Hyperacidic lakes and associated solfatara in active volcanoes are the expression of magmatic gas expansion from source to surface. Here we show for the first time, that the vein system that comprises the ~ 2 Ma high-sulfidation, Lepanto copper–gold deposit in the Mankayan district (Philippines) was associated with a contemporary hyperacidic volcanic lake complex—possibly the first such lake recognized in the geological record. A 15–20‰ difference in sulfur isotopic composition between barite and sulfides and sulfosalts in the vent fumarole encrustations supports the interpretation that SO₂-rich volcanic gas vented into the base of the lake and marginal to it and ties the mineralization directly to magmatic gas expansion, fracture propagation, and mineralization that occurred through a series of decompression steps within the feeder fracture network. These data confirm that crater lake environments such as Kawah Ijen (Java, Indonesia) provide modern day analogs of the Lepanto and other high sulfidation Cu–Au depositing environments.

We also provide extensive analysis of sulfosalt–sulfide reactions during vein formation within the hyperacidic lake complex. Pyrite ±  silica deposited first at high temperature followed by enargite that preserves the vapor–solid diffusion of, for example, antimony, tin, and tellurium into the vapor from the crystallizing solid. Subsolidus, intra-crystalline diffusion continued as temperature declined. Pyrite and enargite are replaced by Fe-tennantite in the lodes which initially has low Sb/(Sb + As) atomic ratios around 13.5% close to the ideal tennantite formula, but evolves to higher ratios as crystallization proceeds. Fumarole encrustation clasts and sulfosalts in the lake sediment are more highly evolved with a larger range of trace element substitutions, including antimony. Substitution of especially Zn, Te, Ag, and Sn into tennantite records metal and semi-metal fractionation between the expanding magmatic gas and deposited sulfide sublimates provides a rare insight into the fate of metals and semi-metals in the shallower parts of fracture arrays that feed modern hyperacidic lakes.

These data support a growing understanding of the formation of high-sulfidation gold deposits as the consequence of single-phase expansion of gas from magmatic-gas reservoirs beneath the surface of active volcanoes without the intervention of a later aqueous fluid including groundwater. Aggressive sulfide–sulfosalt reactions, including pitting and the almost complete dissolution of earlier minerals, are persistent characteristics of the vein assemblages and precious metals typically occur late in pits or along brittle fractures. These characteristics support a hypothesis of mineral deposition at temperatures of the order of 600 °C in contrast to available fluid inclusion data from enargite that record temperatures following phase transitions in the sulfosalt during the retrograde devolution of the deposit in the presence of groundwater.