado pela evolução da drenagem na formação, manutenção e degradação dos horizontes espódicos. A degradação dos horizontes espódicos da transeção C-D está ligada à abertura de canais de raízes onde se instalam fluxos preferenciais de água, somado a atividade decompositora de Acidobactérias. Foram realizados levantamentos topográficos e da configuração vertical e lateral dos horizontes dos solos das transeções, sendo instalados 14 poços de monitoramento do nível freático na transeção A-B. As informações do relevo, solo e dinâmica atual do lençol freático permitiram identificar cinco compartimentos morfopedológicos. Os compartimentos I, II e IV, com maior rugosidade do terreno, possuem Espodossolos bem desenvolvidos providos de ortstein na zona próxima ao limite de oscilação do lençol freático, enquanto o compartimento III é mais plano e apresenta Espodossolos Hidromórficos e Organossolos. No compartimento V, mais recente, a podzolização é incipiente. As análises de estatística da distribuição das areias e micromorfologia indicam que a granulometria e o ajuste espacial dos grãos de areia de certas camadas sedimentares, atuam no acúmulo de Matéria Orgânica Dissolvida (MOD) através do acentuado gradiente de condutividade hidráulica ou por quebra de capilaridade. O resultado é a formação de bandas e horizontes cimentados (Bhm) em determinados contatos estratigráficos. Os cordões e entre-cordões praiais convergentes para à Ponta da Trinheira (sudoeste da ilha) controlam a direção dos fluxos hídricos superficiais e subsuperficiais do local, funcionando como escoadouro de MOD, cujo aporte contínuo e lateral explicaria a formação dos horizontes Bhm gigantes que sustentam o limite territorial em forma de \"L\". A descida gradual e contínua do NRM e o efeito de borda na falésia sul ocorrido após sua erosão colaboraram para o dessecamento e hiperdesenvolvimento do ortstein deste local. O horizonte glei (2Cg) é um paleomangue e ocorre de forma pontual na face lagunar da ilha. Seu impedimento à drenagem limita o avanço da podzolização em profundidade, formando o horizonte Bhm acima do horizonte 2Cg. Algumas raízes e paleogalerias tubulares de Callichirus major, preenchidas por areia, promovem bioturbações capazes de condicionar o acúmulo e cimentação de MOD. As galerias formadas pelo crustáceo são holocênicas e a manutenção de seus vestígios até os dias atuais se deve ao processo de pedofossilização por podzolização. / Formed since the late Quaternary period, the Ilha Comprida is made up by a set of geomorphological units depicted whether by rough or smooth surfaces, where both have Spodosols with a range of morphology and development stages. Multiscale approach has been applies through the spatial representation of topochronossequences, soil profiles, soil horizons and soil thin sections. Cartography survey of the south Ilha Comprida has been aided by aerial photos, allowed to mapping geomorphological features: beach ridge and swales; plan surfaces; coves with mangrove recesses; and edge of terrains. The study was based on two transversal profiles (east-west) with nearly 3 km of width, located at southernmost of Ilha Comprida, where there are several growth units. There transections A-B and C-D are located inland and at the cliffs, respectively. The soils from these transections show the role play by drainage conditions on formation and degradation of spodic horizon. The degradation of spodic horizons through transection C-D is linked to the preferential flow channels created by roots growth, plus by the decomposition activities of Acidbacterias. Traditional topography survey and lateral configuration of soils has been draw to depict these transections, where 14 wells were deployed for water table monitoring (transection A-B).The relief, soil, and water table information allowed the delimiting of five morphopedologic compartments. The compartments I, II and IV has rough surfaces (higher and close beach ridges) with Spodosol well developed provided with ortstein at oscillation zone of water table, while compartment III is a flat surface with Hydromorphic Spodosol and Histosols. Compartment V is the youngest surface and has incipient podsolization. Statistic of sand grain size and micromorphology analysis indicates that granulometry and spatial sand arrangement of some sedimentary package, deal with Dissolved Organic Matter (DOM) accumulation through high hydraulic conductivity gradient or capillarity breaks. It results in formation of bands and commentated horizons (Bhm) at some stratigraphic boundaries. The presence of beach ridges and swales alignments convergent towards southwest of Ilha Comprida, plus the directions of local hydrography flows, implies that the swales are channels of DOM, which contribute to ortstein formation at Ponta da Trincheira. The slow decreasing of sea level along the Holocene, in addition to the edge effect upon erosion of the south sandy cliff, also played a role to ortstein genesis. Gley horizon (2Cg) with mineralogical assemblage similar to the soils found in the mangrove, suggest that some mangroves has been buried by the costal dynamics typical in infra-tidal environment. Currently, these buried horizons occur locally and plays a impediments for drainage, which is expressed in accumulation and cementation by organic matter (Bhm horizon). Some roots and Callichirus major fossils entail bioturbation that also enable accumulation and cementation of DOM. This icnofossils might have been preserved through pedofossilization by the podsolization process itself.

