Recent regulation mandates that ships conduct mid ocean ballast water exchange (BWE) prior to discharging foreign ballast in territorial waters of Australia, the U.S. and elsewhere. The enforcement of ballast water exchange legislation is undermined, however, by a lack of sensitive and reliable methods for verifying compliance. One way to assess compliance is to compare the concentrations of chemical tracers in ballast tanks with their known distributions in the open ocean. In this work, dissolved organic matter and trace elements are investigated as potential tracers of mid-ocean ballast water exchange on commercial voyages in the North Pacific and Atlantic Oceans. The optical properties of chromophoric dissolved organic matter (CDOM) are frequently used as tracers of water masses in bays and estuaries. Characterization of the underlying fluorescence spectra in seawater dissolved organic matter was performed using parallel factor analysis, allowing the identification of at least nine independently varying fluorescent components present in varying concentrations in the ocean and in ballast water. Two of the humic components were terrestrial in origin and their signals could be traced in the open ocean (Pacific and Atlantic) at levels of approximately 1.5% of riverine concentrations. One humic terrestrial component was sufficient for predicting the coastal vs. oceanic source of most ballast water samples, suggesting that single and dual channel fluorometers could be optimized for verifying ballast water exchange. Barium, manganese and phosphorus were also investigated as potential tracers. Measurements of Ba and P obtained via engine-cooling pipes on commercial vessels were consistent with previous oceanographic measurements. While Ba behaved conservatively in ballast water, concentrations of phosphorus fluctuated and Mn was removed in ballast tanks over time. Ba and P demonstrated considerable promise as ballast water tracers, exhibiting predictable concentrations in exchanged ballast tanks, given a priori knowledge of the ocean (Atlantic versus Pacific) in which BWE was performed.

Recent regulation mandates that ships conduct mid ocean ballast water exchange (BWE) prior to discharging foreign ballast in territorial waters of Australia, the U.S. and elsewhere. The enforcement of ballast water exchange legislation is undermined, however, by a lack of sensitive and reliable methods for verifying compliance. One way to assess compliance is to compare the concentrations of chemical tracers in ballast tanks with their known distributions in the open ocean. In this work, dissolved organic matter and trace elements are investigated as potential tracers of mid-ocean ballast water exchange on commercial voyages in the North Pacific and Atlantic Oceans. The optical properties of chromophoric dissolved organic matter (CDOM) are frequently used as tracers of water masses in bays and estuaries. Characterization of the underlying fluorescence spectra in seawater dissolved organic matter was performed using parallel factor analysis, allowing the identification of at least nine independently varying fluorescent components present in varying concentrations in the ocean and in ballast water. Two of the humic components were terrestrial in origin and their signals could be traced in the open ocean (Pacific and Atlantic) at levels of approximately 1.5% of riverine concentrations. One humic terrestrial component was sufficient for predicting the coastal vs. oceanic source of most ballast water samples, suggesting that single and dual channel fluorometers could be optimized for verifying ballast water exchange. Barium, manganese and phosphorus were also investigated as potential tracers. Measurements of Ba and P obtained via engine-cooling pipes on commercial vessels were consistent with previous oceanographic measurements. While Ba behaved conservatively in ballast water, concentrations of phosphorus fluctuated and Mn was removed in ballast tanks over time. Ba and P demonstrated considerable promise as ballast water tracers, exhibiting predictable concentrations in exchanged ballast tanks, given a priori knowledge of the ocean (Atlantic versus Pacific) in which BWE was performed.

