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Les sols boréaux représentent l’un des plus grands stocks de carbone terrestre à l’échelle globale. Ainsi, l'un des principaux transferts de matière des écosystèmes terrestres vers les écosystèmes aquatiques concerne le transport du carbone organique. Le carbone organique dissous (COD) joue un rôle crucial dans les cycles du carbone des systèmes aquatiques boréaux, reliant les écosystèmes terrestres et aquatiques. Il constitue une source d'énergie pour les micro-organismes présents dans le sol et dans l'eau. La matière organique dissoute (MOD) dans les lacs et les sols présente diverses compositions influencées par leur source et leur temps de résidence. Elle se compose principalement de matière organique allochtone caractérisée par des composés résistants de type humique et de matière organique autochtone contenant des composés facilement dégradables de type protéique. Les processus biogéochimiques le long du continuum terre-eau boréal influencent le cycle global du carbone et, par conséquent, le climat de la Terre. Les zones riveraines (ZR) constituent des passages critiques pour le transport hydrologique latéral de la matière organique dans les écosystèmes boréaux, facilitant la connexion entre les puits de matière organique terrestres et aquatiques. Les sols riches en matières organiques des ZR sont des processeurs biogéochimiques importants dans les bassins versants, influençant considérablement la concentration et la composition de la matière organique le long du continuum terre-eau. Malgré notre compréhension du budget de carbone dans les écosystèmes terrestres et aquatiques, la transformation de la MOD le long du gradient terre-eau, en particulier aux interfaces terre-eau, demeure mal comprise.. Dans notre étude portant sur 16 bassins versants des bassins des rivières La Romaine et Eastmain des régions de la Côte-Nord et de la Baie James, respectivement, nous avons déterminé la concentration, la composition et la réactivité de la MOD dans des compartiments clés des bassins versants: le sol forestier, la ZR, les cours d'eau et les lacs. Nous avons observé des différences significatives dans la concentration et la variabilité du COD entre les compartiments du bassin versant (forêt, ZR, ruisseau, lac). Dans l'ensemble, il y a eu une diminution des concentrations et de la variabilité du COD des milieux terrestres aux milieux aquatiques, accompagnée de changements prononcés lors du passage dans la ZR. Nos recherches ont révélé le rôle central des interfaces terre-eau sur les transformations quantitatives et qualitatives de la MOD. Les diminutions rapides des concentrations totales de COD et des 4 proportions de COD dégradable pendant le passage vers les cours d'eau indiquent des pertes immédiates se produisant soit dans les cours d'eau eux-mêmes, soit par dégradation dans la ZR. Cependant, nous avons observé une présence relativement persistante de MOD d'origine terrestre dans de multiples compartiments du bassin versant. En outre, nos résultats montrent des concentrations élevées de MOD de type protéique dans les échantillons de la forêt et de la ZR, ce qui permet de mieux comprendre les sources de la MOD potentiellement terrestres de type protéique. En résumé, notre recherche met en lumière la dynamique complexe de la MOD le long des continuums terre-eau, en fournissant des informations qui améliorent notre compréhension de ces éléments vitaux au sein des écosystèmes aquatiques. / A considerable portion of the Earth's carbon is stored within boreal soils. Thus, one of the predominant transfers of mass from terrestrial to aquatic ecosystems involves the movement of organic carbon. Dissolved organic carbon (DOC) is a crucial contributor to the carbon cycles of boreal aquatic systems, linking land and water ecosystems and representing an energy source for microorganisms in both soil and water. Dissolved organic matter (DOM) in lakes and soil embodies diverse compositions influenced by their source and residence time. It predominantly consists of allochthonous DOM characterized by resistant humic-like compounds and autochthonous DOM featuring easily degradable, protein-like compounds. The biogeochemical processes along the boreal land-water gradient influence the global carbon cycle and, consequently, the Earth's climate. The riparian zones (RZ) act as critical passages for lateral hydrological transport of DOM within boreal ecosystems, facilitating the connection between diverse terrestrial DOM pools and stream DOM pools. The organic-rich soils in RZ, highlighted as biogeochemical hotspots in watersheds, significantly influence the concentration and composition of DOM along the land-water continuum. Despite our grasp of carbon budgets in terrestrial and aquatic ecosystems, the processing of DOM along the land-water gradient, particularly at land-water interfaces, remains unclear. In our study across 16 watersheds in the "La Romaine" and "Eastmain" catchments, we identified the concentration, composition, and reactivity of DOM in key watershed compartments: forest soil, RZ, streams, and lakes. We observed significant distinctions in DOM concentration and variability across watershed compartments (forest, RZ, stream, lake). Overall, there was a decrease in DOC concentrations and variability from land to aquatic environments, accompanied by abrupt shifts as it passed through the RZ. Our research revealed the pivotal role of land-water interfaces on both the quantitative and qualitative changes observed in DOM. The rapid declines in total DOC concentrations and degradable DOC proportions during the transition to streams indicate immediate losses occurring either within the streams themselves or through degradation within the RZ. However, we observed a relatively persistent presence of terrestrially derived DOM in multiple compartments within the watershed. Additionally, our finding shows high concentrations of protein-like DOM in forest and RZ samples, providing insights into the probable terrestrial sources of protein-like DOM elements. In summary, our research illuminates 6 the complex dynamics of DOM along land-water continua, enhancing our understanding our comprehension of these vital elements within aquatic ecosystems.

