Quantification of amorphous Si, Al, and Fe in palagonitic Mars analogs by chemical extraction and X-ray spectroscopy

Abstract

Data collected by orbiters and landers have consistently shown abundant amorphous materials on Mars. Developing analytical techniques that target amorphous materials in terrestrial analogs can help determine the environmental conditions under which the amorphous assemblages on Mars were formed. However, the inherent short-range order, chemical heterogeneity, and nanoscale phase interactions create challenges in characterizing these phases. This study is aimed to overcome these challenges by combining chemical dissolution rate analysis with spectroscopy-based mass balance calculations (MBC) to characterize different pools of amorphous materials in terrestrial analogs. The differences in dissolution rates between rapidly dissolving Si, Al, and Fe amorphous materials and the slowly dissolving crystalline minerals were modeled to predict amorphous composition in five palagonitic samples from Hawaii (Mauna Kea) and four hyaloclastite tuffs from the subglacial volcanoes in southwest Iceland. These samples were selected as potential analogs because of their spectral and compositional resemblance to Mars's surface materials.The amorphous Si, Al, and Fe compositions from both sites varied based on the degree of aqueous alteration, grain size, and location. The amorphous fractions of the unconsolidated palagonitic analogs from Hawaii are composed of alteration products such as opal CT and ferrihydrite with minor amounts of unaltered basaltic glass. In contrast, the amorphous fractions of the cemented Icelandic samples were composed mainly of unaltered glass and mixed Fe(II, III) iron phases. Amorphous compositions of the loose Hawaiian and the consolidated Icelandic palagonites are comparable with the Martian modern and ancient aeolian materials respectively. The amorphous compositions in the Hawaiian sample, HWMK101, closely resemble the amorphous materials in Rocknest, a modern aeolian material from the sand shadow, and the Icelandic samples are comparable to the ancient aeolian materials from the Stimson formation. Our analysis indicates the presence of hydrated secondary alteration products such as ferrihydrite and allophane in Rocknest, and a mixture of reduced iron phases and silicate glass outlined with finer altered opaline silicates in Greenhorn. The chemical extraction analysis combined with MBC can be used to characterize amorphous phases in terrestrial analogs to better constrain the formation and characterization of the abundant amorphous materials on Mars.