Deuterium and oxygen-18 enrichment in river water during its transit across dryland region is found to occur systematically along evaporation lines with slopes of close to 4 in (2)H-(18)O space, largely consistent with trends predicted by the Craig-Gordon model for an open-water dominated evaporating system. This, in combination with reach balance assessments and derived runoff ratios, strongly suggests that the enrichment signal and its variability in the Barwon-Darling river, Southeastern Australia is acquired during the process of evaporation from the river channel itself, as enhanced by the presence of abundant weirs, dams and other storages, rather than reflecting inherited enrichment signals from soil water evaporation in the watershed. Using a steady-state isotope mass balance analysis based on monthly (18)O and (2)H, we use the isotopic evolution of river water to re-construct a perspective of net exchange between the river and its contributing area along eight reaches of the river during a drought period from July 2002 to December 2003, including the duration of a minor flow event. The resulting scenario, which uses a combination of climatological averages and available real-time meteorological data, should be viewed as a preliminary test of the application rather than as a definitive inventory of reach water balance. As expected for a flood-driven dryland system, considerable temporal variability in exchange is predicted. While requiring additional real-time isotopic data for operational use, the method demonstrates potential as a non-invasive tool for detecting and quantifying water diversions, one that can be easily incorporated within existing water quality monitoring activities.