US Geological Survey


Date of this Version



Published in Chemical Geology 215 (2005)


The Pierina high-sulfidation Au–Ag deposit formed 14.5 my ago in rhyolite ash flow tuffs that overlie porphyritic andesite and dacite lavas and are adjacent to a crosscutting and interfingering dacite flow dome complex. The distribution of alteration zones indicates that fluid flow in the lavas was largely confined to structures but was dispersed laterally in the tuffs because of a high primary and alteration-induced permeability. The lithologically controlled hydrodynamics created unusual fluid, temperature, and pH conditions that led to complete SO4 2‒–H2S isotopic equilibration during the formation of some magmatic-steam and steam-heated alunite, a phenomenon not previously recognized in similar deposits. Isotopic data for early magmatic hydrothermal and main-stage alunite (δ34S=8.5%◦ to 31.7%◦; δ18OSO4 =4.9%◦ to 16.5%◦; δ18OOH=2.2%◦ to 14.4%◦ ; δD=‒97%◦ to ‒39%◦), sulfides (δ34S=‒3.0%◦ to 4.3%◦), sulfur (δ34S=‒1.0%◦ to 1.1%◦), and clay minerals (δ18O=4.3%◦ to 12.5%◦; δD=‒126%◦ to ‒81%◦) are typical of high-sulfidation epithermal deposits. The data imply the following genetic elements for Pierina alteration–mineralization: (1) fluid and vapor exsolution from an I-type magma, (2) wallrock buffering and cooling of slowing rising vapors to generate a reduced (H2S/SO4≈6) highly acidic condensate that mixed with meteoric water but retained a magmatic δ34SΣS signature of ~1%◦, (3) SO2 disproportionation to HSO4and H2S between 320 and 180 °C, and (4) progressive neutralization of laterally migrating acid fluids to form a vuggy quartz→alunite– quartz±clay→intermediate argillic→propylitic alteration zoning. Magmatic-steam alunite has higher δ34S (8.5%◦ to 23.2%◦) and generally lower δ18OSO4 (1.0 to 11.5%◦), δ18OOH (‒3.4 to 5.9%◦), and δD (‒93 to ‒77%◦) values than predicted on the basis of data from similar occurrences. These data and supporting fluid-inclusion gas chemistry imply that the rate of vapor ascent for this environment was unusually slow, which provided sufficient time for the uptake of groundwater and partial to complete SO4 2‒–H2S isotopic exchange. The slow steam velocities were likely related to the dispersal of the steam column as it entered the tuffs and possibly to intermediate exsolution rates from magmatic brine. The low δD values may also partly reflect continuous degassing of the mineralizing magma. Similarly, data for

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