Made available in DSpace on 2017-05-12T14:47:13Z (GMT). No. of bitstreams: 1 Thaisa _Pegoraro.pdf: 1491826 bytes, checksum: 1b9380fd12ae09c6e6128b1816c0215e (MD5) Previous issue date: 2015-02-23 / Biochar, also known as terra preta do índio, is a highly porous material and is a result of biomass pyrolysis in oxygen-controlled conditions and low temperatures (up to 600 oC). Due to the viable manufacturing process and the wide variety of applications, it is a promising material for various uses. Among the main uses of biochar, studies indicate its potential in improving soil quality, besides being a way of contributing to carbon sequestration from the atmosphere and used in the retention of organic and inorganic contaminants in the environment. This work aimed to present a review of the concepts and current studies on biochar, for a better understanding of the subject (Paper 1). The objective was to also investigate the adsorption of pharmaceuticals carbamazepine (CBZ) and lincomycin (LMC) by six biochars under the influence of surface characteristics of biochar (produced from Brazilian pepper and sugarcane bagasse, in temperatures of 300 o, 400 o and 600o C) and environmental factors (pH and adsorption competition between CBZ and LMC) (Paper 2). The latest study aimed to understand the effects of exposure of dissolved organic matter (DOM) in the surface properties of three biochars produced from sugarcane bagasse, in the CBZ adsorption (Paper 3). Batch equilibrium tests were performed in constant temperature, varying pH, and the data were adjusted in Freundlich isotherms. For the DOM test, the biochars were previously loaded with humic acid, tannic acid, gallic acid, and catechol in concentrations equivalent to those found in soils. The values of Kd, n and KF were reported and analyzed. As a result, it was found that biochars produced from sugarcane bagasse and high pyrolysis temperature were more effective in CBZ and LMC adsorption. In the biochar produced from bagasse at 300° C, the adsorption of CBZ was not affected by the presence of functional groups on the surface of biochar. LMC, which is ionized at pH 7.6, is more easily binded to negatively charged biochars when pH is acidic (pH<pKa). Furthermore, it was found that the CBZ and LMC compete for the same adsorption sites, regardless the variation of pH solution. In general, DOM affected adsorptive properties of biochars and attenuated CBZ adsorption, especially for biochars produced in higher temperatures because of the greater complexity of its structure, when DOM enters or blocks the biochar micro and mesoporous. It was concluded that the use of biochar as a product of sustainable feature looks promising, but there are still some gaps in the current literature about the positive and negative impacts of its use. Laboratory results indicate a possible use of biochar in removing organic compounds from water, which can replace less effective existing treatment technologies. There is to be considered, however, several factors that influence this process and more studies are needed to corroborate such evidence. / O biocarvão, também conhecido como terra preta do índio, é um material de alta porosidade e é resultado da pirólise da biomassa em condições de oxigênio controlado e baixas temperaturas (até 600 oC). Devido ao viável processo de produção e à ampla variedade de aplicações, trata-se de um material promissor para diversos usos. Dentre as principais utilidades do biocarvão, estudos indicam seu potencial na melhoria da qualidade do solo, além de ser uma forma de contribuir para o sequestro de carbono da atmosfera e ser utilizado na retenção de contaminantes orgânicos e inorgânicos no ambiente. Nesse trabalho, objetivou-se realizar uma revisão sobre os conceitos e estudos atuais sobre biocarvão, para uma melhor compreensão do tema (Artigo 1). Objetivou-se também investigar o processo de adsorção dos fármacos carbamazepina (CBZ) e lincomicina (LMC) por seis biocarvões, sob a influência de características superficiais do biocarvão (produzidos a partir de pimenta brasileira e bagaço de cana-de-açúcar, a 300o, 400o e 600o C) e fatores ambientais (pH e competição sortiva entre CBZ e LMC) (Artigo 2). No último estudo, objetivou-se compreender os efeitos da exposição da matéria orgânica dissolvida (MOD) nas propriedades