As well as gases that regulate climate over geological time, volcanoes emit prodigious quantities of metals into the atmosphere, where they have key roles as catalysts, pollutants and nutrients. Here we compare measurements of arc basaltic volcano metal emissions with those from hotspot settings. As well as emitting higher fluxes of metals (similar to those building ore deposits), these arc emissions possess a distinct compositional fingerprint, particularly rich in tungsten, arsenic, thallium, antimony and lead when compared with those from hotspots. We propose that volcanic metal emissions are controlled by magmatic water content and redox: hydrous arc magmas that do not undergo sulfide saturation yield metal-rich, saline aqueous fluid; shallow degassing and resorption of late-stage sulfides feeds volcanic gases in Hawai’i and Iceland. Although global arc magma chemistries vary considerably, our findings suggest that volcanic emissions in arcs have a distinct fingerprint when compared with other settings. A shift in global volcanic metal emissions may have occurred in Earth’s past as more oxidized, water-rich magmas became prevalent, influencing the surface environment.