Sediments negatively impact the quality of surface waters and are a significant source of contaminants, such as nutrients and pesticides in agricultural watersheds. Sediment fingerprinting is a relatively recent technique capable of determining the origin of suspended sediment. In this thesis, we investigated the sources of suspended sediments in a predominantly rural watershed in Atlantic Canada. Our first objective was to determine sediment source apportionment estimates by treating the watershed as a single catchment, and making the assumption that conditions affecting source production and transport, from the land to the stream, were uniform across the watershed. For the first objective, suspended sediments were collected at a single target location for sediment apportionment (main outlet) and used to represent sediment dynamics throughout the entire catchment. For the second objective, we examined not only the whole watershed but also sub-watersheds within it, to better understand processes affecting sediment dynamics. / October 2016

A travers l’exemple himalayen, nous étudions les mécanismes influençant la composition en osmium des sédiments durant l’érosion, le transport sédimentaire et le dépôt dans les zones estuariennes. Au niveau du bassin himalayen de la Kali Gandaki, les relations observées entre les concentrations en osmium et les quantités de carbone organique confirment le rôle important des schistes noirs appartenant aux TSS (non radiogéniques) et au LH (radiogénique) malgré leurs faibles répartitions géographiques. Cependant, la composition fortement radiogénique mesurée dans les sédiments du Gange n'est pas couplée a un enrichissement en 187Os dont la quantité moyenne est comparable à celle mesurée dans la croûte continentale. La signature isotopique du Gange résulterait d'un appauvrissement en Os non-radiogénique, témoignant d'une forte dilution par des sédiments dérivés de l'érosion des roches cristallines de l'HHC. Nous montrons à travers l’étude de sédiments estuariens que le comportement de l’osmium en contact avec l’eau de mer est complexe et des échanges sont possibles à l’interface. Le développement analytique réalisé en parallèle des études sur les sédiments a permis de documenter pour la première fois la composition en osmium des eaux souterraines. L’étude des aquifères de la plaine du Bengale montre que les eaux souterraines possèdent des concentrations en osmium significativement plus élevées que les eaux de rivière ou l’eau de mer. Si ce résultat est généralisable aux aquifères mondiaux, un flux global de l’ordre de 170 kg d’osmium par an pourrait être apporté à l’océan. Cet apport est significatif et impliquerait la réévaluation du bilan océanique mondial et une diminution significative du temps de résidence de l’osmium dans les océans. Ce résultat n’est pas anodin puisqu’il pourrait en partie réconcilier le temps de résidence estimé par bilan de masse océanique et les variations glaciaires-interglaciaires observées par le rapport 187Os/188Os dans de nombreux enregistrements marins / Using the Himalayan example, this study documents the systematics controlling the osmium composition of sediments during weathering processes, sedimentary transport and sediment deposition in tidal areas. The relationships observed between osmium concentrations and organic carbon contents in sediments of the Himalayan Kali Gandaki catchment underscore the role of black shales from the TSS (mostly unradiogenic) and LH (highly radiogenic) Himalayan units, despite their limited geographic distribution. However, the highly radiogenic composition displayed by Ganges sediments is not coupled to an enrichment in 187Os in these sediments, which on average are comparable to that of typical continental crust. Instead, the Ganges radiogenic signature results from an impoverishment in non-radiogenic osmium, reflecting a strong dilution by erosion products of crystalline rocks of the HHC unit. Moreover, based on the study of rivers in the tidal zone, we document the complex behavior of osmium at the salt/fresh water transition, potentially involving exchange between sediments and dissolved osmium. Analytical development performed concurrently with the sediment studies allowed the first measurements of groundwater osmium compositions. Groundwaters of Bengal plain aquifers have osmium contents significantly higher than those previously documented for river water or seawater. If this result can be generalized to other aquifers a global osmium groundwater flux to the ocean of about 170 kg per year could be expected. This contribution is significant and would require a reevaluation of both the osmium marine budget and the residence time of osmium in the ocean. This result could partially reconcile the diverging marine Os residence times estimated from mass balance and from glacial-interglacial variations in the 187Os/188Os marine record

