Subvolcanic environments in supra-subduction zones are renowned for hosting epithermal deposits that often contain electrum and native gold, including bonanza examples. This study examined mineral assemblages and processes occurring in shallow-crust volcanic settings using recent eruption (2012–2013) of the basaltic Tolbachik volcano in the Kamchatka arc. The Tolbachik eruptive system is characterized by an extensive system of lava tubes. After cessation of magma input, the tubes maintained the flow of hot oxidized gases that episodically interacted with the lava surfaces and sulphate-chloride precipitates from volcanic gases on these surfaces. The gas-rock interaction had strong pyrometamorphic effects that resulted in the formation of molten salt, oxidized (tenorite, hematite, Cu-rich magnesioferrite) and skarn-like silicate mineral assemblages. By analogy with experimental studies, we propose that a combination of these processes was responsible for extraction of metals from the basaltic wall rocks and deposition of Cu-, Fe- and Cu-Fe-oxides and native gold.