superficiais de três biocarvões produzidos a partir de bagaço de cana-de-açúcar, na adsorção de CBZ (Artigo 3). Ensaios de equilíbrio de adsorção foram realizados em batelada e temperatura constante, variando o pH, e os dados foram ajustados em isotermas de Freundlich. Para o ensaio com MOD, os biocarvões foram previamente carregados com ácido húmico, ácido tânico, ácido gálico e catecol em concentrações equivalentes às de matéria orgânica encontrada em solos. Os valores de Kd, KF e n foram reportados e analisados. Como resultado, verificou-se que biocarvões produzidos a partir da biomassa de bagaço de cana-de-açúcar e altas temperaturas de pirólise foram mais efetivos na adsorção de CBZ e LMC. Em biocarvão produzido a partir de bagaço de cana-de-açúcar, a 300 oC, a adsorção de CBZ não foi afetada pela presença de grupos funcionais na superfície do biocarvão. Já a LMC, que é ionizada a pH 7,6, liga-se mais facilmente a biocarvões carregados negativamente quando o pH é ácido (pH<pKa). Além disso, verificou-se que a CBZ e LMC competem entre si pelos mesmos sítios sortivos, independente da variação do pH da solução. A MOD afetou as propriedades adsortivas de biocarvões para CBZ, principalmente em biocarvões produzidos a maiores temperaturas, devido à maior complexidade de sua estrutura, entrando ou bloqueando os micro e mesoporos do biocarvão. Conclui-se que o uso do biocarvão como um produto de característica sustentável parece ser promissor, porém, lacunas ainda existem na literatura atual sobre os impactos positivos e negativos do seu uso. Os resultados laboratoriais indicam um possível uso do biocarvão na remoção de compostos orgânicos da água, o que pode substituir tecnologias de tratamento existentes menos eficazes. Há, porém, de se considerar diversos fatores de influência nesse processo e mais estudos devem ser realizados a fim de corroborar com tais evidências.

Bio-optical variability of surface waters in Northeastern Gulf of Mexico (NEGOM) was examined using satellite and in situ data. Relatively high chlorophyll-a concentration (chl>=1 mg m-3) and high colored dissolved organic mater (ag443>=0.1 m-1) were generally observed inshore, near major river mouths, and in plumes of Mississippi River water that extended offshore during the three consecutive summer seasons (1998, 1999, and 2000). River discharge dominated chlorophyll-a concentration variability inshore, particularly near major river mouths. Strong interannual variability in chlorophyll-a concentration was observed inshore from Escambia to Tampa Bay region during the winter to spring transition, which was different in 1998 compared to the winter to spring transition in 1999 and 2000. This was related to higher fresh water discharge during the 1997-1998 El Niño-Southern Oscillation event as well as strong upwelling in spring 1998. The Mississippi plume extended >500 km southeast of the Mississippi delta and up to the Florida Keys was observed for the periods extending over 14 weeks between May and September every year of the study. In general, ag443 covaried linearly and inversely with salinity inshore during spring and fall, indicating conservative mixing. The NEGOM salinity-ag443 relationship of fall 1998, i.e., Salinity=36.59-29.86*ag443 (n=8771, r2=0.86; 0.01<=ag443<=0.52, 16 <=S<=36), served as the best predictor of NEGOM salinity based on in situ ag443 observations for spring and fall seasons from all years (<3% mean percentage errors; corresponding to <1.03 psu). This may help estimate salinity from satellite ocean color data, but further testing using data from multiple years is needed to improve such relationship. While river discharge was an important source of colored dissolved organic matter (CDOM), phytoplankton blooms also contributed to CDOM formation in the NEGOM. Using a pigment index of phytoplankton taxonomic groups, the variability in biomass proportion of microphytoplankton explained up to 76% of the variability of the average of normalized phytoplankton absorption coefficients (545, 625, and 673 nm). The clorophyll-specific absorption coefficient, a*ph(440), varies by a factor of 7 (0.02-0.15 m2mg-1). Particle size and pigment composition played important roles in determining a*ph(440) variability. This must be accounted for in chlorophyll-a concentration algorithms based on aph.

