Within aquatic environments sediment water interfaces (SWIs) are the most important areas concerning exchange processes between the water body and the sediment. These spatially restricted regions are characterized by steep biogeochemical gradients that determine the speciation and fate of natural or artificial substances. Apart from biological mediated processes (e.g., burrowing organisms, photosynthesis) the determining exchange processes are diffusion or a colloid-mediated transport. Hence, methods are required enabling to capture the fine scale structures at the boundary layer and to distinguish between the different transport pathways. Regarding emerging substances that will probably reach the aquatic environment engineered nanomaterials (ENMs) are of great concern due to their increased use in many products and applications. Since they are determined based on their size (<100 nm) they include a variety of different materials behaving differently in the environment. Once released, they will inevitable mix with naturally present colloids (< 1 μm) including natural nanomaterials. With regard to existing methodological gaps concerning the characterization of ENMs (as emerging substances) and the investigation of SWIs (as receiving environmental compartments), the aim of this thesis was to develop, validate and apply suitable analytical tools. The challenges were to i) develop methods that enable a high resolution and low-invasive sampling of sediment pore water. To ii) develop routine-suitable methods for the characterization of metal-based engineered nanoparticles and iii) to adopt and optimize size-fractionation approaches for pore water samples of sediment depth profiles to obtain size-related information on element distributions at SWIs. Within the first part, an available microprofiling system was combined with a novel micro sampling system equipped with newly developed sample filtration-probes. The system was thoroughly validated and applied to a freshwater sediment proving the applicability for an automatic sampling of sediment pore waters in parallel to microsensor measurements. Thereby, for the first time multi-element information for sediment depth profiles were obtained at a millimeter scale that could directly be related to simultaneously measured sediment parameters. Due to the expected release of ENMs to the environment the aim was to develop methods that enable the investigation of fate and transport of ENMs at sediment water interfaces. Since standardized approaches are still lacking, methods were developed for the determination of the total mass concentration and the determination of the dissolved fraction of (nano)particle suspensions. Thereby, validated, routine suitable methods were provided enabling for the first time a routine-suitable determination of these two, among the most important properties regarding the analyses of colloidal systems, also urgently needed as a basis for the development of appropriate (future) risk assessments and regulatory frameworks. Based on this methodological basis, approaches were developed enabling to distinguish between dissolved and colloidal fractions of sediment pore waters. This made it possible for the first time to obtain fraction related element information for sediment depth profiles at a millimeter scale, capturing the fine scale structures and distinguishing between diffusion and colloid-mediated transport. In addition to the research oriented parts of this thesis, questions concerning the regulation of ENPs in the case of a release into aquatic systems were addressed in a separate publication (included in the Appendix) discussing the topic against the background of the currently valid German water legislation and the actual state of the research.