Abstract
Advanced argillic minerals, as defined, include alunite and anhydrite, aluminosilicates (kaolinite, halloysite, dickite, pyrophyllite, andalusite, zunyite, and topaz), and diaspore. One or more of these minerals form in five distinctly different geologic environments of hydrolytic alteration, with pH 4–5 to <1, most at depths <500 m. (1) Where an intrusion-related hydrothermal system, typical of that associated with porphyry Cu ± Au deposits, evolves to white-mica stability, continued ascent and cooling of the white-mica–stable liquid results in pyrophyllite (± diaspore) becoming stable near the base of the lithocap. (2) A well-understood hypogene environment of formation is vapor condensation near volcanic vents, where magmatic SO2 and HCl condense into local groundwater to produce H2SO4 and HCl-rich solutions with a pH of 1–1.5. Close to isochemical dissolution of the host rock occurs because of the high solubility of Al and Fe hydroxides at pH <2, except for the SiO2 component, which remains as a siliceous residue because of the relatively low solubility of SiO2. This residual quartz, commonly with a vuggy texture, is largely barren of metals because of the low metal content in high-temperature but low-pressure volcanic vapor. Rock dissolution causes the pH of the acidic solution to increase, such that alunite and kaolinite (or dickite or pyrophyllite at higher temperatures) become stable, forming a halo to the residual quartz. This initially barren residual quartz, which forms a lithocap horizon where permeable lithologic units are intersected by the feeder structure, may become mineralized if a subsequent white-mica–stable liquid ascends to this level and precipitates copper and gold. (3) Boiling of a hydrothermal liquid generates vapor with CO2 and H2S. Where the vapor condenses above the water table, atmospheric O2 in the vadose (unsaturated) zone causes oxidation of H2S to sulfuric acid, forming a steam-heated acid-sulfate solution with pH of 2–3. In this environment, kaolinite and alunite form in horizons above the water table at <100°C. Silica derived within the vadose zone will precipitate as amorphous silica at the water table, as the condensate follows the hydraulic gradient, causing opal replacement above and at the aquifer. (4) By contrast, where condensation of this vapor occurs below the water table, the CO2 in solution forms carbonic acid (H2CO3), leading to a pH of 4–5. This marginal carapace of condensate, with temperatures up to 150°–170°C, commonly acts as a diluent of the ascending parental NaCl liquid. This steam-heated liquid forms intermediate argillic alteration of clays, kaolinite, and Fe-Mn carbonates; this kaolinite, which can be present at depths of several hundreds of meters, can potentially be mistaken as having been caused by a steam-heated acid-sulfate or supergene overprint. (5) The final setting is supergene, caused by posthydrothermal weathering and oxidation of mainly pyrite, locally creating pH <1 liquid because of high concentrations of H2SO4 within the vadose zone and forming kaolinite, alunite, and Fe oxyhydroxides.
This genetic framework of formation environments of advanced (and intermediate) argillic alteration provides the basis to interpret alteration mineralogy, in combination with alteration textures and morphology plus zonation, including the overprint of one alteration style on another. This framework can be used to help focus exploration for and assessment of hydrothermal ore deposits, including epithermal, porphyry, and volcanic-hosted massive sulfide.
Waste Storage in the Vadose Zone Affected by Water Vapor Condensation and Leaching