The period of ice break-off in spring is a key event for many biogeochemical processes in lakes globallly. The biogeochemical processes occurring at ice break-off have the potential of influencing characteristics of lakes throughout spring and summer, including algal blooms and greenhouse gas emission. This makes it important to study lakes in the period of ice break-off. At ice break-off, soil bacteria from the catchment area usually enter the lake via spring floods and mix with the bacteria already occurring in the lake water. In this study, the effects of mixing soil- and lake microbial communities during ice break-off-like conditions were tested by performing an experiment under controlled conditions in the laboratory. In the experiment, light, microbial community composition and concentration of soil-derived organic matter were manipulated to simulate different conditions associated with ice break-off. The variables investigated were bacterial activity and functionality, measured as cell abundance and enzymatic activity, as well as primary production and concentration of dissolved organic matter. The results showed that a mix of soil and lake microbial communities had enzymatic activity patterns resembling lake communities, and then shifted to being more similar to soil communities. The experiment also showed that degradation of measured dissolved organic matter was not linked to biotic processes, and that the observed decrease was most likely due to photo degradation. Finally, the experiment showed that primary production, here measured as chlorophyll a, was only stimulated by the mixed community with light and added soil dissolved organic matter. The results found in this study are important as they show that microbial communities do alter their function and enzymatic activity based on composition. Furthermore, the result that primary production was only seen in the presence of light, soilderived organic matter and a mixed community of lake and soil bacteria may be seen as an indication that primary producers in lake ecosystems to some extent depend on the inflow of terrestrial microbes and organic matter. It also possible that the coalescence of microbial communities enables the communities to perform tasks they were unable to prior to coalescence (i.e. perform tasks that allows primary production to take place). These results give the basis for further, more detailed studies.

<p>Heterotrophic bacteria utilize dissolved organic matter, and the carbon flow through an ecosystem depends on the fractions of the utilized carbon that is either respired or transferred to higher trophic levels. The major aim this thesis is to investigate 1) the relationship between composition and functioning in heterotrophic bacterioplankton communities and 2) the influence of environmental conditions on both parameters. I set up several batch culture experiments, where lake water filtrates containing bacteria but no grazers were inoculated into sterile freshwater medium to investigate the importance of the origin of the source community (the inoculum) versus the environmental conditions (the medium) for the composition and functional performance of bacterial communities. In some experiments the medium was manipulated to simulate changes in salinity, pH and dissolved organic matter quantity and quality. Functional parameters (biomass yield, respiration, growth efficiency and enzyme activities) and the genetic composition of the emerging bacterial communities were determined.</p><p>When bacterial inocula obtained from different habitats were re-grown under identical conditions, differently composed communities emerged. This indicates that the history and distribution of taxa within the inoculum was an important regulating factor of community composition. The coupling between community composition and functioning was not very tight, and there was functional equivalency with respect to aggregated functions important at the ecosystem scale (e.g., biomass production and respiration). The functional performance of bacterial communities could to a large extent be predicted from the medium alone, except when it deviated strongly from the ambient settings. When bacterial communities were exposed to dilution, a strong change in pH or an increase in salinity, growth of structurally and functionally distinct communities occurred. I therefore suggest that it depends on the disturbance regime how bacterial community structure and function are related to each other. </p>

