Fumarolic Activity, Acid-Sulfate Alteration, and High Sulfidation Epithermal Precious Metal Mineralization in the Crater of Kawah Ijen Volcano, Java, Indonesia

Abstract Opinion is divided over whether the fluid responsible for the formation of high sulfidation epithermal deposits is a vapor or a liquid, and whether it is entirely volcanic or of mixed volcanic-meteoric origin. Observations made at Kawah Ijen, an active stratovolcano (mainly andesitic in composition) located in the Ijen Caldera Complex in Java, Indonesia, are used to address these issues. The Kawah Ijen crater is approximately 1 km in diameter, and hosts one of the world’s largest hyperacidic lakes (pH ~0). On the lake edge is a small and actively degassing solfatara field, which is surrounded by a much larger area of acid-sulfate alteration. This area was exposed during a phreatomagmatic eruption in 1817, which excavated the crater to a depth of 250 m, and comprises zones of residual silica, alunite-pyrite, and dickite/kaolinite. Based on the fractionation of 34S and 32S between alunite and pyrite, the acid-sulfate alteration occurred at a temperature between 200° and 300°C. High sulfidation epithermal mineralization accompanied the alteration in the form of massive and vein-hosted pyrite that contains up to 192 ppb Au, 9.2 ppm Ag, 6,800 ppm Cu, and 3,430 ppm As; these elements are invisible at the highest resolution of scanning electron microscopy, and thus either occur in the form of nanoparticles or are in solid solution in the pyrite. Condensed fumarolic gases released from the solfatara field and sampled at temperatures between 330° and 495°C contain up to 3 ppm Cu and 3.8 ppm As; the concentrations of Au and Ag are below detection. The pH of the condensed gas (water vapor) is ~−0.5. The above observations support a model in which highly acidic gases condensed ~250 m beneath the floor of the crater. Depending on the fluid/rock ratio, the condensed liquids altered the andesitic host rocks by leaching them to leave behind a residue of “vuggy silica” (high fluid/rock ratio), by replacing the primary minerals with alunite and pyrite (intermediate fluid/rock ratio), or by converting them to dickite/kaolinite (lower fluid/rock ratio). Gold-, silver-, and copper-bearing phases were undersaturated in the condensed liquids. However, they were able to concentrate by adsorbing on the surfaces of the growing pyrite crystals, which developed p-type conductive properties as a result of the uptake of arsenic. The metals were incorporated in the pyrite either by their electrochemical reduction to form native metal nanoparticles or through coupled substitutions with arsenic for iron and sulfur. The results of this study provide compelling evidence that high sulfidation epithermal precious metal mineralization can form directly from condensed magmatic gases.