The Yellowstone Plateau Volcanic Field (YPVF) contains >10,000 thermal features including hot springs, pools, geysers, mud pots, and fumaroles with diverse chemical compositions. Arsenic (As) concentrations in YPVF thermal waters typically range from 0.005 to 4 mg/L, but an As concentration of 17 mg/L has been reported. Arsenic data from thermal springs, outflow drainages, rivers, and from volcanic rocks and silica sinter were used to identify the sources, characterize geochemical and microbial processes affecting As, and quantify As fluvial transport. Arsenic in YPVF thermal waters is mainly derived from high temperature leaching of rhyolites. Arsenic concentrations in thermal waters primarily depend on water type, which is controlled by boiling, evaporation, mixing, and mineral precipitation and dissolution. Springs with low As concentrations include acid-SO₄ (0.1 ± 0.1 mg/L), NH₄-SO₄ rich (0.003 ± 0.007 mg/L), and dilute thermal waters (0.1 ± 0.1 mg/L); travertine-forming waters have moderate As concentrations (0.4 ± 0.2 mg/L); and neutral- Cl waters (1.2 ± 0.8 mg/L) common in the western portion of the Yellowstone Caldera and Cl-rich waters (1.9 ± 1.2 mg/L) primarily from Basins near the Caldera boundary have elevated As concentrations. Reduced As species (arsenite and thiolated-As species) are most prevalent near the orifice of hot springs, and then As rapidly oxidizes to arsenate along drainages. Previously published cultivation-based studies and metagenomic data from microbial communities inhabiting a variety of hot springs indicate a widespread distribution of arsenite oxidation and arsenate reduction capabilities among the hot springs. Widespread use and transformation of As by thermophilic microorganisms promotes more soluble and toxic forms. Most of the water discharged from thermal springs eventually ends up in a nearby river where As remains soluble and exhibits little attenuation during downstream transport. Since 2010, 183 ± 10 metric tons/year of As were transported from Yellowstone National Park (YNP) via rivers. The discharge from YPVF thermal features impairs river water quality whereby As concentrations exceed 10 μg/L for many rivers reaches within and downstream from YNP.