Dramatic changes in the brightness and shape of Jupiter's extended sodium nebula are found to be correlated with the infrared emission brightness of Io. Previous imaging and modeling studies have shown that varying appearances of the nebula correspond to changes in the rate and the type of loss mechanism for atmospheric escape from Io. Similarly, previous IR observational studies have assumed that enhancements in infrared emissions from Io correspond to increased levels of volcanic (lava flow) activity. In linking these processes observationally and statistically, we conclude that silicate volcanism on Io controls both the rate and the means by which sodium escapes from Io's atmosphere. During active periods, molecules containing sodium become an important transient in Io's upper atmosphere, and subsequent photochemistry and molecular-ion driven dynamics enhance the high speed sodium population, leading to the brightest nebulas observed. This is not the case during volcanically quiet times when omni-present atmospheric sputtering ejects sodium to form a modest, base-level nebula. Sodium's role as a "trace gas" of the more abundant species of sulfur (S) and oxygen (O) is less certain during volcanic episodes. While we suggest that volcanism must also affect the escape rates of S and O, and consequently their extended neutral clouds, the different roles played by lava and plume sources for non-sodium species are far too uncertain to make definitive comparisons at this time.