Heterotrophic bacteria utilize dissolved organic matter, and the carbon flow through an ecosystem depends on the fractions of the utilized carbon that is either respired or transferred to higher trophic levels. The major aim this thesis is to investigate 1) the relationship between composition and functioning in heterotrophic bacterioplankton communities and 2) the influence of environmental conditions on both parameters. I set up several batch culture experiments, where lake water filtrates containing bacteria but no grazers were inoculated into sterile freshwater medium to investigate the importance of the origin of the source community (the inoculum) versus the environmental conditions (the medium) for the composition and functional performance of bacterial communities. In some experiments the medium was manipulated to simulate changes in salinity, pH and dissolved organic matter quantity and quality. Functional parameters (biomass yield, respiration, growth efficiency and enzyme activities) and the genetic composition of the emerging bacterial communities were determined. When bacterial inocula obtained from different habitats were re-grown under identical conditions, differently composed communities emerged. This indicates that the history and distribution of taxa within the inoculum was an important regulating factor of community composition. The coupling between community composition and functioning was not very tight, and there was functional equivalency with respect to aggregated functions important at the ecosystem scale (e.g., biomass production and respiration). The functional performance of bacterial communities could to a large extent be predicted from the medium alone, except when it deviated strongly from the ambient settings. When bacterial communities were exposed to dilution, a strong change in pH or an increase in salinity, growth of structurally and functionally distinct communities occurred. I therefore suggest that it depends on the disturbance regime how bacterial community structure and function are related to each other.

Increasing human populations and activities in coastal areas have led to high nutrient loading and estuarine ecosystem decline. Natural hydrological patterns in South Florida have been drastically altered by changes in water management and land use practices. As a result Florida Bay has experienced a series of negative ecosystem effects including hypersalinity events, degradation of water quality, and harmful algal blooms and declines in upper trophic level populations. To remediate ecosystem decline in Florida's coastal ecosystems, the Comprehensive Everglades Restoration Plan proposes to restore a more natural hydrologic flow in the Everglades. It is expected hydrologic restoration efforts will change the amount, sources and ratios of dissolved nutrients (organic and inorganic) delivered to the bay potentially inducing an ecosystem response of changing structure and function in both planktic and benthic habitats. Identifying biogeochemical linkages between external nutrient inputs from the Everglades and internal cycling processes of Florida Bay is critical to understanding the effects of hydrological restoration and changing nutrient regimes on Florida Bay. A nitrogen (δ15N) and carbon (δ13C ) stable isotopic approach affords an effective means of assessing the fate of varying nutrient sources and delineating the dominant biogeochemical processes governing nutrient cycling in the bay. This study's main goals were to use stable isotopic analyses of C and N in dissolved and particulate materials to determine spatial and seasonal relationships between Everglades nutrient sources and their biological sinks in Florida Bay, examine the biogeochemical relationships among inorganic and organic components of the water column and benthos in Florida Bay, and assess future ecological response to changing nutrient inputs resulting from restoration efforts. A large east to west gradient from more enriched to more depleted δ15N values was noted in both dissolved nitrogen pools and organic components of the bay. This trend indicates that there are differing nutrient sources and biogeochemical processes influencing the various regions of the bay. Isotopic similarity of the dissolved nitrogen pools from the Everglades and particulate organic matter in the bay points to a strong relationship between both ecosystems. Everglades nutrient inputs delivered to the bay in the wet season directly influence ecological responses in the bay, in some cases increases in algal biomass. Seasonality also influences nitrogen transformations in the dissolved nitrogen pools and the sediments. During dry periods when there is little or no hydrologic flow from the Everglades into the bay, denitrification is a major process affecting nitrogen cycling in the eastern and central regions of the bay. During the wet periods, denitrification becomes suppressed and dissimilatory nitrate reduction (DNRA) is favored. Increased hydrologic flow brings fresh organic matter that fuels DNRA. There was a consistent spatial pattern from more depleted to more enriched δ13C values, onshore to offshore relative to the mainland which indicates strong terrestrial influence on Florida Bay sites along the mangrove boundary with the Everglades. Particulate organic matter exhibited a shift to more enriched δ13C values during the wet season which reflects an increase in algal biomass. A shift to more depleted δ13C values of DOM indicated increased terrestrial influence from the Everglades during the wet season. The approach undertaken in this study identifies a strong linkage between nutrient inputs from the Everglades and biogeochemical processes in the bay. These findings underscore the need to consider the impact of both allochtonous nutrient inputs and the dominant processes governing cycling in the bay when making management decisions that continue to refine hydrologic restoration plans.