Spatial and temporal information on catchment sediment sources and sinks can provide an improved understanding of catchment response to human-induced disturbances. This is essential for the implementation of well-targeted catchment-management decisions. This thesis investigates the nature and timing of catchment response to human activities by examining changes in sediment sources and sinks in a dry-tropical subcatchment of the Great Barrier Reef (GBR) catchment area, in northeastern Australia. Changes in catchment sediment sources, both in terms of spatial provenance and erosion type, are determined using sediment tracing techniques. Results indicate that changes in sediment source contributions over the last 250 years can be linked directly to changes in catchment land use. Sheetwash and rill erosion from cultivated land (40???60%) and channel erosion from grazed areas (30-80%) currently contribute most sediment to the river system. Channel erosion, on a basin-wide scale, appears to be more important than previously considered in this region of Australia. Optically stimulated luminescence and 137Cs dating are used to determine pre-and post- European settlement (ca. 1850) alluvial sedimentation rates. The limitations of using 137Cs as a floodplain sediment dating tool in a low fallout environment, dominated by sediment derived from channel and cultivation sources, are identified. Low magnitude increases in post-disturbance floodplain sedimentation rates (3 to 4 times) are attributed to the naturally high sediment loads in the dry-tropics. These low increases suggest that previous predictions which reflect order of magnitude increases in post-disturbance sediment yields are likely to be overestimates. In-channel bench deposits, formed since European settlement, are common features that appear to be important stores of recently eroded material. The spatially distributed erosion/sediment yield model SedNet is applied, both with generic input parameters and locally-derived data. Outputs are evaluated against available empirically-derived data. The results suggest that previous model estimates using generic input parameters overestimate post-disturbance and underestimate pre-disturbance sediment yields, exaggerating the impact of European catchment disturbance. This is likely to have important implications for both local-scale and catchment-wide management scenarios in the GBR region. Suggestions for future study and the collection of important empirical data to enable more accurate model performance are made.

In the studies underlying this thesis, various source tracing techniques were applied to environmental samples from the Baltic region. Comprehensive sampling and analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surface sediments in Swedish coastal and offshore areas resulted in a unique data set for this region. Nearly 150 samples of surface sediments were analyzed for all tetra- to octa-chlorinated PCDD/Fs. The levels showed large spatial variability with hotspots in several coastal regions. Neither Sweden nor the EU has introduced guideline values for PCDD/Fs in sediment, but comparisons to available guidelines and quality standards from other countries indicate that large areas of primarily coastal sediments may constitute a risk to marine organisms. Multivariate pattern analysis techniques and receptor models, such as Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF), were used to trace sources. These analyses suggested that three to six source types can explain most of the observed pattern variations found in the sediment samples. Atmospheric deposition was suggested as the most important source to offshore areas, thus confirming earlier estimates. However, spatial differences indicated a larger fraction of local/regional atmospheric sources, characterized by PCDFs, in the south. This was indicated by the identification of several patterns of atmospheric origin. In coastal areas, the influence of direct emission sources was larger, and among these, chlorophenol used for wood preservation and emissions from pulp/paper production and other wood related industry appeared to be most important. The historic emissions connected to processes involving chemical reactions with chlorine (e.g. pulp bleaching) were found to be of less importance except at some coastal sites. The analysis of PCDD/Fs in Baltic herring also revealed spatial variations in the levels and pollution patterns along the coast. The geographical match against areas with elevated sediment levels indicated that transfer from sediments via water to organisms was one possible explanation. Fugacity, a concept used to predict the net transport direction between environmental matrices, was used to explore the gas exchange of hexachlorocyclohexanes (HCHs) and polychlorinated biphenyls (PCBs) between air and water. These estimates suggested that, in the Kattegat Sea, the gaseous exchange of HCHs primarily resulted in net deposition while PCBs were net volatilized under certain environmental conditions. The study also indicated that, while the air concentrations of both PCBs and γ-HCH are mostly dependent upon the origin of the air mass, the fluctuations in α-HCH were primarily influenced by seasonal changes.