Since the 1970s, temporal variations of hydrothermal discharge and thermal output from the numerous hydrothermal features in the Yellowstone Plateau Volcanic Field (YPVF) have been studied by measuring the chloride flux in the major rivers. In this study, the sources, fate, and flux of solutes in the Fall River and its major tributaries, in southwest Yellowstone National Park, were determined. The considerable precipitation in southwest YPVF and high groundwater flow through Quaternary rhyolites results in river solute fluxes that originate from shallow non-thermal groundwater and deep-thermal water. Specific conductance serves as a surrogate measure for thirteen riverine solute concentrations. Combining continuous 15-minute specific conductance and discharge data, the annual chloride, arsenic, fluoride, and silica fluxes from the Fall River were determined to be 11%, 5%, 25%, and 19% of the total flux exiting YPVF. Approximately 11% of the Fall River chloride flux is from non-thermal waters, which is larger than the previous estimate of 4 to 6%. Furthermore, a large proportion of fluoride and silica in the Fall River are derived from water-rock interaction in the shallow non-thermal groundwater system and the non-thermal weathering rate (30 ± 2 t/yr·km²) is higher than other rivers draining the Yellowstone caldera. Consequently, 73 ± 3% of the annual total dissolved solid flux in the Fall River is from thermal sources. Synoptic sampling of river water and discharge measurements was performed during low-flow conditions that allowed for the determination of solute sources and their downstream fate. It was determined that chloride, sodium, arsenic, rubidium, lithium, and boron are primarily (>89%) associated with thermal waters and the Bechler River is the primary source of most hydrothermal solutes in the Fall River, but the major source of arsenic is Boundary Creek. Using the chloride inventory method, the thermal water discharge from several thermal areas was also determined.