O difosfato de cloroquina é um fármaco antimalárico, de conhecida fotossensibilidade. O presente trabalho teve como objetivo desenvolver, caracterizar e avaliar a fotodegradação de complexos binários e ternários de difosfato cloroquina. Para tanto, foi desenvolvida uma metodologia analítica que permitiu identificar e quantificar o fármaco por CLAE com detecção UV, que mostrou seletividade, além de adequada especificidade, sensibilidade, linearidade, precisão exatidão, frente a seus respectivos produtos de degradação e fotodegradação. Os complexos com β-ciclodextrina e HP-β-ciclodextrina obtidos não foram capazes proteger o fármaco da degradação promovida pela luz nos meios água, HCI 0,1N e tampão fosfato pH 6,8. Em HCI 0,1N verificou-se que alguns complexos capazes, inclusive, de acelerar a degradação promovida pela luz. Foram também realizados estudos de recristalização do fármaco em diferentes solventes para avaliar o impacto sobre suas características físico-químicas, os quais resultaram possíveis modificações cristalinas observadas mediante técnica de DSC quando foram utilizados etanol e clorofórmio como solventes para o processo. / The chloroquine diphosphate is an antimalarial drug of know photosensibility. The present work had as objective to development, characterize and evaluate photodegradation of binary and ternary complex of chloroquine diphosphate. For such a way, an analytical methodology was developed that allowed to identify and quantify the drug for CLAE with detection UV, that showed good selectivity, beyond adjusted specificity, sensitivity, linearity, precision and accuracy, front its respective products of degradation and photodegradation. The complexes with &#946-ciclodextrin and HP-&#946-ciclodextrin had not been capable to protect the drug of the degradation promoted by the light in solvent water, HCl 0,1N and buffer phosphate pH 6,8. In HCl 0,1N is verified that some complex are capable to speed up the degradation promoted by the light. Also studies of recrystallization of the drug in different solvents were carried trough to evaluate the impact on its physical-chemistry characteristics, which had resulted in possible observed by DSC crystalline modifications technique when ethanol and chloroform had been used as solvent for the process.

O difosfato de cloroquina é um fármaco antimalárico, de conhecida fotossensibilidade. O presente trabalho teve como objetivo desenvolver, caracterizar e avaliar a fotodegradação de complexos binários e ternários de difosfato cloroquina. Para tanto, foi desenvolvida uma metodologia analítica que permitiu identificar e quantificar o fármaco por CLAE com detecção UV, que mostrou seletividade, além de adequada especificidade, sensibilidade, linearidade, precisão exatidão, frente a seus respectivos produtos de degradação e fotodegradação. Os complexos com β-ciclodextrina e HP-β-ciclodextrina obtidos não foram capazes proteger o fármaco da degradação promovida pela luz nos meios água, HCI 0,1N e tampão fosfato pH 6,8. Em HCI 0,1N verificou-se que alguns complexos capazes, inclusive, de acelerar a degradação promovida pela luz. Foram também realizados estudos de recristalização do fármaco em diferentes solventes para avaliar o impacto sobre suas características físico-químicas, os quais resultaram possíveis modificações cristalinas observadas mediante técnica de DSC quando foram utilizados etanol e clorofórmio como solventes para o processo. / The chloroquine diphosphate is an antimalarial drug of know photosensibility. The present work had as objective to development, characterize and evaluate photodegradation of binary and ternary complex of chloroquine diphosphate. For such a way, an analytical methodology was developed that allowed to identify and quantify the drug for CLAE with detection UV, that showed good selectivity, beyond adjusted specificity, sensitivity, linearity, precision and accuracy, front its respective products of degradation and photodegradation. The complexes with &#946-ciclodextrin and HP-&#946-ciclodextrin had not been capable to protect the drug of the degradation promoted by the light in solvent water, HCl 0,1N and buffer phosphate pH 6,8. In HCl 0,1N is verified that some complex are capable to speed up the degradation promoted by the light. Also studies of recrystallization of the drug in different solvents were carried trough to evaluate the impact on its physical-chemistry characteristics, which had resulted in possible observed by DSC crystalline modifications technique when ethanol and chloroform had been used as solvent for the process.

The kinetics of drugs photodegradation have traditionally been treated using thermal kinetic analysis methods consisting most commonly in zero and first order kinetics. These treatment strategies were shown to lack specificity and present a number of limitations when applied to photoreactions kinetics. Nevertheless, these methods have widely been used due to a lack of integrated rate-laws for the majority of photoreactions types, in turn, due to the presence of a variable time-dependent factor in most photoreactions rate-laws that prevents their mathematical integration. To address these limitations, a new methodology for the development and validation of semi-empirical integrated rate-laws that faithfully describe photoreactions kinetics and photoreactions simulated cases generated by numerical integration methods (NIMs), is hereby presented. Using this methodology, a new kinetic order was ascribed to photoreactions namely the Φ-order kinetics. Semi-empirical integrated rate-laws were, thus, developed for three photoreaction types namely, unimolecular, AB(1Φ), photoreversible ,AB(2Φ), and consecutive, AB4(4Φ), photoreactions. The proposed models were further tested experimentally on drugs following these photodegradation mechanisms using; nifedipine and nisoldipine for unimolecular photoreactions; montelukast and fluvoxamine for photoreversible reactions; and riboflavin for consecutive photoreactions. The developed models not only accurately described the photoreaction kinetics of these drugs but also allowed the determination of all the kinetic parameters that characterise them. Furthermore, the above studied drugs were shown to act as precise and simple actinometers when analytically treated with the Φ-order kinetic methods, hereby presented. A universal standard method for the precise and worldwide reproducible study of drugs stability and compounds photoreactions, based on monochromatic irradiation and Φ-kinetics data analysis, is also detailed and adopted throughout the thesis. Finally, two new kinetic parameters namely, the pseudo-rate-constant and pseudo-initial velocity have been identified and shown to be more reliable and accurate in the description and universal comparison of photoreactions kinetics.