Transport processes and pathways through many hydrodynamic systems vary over time, often driven by variations in total water storage. This paper develops a very general approach to modeling unsteady transport through an arbitrary control volume (such as a watershed) that accounts for temporal variability in the underlying transport dynamics. Controls on the selection of discharge from stored water are encapsulated in probability distributions X Q ðS T ; tÞ of age-ranked storage S T (the volume of water in storage ranked from youngest to oldest). This framework is applied to a long-term record of rainfall and streamflow chloride in a small, humid watershed at Plynlimon, UK. While a time-invariant gamma distribution for X Q produced a good fit to data, the fit was significantly improved when the distribution was allowed to vary with catchment storage. However, the variation was inverse to that of a ''well-mixed'' system where storage has a pure dilution effect. Discharge at high storage was predicted to contain a larger fraction of recent event water than at low storage. The effective volume of storage involved in transport was 3411 mm at mean catchment wetness, but declined by 71 mm per 1 mm of additional catchment storage, while the fraction of event water in discharge increased by 1.4%. This ''inverse storage effect'' is sufficient to reproduce the observed long-memory 1=f fractal spectral structure of stream chloride. Metrics quantifying the strength and direction of storage effects are proposed as useful signatures, and point toward a unified framework for observing and modeling coupled watershed flow and transport.

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[1] Human activities exert global-scale impacts on our environment with significant implications for freshwater-driven services and hazards for humans and nature. Our approach to the science of hydrology needs to significantly change so that we can understand and predict these implications. Such an adjustment is a necessary prerequisite for the development of sustainable water resource management strategies and to achieve long-term water security for people and the environment. Hydrology requires a paradigm shift in which predictions of system behavior that are beyond the range of previously observed variability or that result from significant alterations of physical (structural) system characteristics become the new norm. To achieve this shift, hydrologists must become both synthesists, observing and analyzing the system as a holistic entity, and analysts, understanding the functioning of individual system components, while operating firmly within a well-designed hypothesis testing framework. Cross-disciplinary integration must become a primary characteristic of hydrologic research, catalyzing new research and nurturing new educational models. The test of our quantitative understanding across atmosphere, hydrosphere, lithosphere, biosphere, and anthroposphere will necessarily lie in new approaches to benchmark our ability to predict the regional hydrologic and connected implications of environmental change. To address these challenges and to serve as a catalyst to bring about the necessary changes to hydrologic science, we call for a long-term initiative to address the regional implications of environmental change.Citation: Wagener, T

Bedrock fracture systems facilitate weathering, allowing fresh mineral surfaces to interact with corrosive waters and biota from Earth's surface, while simultaneously promoting drainage of chemically equilibrated fluids. We show that topographic perturbations to regional stress fields explain bedrock fracture distributions, as revealed by seismic velocity and electrical resistivity surveys from three landscapes. The base of the fracture-rich zone mirrors surface topography where the ratio of horizontal compressive tectonic stresses to near-surface gravitational stresses is relatively large, and it parallels the surface topography where the ratio is relatively small. Three-dimensional stress calculations predict these results, suggesting that tectonic stresses interact with topography to influence bedrock disaggregation, groundwater flow, chemical weathering, and the depth of the "critical zone" in which many biogeochemical processes occur.

We discuss a recent theoretical approach combining catchment-scale flow and transport processes into a unified framework. The approach is designed to characterize the hydrochemistry of hydrologic systems and to meet the challenges posed by empirical evidence. StorAge Selection functions (SAS) are defined to represent the way catchment storage supplies the outflows with water of different ages, thus regulating the chemical composition of out-fluxes. Biogeochemical processes are also reflected in the evolving residence time distribution and thus in age-selection. Here we make the case for the routine use of SAS functions and look forward to areas where further research is needed.