Solfataric alteration at the South Sulfur Bank of the former Kilauea caldera produced opal, Mg- and Fe-rich smectites, gypsum, and jarosite through silica replacement of pyroclastic Keanakako’i ash and leaching of basaltic lavas. This site on the island of Hawaii serves as an analog for formation of several minerals found in altered deposits on Mars. Two distinct alteration environments were characterized in this study including a light-toned, high-silica, friable outcrop adjacent to the vents, and a bedded outcrop containing alternating orange/tan layers composed of smectite, gypsum, jarosite, hydrated silica, and poorly crystalline ferric oxide phases. This banded unit likely represents deposition of pyroclastic material with variations in chemistry over time that was subsequently altered via moderate hydrothermal and pedogenic processes and leaching of basaltic caprock to enhance the Si, Al, Mg, Fe, and Ca in the altered layers. In the light-toned, friable materials closest to the vents along the base of the outcrop glassy fragments were extensively altered to opal-A plus anatase.

Lab measurements of samples returned from the field were conducted to replicate recent instruments at Mars and provide further characterization of the samples. These include elemental analyses, sample texture, XRD, SEM, VNIR/mid-IR reflectance spectroscopy, TIR emittance spectroscopy, and Mössbauer spectroscopy. Variations in the chemistry and mineralogy of these samples are consistent with alteration through hydrothermal processes as well as brines that may have formed through rain interacting with sulfuric fumes. Silica is present in all altered samples and the friable pyroclastic ash material with the strongest alteration contains up to 80 wt.% SiO2.

Sulfate mineralization occurred at the South Sulfur Bank through fumarolic action from vents and likely included solfataric alteration from sulfuric gases and steam, as well as oxidation of sulfides in the basaltic caprock. Gypsum and jarosite are typically present in different layers of the altered wall, likely because they require different cations and pH regimes. The presence of both jarosite and gypsum in some samples implies high sulfate concentrations and the availability of both Ca2+ and Fe3+ cations in a brine percolating through the altered ash. Pedogenic conditions are more consistent with the observed Mg-smectites and gypsum in the tan layers, while jarosite and nontronite likely formed under more acidic conditions in the darker orange layers. Assemblages of smectite, Ca-sulfates, and jarosite similar to the banded orange/tan unit in our study are observed on Mars at Gale crater, Noctis Labyrinthus, and Mawrth Vallis, while high-silica outcrops have been identified in parts of Gusev crater, Gale crater, and Nili Patera on Mars.

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