Hydrologic catchment response varies in time. The goal of this dissertation is to investigate how and why it varies and what controls these variations. In order to tackle these questions the first step is to develop a method that permits the capturing of the temporal variation of transit time distributions (TTDs). To this end, the established transfer function-convolution approach using time series of stable water isotopes was modified so that it is now able to determine variable mean transit times (mTTs). The type and the shape parameter of the transfer function also vary in time. We found that antecedent moisture content, saturated hydraulic conductivity, soil depth and subsequent precipitation intensity are all potential controls. We propose a dimensionless number that integrates these controls and relates available storage to incoming and outgoing water fluxes in combination with information on antecedent moisture conditions to predict TTD type and shape. The individual TTDs for every time step produced by this model can be superimposed, summed and normalized to create a classification tool for catchments that is based on its general response behavior to precipitation events: the master transit time distribution. With this model in hand the hydrologic response for three consecutive monsoon seasons in ten nested subcatchments was examined. It was found that the major response controls were changing between the years in accordance with three hydrologic response modes. The mTT correlated most strongly with soil depth in the first year, with hydraulic conductivity in the second year and with curvature in the third year. These variations were produced by differences in precipitation patterns that led to differences in soil saturation and consequently to different dominant flow processes: in the first year most of the water left the catchment via fast flow paths (macropore flow, overland flow), in the second year shallow subsurface flow in the soil matrix was more dominant and in the third year most outflowing water derived from slow base flow. To better predict hydrologic catchment response we propose to apply a dimensionless number to determine the catchment response mode for every time step before selecting the appropriate response control.

Inland freshwater salinity is rising worldwide and threatens the quality of our water resources, a phenomenon called the freshwater salinization syndrome (FSS). Simultaneously, the practice of indirect potable reuse (IPR) that augments critical water supplies with treated wastewater to enhance water security presents complexities in water quality management. This dissertation explores the complex interplay between FSS and IPR in the Occoquan Reservoir, an important drinking-water source in the Mid-Atlantic United States, within its diverse environmental, social and political contexts. Using extensive data collected over 25 years, this research quantifies contributions of multiple salinity sources to the rising concentration of sodium (a major ion associated with the FSS) in the reservoir and the finished drinking water. These sources encompass two rapidly urbanizing watersheds, a sophisticated water reclamation facility and the drinking water treatment utility. The novel application of unsteady transit time theory reveals that stream salinization can be linked to watershed salt sources using stream water age as a master variable and provides a real-time prediction model for sodium concentration in the reservoir. These results identify substantial opportunities to mitigate sodium pollution and help set the stage for stakeholder-driven bottom-up management by improving the predictability of system dynamics, enhancing knowledge of this social-ecological system and supporting the development of collective action rules. / Doctor of Philosophy / The global rise in freshwater salinity, termed as the freshwater salinization syndrome (FSS), poses a significant threat to water quality in our freshwater resources. The practice of indirect potable reuse (IPR), which involves reusing treated wastewater to supplement and secure our water supplies presents significant challenges in managing water quality. This dissertation delves into the intricate relationship between FSS and IPR, focusing on the Occoquan Reservoir-a vital drinking water source in the Mid-Atlantic United States-within its multifaceted environmental, social, and political contexts. This study uncovers the contributions of various sources of salinity to rising sodium ion concentrations (a key FSS-associated ion) in the reservoir and in finished drinking water. Sodium ions are contributed by road salts, chemicals used in water and wastewater treatment, commercial and industrial discharges, household products (e.g., laundry detergents) and human excretion. An innovative approach of examining the age of water in the stream and in the reservoir outflow enables us to trace origins of salinity within the watershed and predict the concentration of sodium ions in the reservoir, respectively. These findings reveal promising avenues for effectively addressing sodium pollution at this site. Furthermore, this research underscores the significance of convergence research, bringing diverse stakeholders together to develop collaborative strategies to manage freshwater salinization using a bottom-up approach.

La contamination des aquifères de proche subsurface par les intrants d'origine agricole (nitrates) est un problème mondial.L'utilisation excessive d'engrais depuis plusieurs décennies a impacté la qualité des masses d'eau souterraines et soulève des enjeux pour la santé humaine comme pour celle des écosystèmes. Les nitrates dans les aquifères peuvent être réduits en diazote gazeux par l'activité microbienne hétérotrophique (la biomasse microbienne obtenant l'énergie nécessaire à ce processus via le carbone organique issu de la surface) et/ou par l'activité autotrophique (la biomasse microbienne obtenant cette fois ci son énergie depuis une source proche, lithologique). Les taux de dénitrification sont très variables spatialement, et sont régulés par l'interaction entre la structure des flux d'eau souterrains avec l'activité biogéochimique. Localiser l'activité biogéochimique dans les aquifères est difficilement réalisable à l'échelle des bassins versants, mais paraît crucial pour la gestion des masses d'eau souterraines. Bien que les processus de l'activité microbienne ne puissent pas être entièrement résolus à l'échelle locale, ce manuscrit de thèse propose une caractérisation des taux de dénitrification à l'échelle du bassin versant, basée sur l'analyse de données et sur une approche de modélisation intégrée. Cette thèse propose d'utiliser de manière extensive des traceurs conservatifs et réactifs associés aux flux d'eau souterraine et des modèles de transport afin d'identifier les contrôles géologiques et biogéochimiques sur les capacités de dénitrification dans les aquifères. Cette méthodologie a été appliquée à un aquifère libre cristallin de 76 km² situé en Bretagne. A partir des concentrations en CFC-12, O2, NO3- et N2 dissous mesurées dans 16 puits, il a été possible de reconstituer les chroniques d'apports de nitrate dans la zone saturée et de définir les variations spatio-temporelles de la dénitrification. Il est prouvé ici que la dénitrification est en premier lieu contrôlée par la position des donneurs d'électron. Ce travail propose un cadre d'interprétation général sur la base de l'utilisation combinée et complémentaire des traceurs et sur la modélisation semi-explicite pour estimer à l'échelle régionale les capacités de dénitrification et les stocks de nitrates dans les aquifères. / Unconfined shallow aquifers in agricultural areas are contaminated by nitrates worldwide. Excessive fertilization over the last decades has affected groundwater quality as well as human and ecosystem wellbeing. Nitrate in groundwater can be microbially reduced to dinitrogen gas by heterotrophic (microbes obtaining their energy from surface-derived organic carbon) and autotrophic (microbes obtaining their energy from a lithological source) processes. However, denitrification rates are highly spatially variable, following involved interactions between groundwater flow structures and biogeochemical activity. The location of biogeochemical activity in the aquifer is difficult to access at the catchment scale, but of vast importance to gain predictive capabilities for groundwater management. Even though microbial processes cannot be resolved at the local scale, this dissertation proposes a catchment scale characterization of denitrification rates based on an integrated model- and data-driven approach. The dissertation proposes an extensive use of conservative and reactive tracers combined with groundwater flow and transport models to identify the geological and biogeochemical controls on aquifer denitrification capacities. The methodology is applied to a crystalline unconfined aquifer of 76 km2 size in Brittany, France. Based on CFC-12, O2, NO3-, and dissolved N2 concentrations measured in 16 wells, it is possible to reconstruct historical nitrate inputs to the saturated zone and to define spatiotemporal denitrification activity. It is shown that denitrification is primarily controlled by the location of electron donors. The dissertation proposes a general interpretation framework based on tracer information combined with complementary semi-explicit lumped parameter models to assess regional denitrification capacities and nitrate legacy.