The feedbacks between hydrology and biogeochemical cycling of nitrogen (N) are of critical importance to global bioavailable N budgets. Human activities are dramatically increasing the amount of bioavailable N in the biosphere, which is causing increasingly frequent and severe impacts on ecosystems and human welfare. Streams are important features in the landscape for N cycling, because they integrate many sources of terrestrially derived N and control export to downgradient systems via internal source and sink processes. N transformations in stream ecosystems are typically very complex due to spatiotemporal variability in the factors controlling N biogeochemistry. Thus, it is difficult to predict if a particular stream system will function as a net source or sink of bioavailable N. A key location for N transformations in stream ecosystems is the hyporheic zone, where stream and ground waters mix. The hyporheic zone can be a source of bioavailable N via nitrification or a sink via denitrification. These N transformations are regulated by the physical and biogeochemical conditions of hyporheic zones. Natural heterogeneity in streams leads to unique combinations of both the physical and biogeochemical conditions which in turn result in unique N source and sink conditions.

This dissertation investigates the relationships between physical and biogeochemical controls and the resulting fate of bioavailable N in hyporheic zones. The key physical factor investigated is the supply rate of solutes which is a function of transport processes—advection and dispersion, and transport conditions—hydraulic conductivity and flowpath length. Different physical conditions result in different characteristic residence times of water and solutes in hyporheic zones. The key biogeochemical factors investigated are the dynamics of oxygen (O₂), labile dissolved organic carbon (DOC), and inorganic bioavailable N (NH₄ ⁺ and NO₃⁻). This dissertation uses ¹⁵N isotope experiments, numerical modeling of coupled transport of the bioavailable N species, O₂ and DOC, and a suite of geophysical measurements to identify the key linkages between hydrological and biogeochemical controls on N transformations in hyporheic zones. Specifically, it was determined that the conditions governing the fate of hyporheic N are both the physical transport and reaction kinetics—the residence time of water and the O₂ uptake rate. An important scaling relationship is developed by relating the characteristic timescales of residence time and O₂ uptake. The resulting dimensionless relationship, the Damköhler number for O₂, is useful for scaling different streams hyporheic zones and their role on stream N source – sink dynamics. More generally, these investigations demonstrate that careful consideration and quantification of hydrological processes can greatly inform the investigation of aquatic biogeochemical dynamics and lead to the development of process-based knowledge. In turn, this process-based knowledge will facilitate more robust approaches to quantifying and predicting biogeochemical cycles and budgets.