Este trabalho refere-se à variabilidade da origem dos sedimentos transportados durante eventos de chuva-vazão em uma pequena bacia hidrográfica rural (1,19 Km2). Esta bacia está localizada no sul do Brasil e a área é caracterizada pela presença de agricultores familiares que principalmente cultivam fumo em áreas consideradas inaptas para atividades agrícolas, de acordo com o sistema de aptidão agrícola do solo. Isto ocasiona severas perdas de solo por erosão hídrica. Neste estudo foram utilizadas técnicas hidrossedimentométricas com análises estatísticas multivariadas para determinação da procedência dos sedimentos durante a subida e a descida da onda de cheia em eventos de precipitação variada. A metodologia utilizada é denominada “método Fingerprinting” e possibilita avaliar quais são as áreas contribuintes para a produção de sedimentos intra-eventos de chuva-vazão. Foram definidas três áreas com potencial para produção de sedimentos, sendo as fontes, o canal de drenagem, as estradas e as lavouras da bacia. Foram coletadas um total de quarenta amostras distribuídas nas áreas fontes de sedimentos. Sete eventos foram monitorados entre os anos de 2009 e 2011 e 24 amostras foram coletadas ao longo destes eventos. Como traçadores foram utilizados elementos químicos, de proveniência natural ou antrópica: sódio (Na), potássio (K), magnésio (Mg), cromo (Cr), manganês (Mn), ferro (Fe), cobre (Cu), zinco (Zn), cádmio (Cd), mercúrio (Hg), chumbo (Pb) e fósforo (P). Foi demonstrado que os elementos determinados como o melhor conjunto de traçadores (P, Fe, Mn, Mg e K) possuem capacidade em determinar a origem dos sedimentos. Pode-se afirmar que há variabilidade de fontes de sedimentos durante os eventos de chuva-vazão. O estudo revelou que o canal de drenagem contribui com boa parcela dos sedimentos (0 a 72%), principalmente no início do hidrograma. Mesmo utilizando práticas agrícolas de conservação dos solos e dos recursos hídricos as lavouras são as principais fontes fornecedoras de sedimentos, crescendo sua contribuição ao longo do evento (27 a 100%). Os sedimentos oriundos das estradas não possuíram contribuição relevante (0 a 23%) durante os eventos monitorados. Existem evidências da variabilidade das fontes de sedimentos durante a subida e a descida da onda de cheia ocorrida em eventos de chuva. / This work refers to the variability of the source of sediment transported during rainfall-runoff events in a small rural catchment (1.19 km2). This basin is located in the south of Brazil and the area is characterized by the presence of family farmers who mainly cultivate tobacco in areas considered unsuitable for agricultural activities, according to the system of agricultural capability of the soil. This causes severe soil loss by water erosion. In this study we used techniques hydrosedimentometrics with multivariate statistical analyzes to determine the provenance of sediments during the rise and fall of the flood wave in precipitation events varied. The methodology is called "fingerprinting method" and allows assessing which areas are contributors to sediment yield intra-rainfall-runoff events. We defined three areas with potential for sediment production, and sources, channel drainage, roads and crops in the basin. We collected a total of forty samples distributed in source areas of sediment. Seven events were monitored between 2009 and 2011 and 24 samples were collected during these events. Tracers were used as chemicals, natural or manmade origin of sodium (Na), potassium (K), magnesium (Mg), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu), zinc ( Zn), cadmium (Cd), mercury (Hg), lead (Pb) and phosphorus (P). It has been demonstrated that certain elements like the best set of tracers (P, Fe, Mn, Mg and K) have the ability to determine the origin of sediments. It can be said that there is variability of sediment sources during rainfall-runoff events. The study revealed that the drainage channel contributes good portion of the sediments (0-72%), especially early in the hydrograph. Even using agricultural practices to conserve soil and water resources crops are the main sources of sediment supply, growing their contribution throughout the event (27 to 100%). Sediment from roads did not possess relevant contribution (0-23%) during the monitored events. There is evidence of the variability of sediment sources during ascent and descent of the flood wave occurred in rain events.

Este trabalho refere-se à variabilidade da origem dos sedimentos transportados durante eventos de chuva-vazão em uma pequena bacia hidrográfica rural (1,19 Km2). Esta bacia está localizada no sul do Brasil e a área é caracterizada pela presença de agricultores familiares que principalmente cultivam fumo em áreas consideradas inaptas para atividades agrícolas, de acordo com o sistema de aptidão agrícola do solo. Isto ocasiona severas perdas de solo por erosão hídrica. Neste estudo foram utilizadas técnicas hidrossedimentométricas com análises estatísticas multivariadas para determinação da procedência dos sedimentos durante a subida e a descida da onda de cheia em eventos de precipitação variada. A metodologia utilizada é denominada “método Fingerprinting” e possibilita avaliar quais são as áreas contribuintes para a produção de sedimentos intra-eventos de chuva-vazão. Foram definidas três áreas com potencial para produção de sedimentos, sendo as fontes, o canal de drenagem, as estradas e as lavouras da bacia. Foram coletadas um total de quarenta amostras distribuídas nas áreas fontes de sedimentos. Sete eventos foram monitorados entre os anos de 2009 e 2011 e 24 amostras foram coletadas ao longo destes eventos. Como traçadores foram utilizados elementos químicos, de proveniência natural ou antrópica: sódio (Na), potássio (K), magnésio (Mg), cromo (Cr), manganês (Mn), ferro (Fe), cobre (Cu), zinco (Zn), cádmio (Cd), mercúrio (Hg), chumbo (Pb) e fósforo (P). Foi demonstrado que os elementos determinados como o melhor conjunto de traçadores (P, Fe, Mn, Mg e K) possuem capacidade em determinar a origem dos sedimentos. Pode-se afirmar que há variabilidade de fontes de sedimentos durante os eventos de chuva-vazão. O estudo revelou que o canal de drenagem contribui com boa parcela dos sedimentos (0 a 72%), principalmente no início do hidrograma. Mesmo utilizando práticas agrícolas de conservação dos solos e dos recursos hídricos as lavouras são as principais fontes fornecedoras de sedimentos, crescendo sua contribuição ao longo do evento (27 a 100%). Os sedimentos oriundos das estradas não possuíram contribuição relevante (0 a 23%) durante os eventos monitorados. Existem evidências da variabilidade