Dissolved organic matter (DOM) is a central component of the global carbon cycle. Thus, small changes to the amount of DOM imported, processed and produced within lakes can have a large effect on regional carbon budgets. In addition to being a vital energy source at the base of the aquatic food web, DOM is physico-chemically reactive. However, identifying and understanding the controls of DOM processing has remained challenging due to the complex composition of DOM. DOM comprises a mixture of decomposition by-products of terrestrial origin as well as newly synthesized material from in situ production. DOM compounds form gradients of reactivity to biogeochemical processes, such as photodegradation, biodegradation, and flocculation, and they perform a suite of functions in aquatic systems. The overarching goal of this thesis was to investigate controls of DOM processing in Swedish lakes. We do this in two ways: 1) by characterizing the molecular-level composition of DOM in lakes, and 2) by investigating interactions between very labile and relatively recalcitrant DOM. The first three chapters utilize ultrahigh resolution mass spectrometry to show that the detailed chemical composition of DOM varies along a hydrology gradient, and secondarily along a temperature gradient that co-varies with agriculture and nutrients. Next, we illustrate the coherence between molecular-level characteristics and bulk optical characteristics. Together, these studies suggest that protein-like fluorescence, aliphatic compounds, and N-containing compounds are either resistant to degradation or tightly cycled in the system, and thus persist at long water residence times. The most oxidized compounds, such as vascular plant-derived polyphenolic compounds, are abundant in areas with high precipitation and are lost with increasing water residence time. Vascular plant-derived polyphenolic compounds were most strongly related to DOM with high apparent molecular weight, suggesting that hydrophobic interactions drive aggregate formation. Furthermore, the association of high molecular weight DOM with polyphenolic compounds suggests that aggregates are hotspots of reactivity in aquatic systems. Finally, we find no indication that the addition of labile organic matter enhances the biodegradation of less reactive DOM. Thus, we suggest that in freshwaters, intrinsic molecular properties, such as the basic structural features of compounds, dominate over extrinsic factors.

Made available in DSpace on 2017-07-10T19:23:59Z (GMT). No. of bitstreams: 1 Thaisa _Pegoraro.pdf: 1491826 bytes, checksum: 1b9380fd12ae09c6e6128b1816c0215e (MD5) Previous issue date: 2015-02-23 / Biochar, also known as terra preta do índio, is a highly porous material and is a result of biomass pyrolysis in oxygen-controlled conditions and low temperatures (up to 600 oC). Due to the viable manufacturing process and the wide variety of applications, it is a promising material for various uses. Among the main uses of biochar, studies indicate its potential in improving soil quality, besides being a way of contributing to carbon sequestration from the atmosphere and used in the retention of organic and inorganic contaminants in the environment. This work aimed to present a review of the concepts and current studies on biochar, for a better understanding of the subject (Paper 1). The objective was to also investigate the adsorption of pharmaceuticals carbamazepine (CBZ) and lincomycin (LMC) by six biochars under the influence of surface characteristics of biochar (produced from Brazilian pepper and sugarcane bagasse, in temperatures of 300 o, 400 o and 600o C) and environmental factors (pH and adsorption competition between CBZ and LMC) (Paper 2). The latest study aimed to understand the effects of exposure of dissolved organic matter (DOM) in the surface properties of three biochars produced from sugarcane bagasse, in the CBZ adsorption (Paper 3). Batch equilibrium tests were performed in constant temperature, varying pH, and the data were adjusted in Freundlich isotherms. For the DOM test, the biochars were previously loaded with humic acid, tannic acid, gallic acid, and catechol in concentrations equivalent to those found in soils. The values of Kd, n and KF were reported and analyzed. As a result, it was found that biochars produced from sugarcane