das fontes de sedimentos durante a subida e a descida da onda de cheia ocorrida em eventos de chuva. / This work refers to the variability of the source of sediment transported during rainfall-runoff events in a small rural catchment (1.19 km2). This basin is located in the south of Brazil and the area is characterized by the presence of family farmers who mainly cultivate tobacco in areas considered unsuitable for agricultural activities, according to the system of agricultural capability of the soil. This causes severe soil loss by water erosion. In this study we used techniques hydrosedimentometrics with multivariate statistical analyzes to determine the provenance of sediments during the rise and fall of the flood wave in precipitation events varied. The methodology is called "fingerprinting method" and allows assessing which areas are contributors to sediment yield intra-rainfall-runoff events. We defined three areas with potential for sediment production, and sources, channel drainage, roads and crops in the basin. We collected a total of forty samples distributed in source areas of sediment. Seven events were monitored between 2009 and 2011 and 24 samples were collected during these events. Tracers were used as chemicals, natural or manmade origin of sodium (Na), potassium (K), magnesium (Mg), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu), zinc ( Zn), cadmium (Cd), mercury (Hg), lead (Pb) and phosphorus (P). It has been demonstrated that certain elements like the best set of tracers (P, Fe, Mn, Mg and K) have the ability to determine the origin of sediments. It can be said that there is variability of sediment sources during rainfall-runoff events. The study revealed that the drainage channel contributes good portion of the sediments (0-72%), especially early in the hydrograph. Even using agricultural practices to conserve soil and water resources crops are the main sources of sediment supply, growing their contribution throughout the event (27 to 100%). Sediment from roads did not possess relevant contribution (0-23%) during the monitored events. There is evidence of the variability of sediment sources during ascent and descent of the flood wave occurred in rain events.

Este trabalho refere-se à variabilidade da origem dos sedimentos transportados durante eventos de chuva-vazão em uma pequena bacia hidrográfica rural (1,19 Km2). Esta bacia está localizada no sul do Brasil e a área é caracterizada pela presença de agricultores familiares que principalmente cultivam fumo em áreas consideradas inaptas para atividades agrícolas, de acordo com o sistema de aptidão agrícola do solo. Isto ocasiona severas perdas de solo por erosão hídrica. Neste estudo foram utilizadas técnicas hidrossedimentométricas com análises estatísticas multivariadas para determinação da procedência dos sedimentos durante a subida e a descida da onda de cheia em eventos de precipitação variada. A metodologia utilizada é denominada “método Fingerprinting” e possibilita avaliar quais são as áreas contribuintes para a produção de sedimentos intra-eventos de chuva-vazão. Foram definidas três áreas com potencial para produção de sedimentos, sendo as fontes, o canal de drenagem, as estradas e as lavouras da bacia. Foram coletadas um total de quarenta amostras distribuídas nas áreas fontes de sedimentos. Sete eventos foram monitorados entre os anos de 2009 e 2011 e 24 amostras foram coletadas ao longo destes eventos. Como traçadores foram utilizados elementos químicos, de proveniência natural ou antrópica: sódio (Na), potássio (K), magnésio (Mg), cromo (Cr), manganês (Mn), ferro (Fe), cobre (Cu), zinco (Zn), cádmio (Cd), mercúrio (Hg), chumbo (Pb) e fósforo (P). Foi demonstrado que os elementos determinados como o melhor conjunto de traçadores (P, Fe, Mn, Mg e K) possuem capacidade em determinar a origem dos sedimentos. Pode-se afirmar que há variabilidade de fontes de sedimentos durante os eventos de chuva-vazão. O estudo revelou que o canal de drenagem contribui com boa parcela dos sedimentos (0 a 72%), principalmente no início do hidrograma. Mesmo utilizando práticas agrícolas de conservação dos solos e dos recursos hídricos as lavouras são as principais fontes fornecedoras de sedimentos, crescendo sua contribuição ao longo do evento (27 a 100%). Os sedimentos oriundos das estradas não possuíram contribuição relevante (0 a 23%) durante os eventos monitorados. Existem evidências da variabilidade das fontes de sedimentos durante a subida e a descida da onda de cheia ocorrida em eventos de chuva. / This work refers to the variability of the source of sediment transported during rainfall-runoff events in a small rural catchment (1.19 km2). This basin is located in the south of Brazil and the area is characterized by the presence of family farmers who mainly cultivate tobacco in areas considered unsuitable for agricultural activities, according to the system of agricultural capability of the soil. This causes severe soil loss by water erosion. In this study we used techniques hydrosedimentometrics with multivariate statistical analyzes to determine the provenance of sediments during the rise and fall of the flood wave in precipitation events varied. The methodology is called "fingerprinting method" and allows assessing which areas are contributors to sediment yield intra-rainfall-runoff events. We defined three areas with potential for sediment production, and sources, channel drainage, roads and crops in the basin. We collected a total of forty samples distributed in source areas of sediment. Seven events were monitored between 2009 and 2011 and 24 samples were collected during these events. Tracers were used as chemicals, natural or manmade origin of sodium (Na), potassium (K), magnesium (Mg), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu), zinc ( Zn), cadmium (Cd), mercury (Hg), lead (Pb) and phosphorus (P). It has been demonstrated that certain elements like the best set of tracers (P, Fe, Mn, Mg and K) have the ability to determine the origin of sediments. It can be said that there is variability of sediment sources during rainfall-runoff events. The study revealed that the drainage channel contributes good portion of the sediments (0-72%), especially early in the hydrograph. Even using agricultural practices to conserve soil and water resources crops are the main sources of sediment supply, growing their contribution throughout the event (27 to 100%). Sediment from roads did not possess relevant contribution (0-23%) during the monitored events. There is evidence of the variability of sediment sources during ascent and descent of the flood wave occurred in rain events.