bagasse and high pyrolysis temperature were more effective in CBZ and LMC adsorption. In the biochar produced from bagasse at 300° C, the adsorption of CBZ was not affected by the presence of functional groups on the surface of biochar. LMC, which is ionized at pH 7.6, is more easily binded to negatively charged biochars when pH is acidic (pH<pKa). Furthermore, it was found that the CBZ and LMC compete for the same adsorption sites, regardless the variation of pH solution. In general, DOM affected adsorptive properties of biochars and attenuated CBZ adsorption, especially for biochars produced in higher temperatures because of the greater complexity of its structure, when DOM enters or blocks the biochar micro and mesoporous. It was concluded that the use of biochar as a product of sustainable feature looks promising, but there are still some gaps in the current literature about the positive and negative impacts of its use. Laboratory results indicate a possible use of biochar in removing organic compounds from water, which can replace less effective existing treatment technologies. There is to be considered, however, several factors that influence this process and more studies are needed to corroborate such evidence. / O biocarvão, também conhecido como terra preta do índio, é um material de alta porosidade e é resultado da pirólise da biomassa em condições de oxigênio controlado e baixas temperaturas (até 600 oC). Devido ao viável processo de produção e à ampla variedade de aplicações, trata-se de um material promissor para diversos usos. Dentre as principais utilidades do biocarvão, estudos indicam seu potencial na melhoria da qualidade do solo, além de ser uma forma de contribuir para o sequestro de carbono da atmosfera e ser utilizado na retenção de contaminantes orgânicos e inorgânicos no ambiente. Nesse trabalho, objetivou-se realizar uma revisão sobre os conceitos e estudos atuais sobre biocarvão, para uma melhor compreensão do tema (Artigo 1). Objetivou-se também investigar o processo de adsorção dos fármacos carbamazepina (CBZ) e lincomicina (LMC) por seis biocarvões, sob a influência de características superficiais do biocarvão (produzidos a partir de pimenta brasileira e bagaço de cana-de-açúcar, a 300o, 400o e 600o C) e fatores ambientais (pH e competição sortiva entre CBZ e LMC) (Artigo 2). No último estudo, objetivou-se compreender os efeitos da exposição da matéria orgânica dissolvida (MOD) nas propriedades superficiais de três biocarvões produzidos a partir de bagaço de cana-de-açúcar, na adsorção de CBZ (Artigo 3). Ensaios de equilíbrio de adsorção foram realizados em batelada e temperatura constante, variando o pH, e os dados foram ajustados em isotermas de Freundlich. Para o ensaio com MOD, os biocarvões foram previamente carregados com ácido húmico, ácido tânico, ácido gálico e catecol em concentrações equivalentes às de matéria orgânica encontrada em solos. Os valores de Kd, KF e n foram reportados e analisados. Como resultado, verificou-se que biocarvões produzidos a partir da biomassa de bagaço de cana-de-açúcar e altas temperaturas de pirólise foram mais efetivos na adsorção de CBZ e LMC. Em biocarvão produzido a partir de bagaço de cana-de-açúcar, a 300 oC, a adsorção de CBZ não foi afetada pela presença de grupos funcionais na superfície do biocarvão. Já a LMC, que é ionizada a pH 7,6, liga-se mais facilmente a biocarvões carregados negativamente quando o pH é ácido (pH<pKa). Além disso, verificou-se que a CBZ e LMC competem entre si pelos mesmos sítios sortivos, independente da variação do pH da solução. A MOD afetou as propriedades adsortivas de biocarvões para CBZ, principalmente em biocarvões produzidos a maiores temperaturas, devido à maior complexidade de sua estrutura, entrando ou bloqueando os micro e mesoporos do biocarvão. Conclui-se que o uso do biocarvão como um produto de característica sustentável parece ser promissor, porém, lacunas ainda existem na literatura atual sobre os impactos positivos e negativos do seu uso. Os resultados laboratoriais indicam um possível uso do biocarvão na remoção de compostos orgânicos da água, o que pode substituir tecnologias de tratamento existentes menos eficazes. Há, porém, de se considerar diversos fatores de influência nesse processo e mais estudos devem ser realizados a fim de corroborar com tais evidências.