Le phénomène de destruction de l’ozone est un sujet vaste mettant en scène de nombreux processus. Il a pour origine l’émission de composés dits gaz sources (SGs) dans la troposphère. Récemment, les espèces à très courte durée de vie (VSLS) ont été identifiées comme SGs possibles. Cependant, elles ne possèdent pas un temps de vie suffisamment long pour atteindre directement la stratosphère. Les VSLS se dégradent au cours de leur transport, conduisant à des composés intermédiaires, les gaz produits (PGs). Les SGs et les PGs des VSLS vont entrer dans la stratosphère au niveau des régions équatoriales où règne un transport vertical rapide, la convection. Les SGs à temps de vie plus long peuvent accéder à la stratosphère par tous les types de transport possibles. Une fois dans la stratosphère, les SGs et PGs vont être convertis en espèces réactives capables de détruire l’ozone. Cette thèse présente l’étude des différentes étapes se produisant avant la destruction de l’ozone : l’émission et le transport des SGs dans l’atmosphère, leur chimie de dégradation au cours de leur transport et enfin leur contribution à la destruction de l’ozone. Les traceurs chimiques tels que CO sont tout d’abord utilisés pour mettre en évidence le transport des SGs et PGs de la troposphère à la stratosphère. Puis, deux études décrivant 2 types d’espèces différentes, entrant dans le processus de destruction de l’ozone, sont présentées : pour OCS (sulfure de carbonyle) et les VSLS bromés (CHBr3 et CH2Br2). OCS est l’un des principaux précurseurs d’aérosols sulfatés présents dans la stratosphère catalysant la destruction de l’ozone par chimie hétérogène. Cependant, sa contribution à cette couche comporte de nombreuses incertitudes. Ses sources d’émissions, sa répartition avec la latitude et sa contribution à la couche d’aérosols sulfatés sont présentées. La contribution des VSLS bromées au brome de la stratosphère est une question en cours de résolution. Leur chimie au cours de leur transport dans l’atmosphère est décrite de manière détaillée. / Ozone depletion is a complex subject involving several processes starting by the emission of the sources gases (SGs) in the lower troposphere. Recently the VSLS (very short lived substances) have been identified as potential SGs. However they do not have a lifetime long enough to reach directly the stratosphere. During the transport, the VSLS undergo degradation leading to products gases (PGs). The SGs and PGs of the VSLS reach the stratosphere in the Tropical region where a rapid vertical transport occurs, the convection. The SGs with longer lifetime can reach the stratosphere by any transport pathway from the location of their emissions. Once in stratosphere the SGs and PGs will be converted into reactive species able to deplete ozone. This thesis presents the study of the several steps occurring before the ozone depletion: SGs emission, SGs and PGs transport into the atmosphere, the chemical degradation occurring during their transport and finally their contribution to the ozone depletion. First, chemical tracers, as CO, are used to highlight the main pathways from the troposphere to the stratosphere. Then two studies of two different types of species entering in the process of ozone destruction are presented: for OCS (carbonyl sulfide) and the brominated VSLS (CHBr3 et CH2Br2). OCS is one of the sulfate aerosols precursors catalyzing the ozone depletion. However, OCS contribution to this layer has some uncertainties. OCS emission sources, the latitude repartition and the contribution to the sulfate aerosols are presented. The contribution of the brominated VSLS to the stratospheric bromine is a key issue that being almost resolved. The brominated VSLS chemical degradation during the atmospheric transport will be described in detail.