¹Yohei Igami,^2,3Akira Tsuchiyama,⁴Tomoya Yamazaki,⁵Megumi Matsumoto,⁴Yuki Kimura
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2020.10.023]
¹Division of Earth and Planetary Sciences, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan
²Research Organization of Science and Technology, Ritsumeikan University, Kusatsu 525-8577, Japan
³Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China
⁴Institute of Low Temperature Science, Hokkaido University, Sapporo 060-0819, Japan
⁵Department of Earth and Planetary Materials Science, Tohoku University, Sendai 980-8578, Japan
Copyright Elsevier

Amorphous silicates, abundant in primitive carbonaceous chondrites, are among the most primitive materials from the early Solar System. They show evidence of some aqueous alteration in the meteorite parent bodies, but it is not clear how this highly reactive material changed at an early stage after contact with water. Herein, we report in-situ experiments on the aqueous alteration of amorphous silicate nanoparticles (typically 70 nm in diameter); we used two different compositions that are similar to forsterite (MgO/SiO2 = 2.02) and enstatite (MgO/SiO2 = 1.15) in the simple MgO–SiO2 system to understand basic reaction principles at the onset of the aqueous alteration. The experiments were performed in pure water at room temperature using X-ray diffraction (XRD), transmission electron microscopy (TEM), and pH measurements. The in-situ TEM images of the nanoparticles—in particular those with the forsterite composition—gradually became difficult to recognize in water. The pH value of the water also increased with time, suggesting that preferential Mg2+ dissolution occurred from the amorphous silicates right after mixing with water. The in-situ XRD patterns showed that magnesium silicate hydrate (M-S-H), which is a poorly crystalline phase like a phyllosilicate, newly appeared. The M-S-H seems to have been formed via a dissolution–precipitation process. Its formation rate from amorphous silicates was considerably higher than from crystalline silicates, because amorphous silicates are highly metastable and have high solubility in water. M-S-H formation from the forsterite composition, which has a highly unstable amorphous structure, is ten times faster than from the enstatite composition. The M-S-Hs show string-like or tiny fragmental textures in the final dried products that are very similar to those observed in the matrices of some primitive carbonaceous chondrites. M-S-H would have been the initial product formed in the aqueous alteration of amorphous silicates in the meteorites; thus, it is an important tracer of early aqueous activity at low temperatures in the early Solar System. By comparing the in-situ observations with those obtained after drying the experimental samples, we found two types of M-S-Hs: epigenetic M-S-Hs—which have a slightly Si-rich composition—formed during drying, and syngenetic M-S-Hs formed by in-situ alteration. Carbonaceous chondrites may also contain these two types of hydrous silicates, and this should be investigated to understand the conditions for aqueous alteration in the early Solar System in more detail. The present study clearly showed the importance of Mg/Si ratio in the precursor materials, although the actual chondrites are in more complicated multi-component system. Future experiments based on the present results can extend the investigation to the system containing Fe, S, and other components as in carbonaceous chondrites.

¹Marine Paquet,¹James M.D.Day,²Arya Udry,¹Ruan Hattingh,¹Ben Kumler,²Rachel R.Rahib,³Kimberly T.Tait,⁴Clive R.Neal
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2020.10.024]
¹Scripps Institution of Oceanography, University of California San Diego, La Jolla, CA 92093-0244, USA
²Department of Geoscience, University of Nevada, Las Vegas, 4505 S. Maryland Parkway, Las Vegas, NV 89154, USA
³Department of Natural History, Royal Ontario Museum, 100 Queens Park, Toronto, ON M5S 2C6, Canada
⁴Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, IN 46556, USA
Copyright Elsevier

Shergottite meteorites are ultramafic to mafic igneous rocks derived from partial melting of distinct regions of the martian mantle. As such, they trace magmatic processes, including fractional crystallization and mixing processes in Mars. New chalcophile (Cu, Se, Zn, Pb), siderophile (Ni, Co, W), and highly siderophile element (HSE: Au, Re, Pd, Rh, Pt, Ru, Ir, Os) abundance data are reported for sulfide assemblages in a suite of thirteen incompatible trace element depleted, intermediate and enriched shergottites, along with new whole-rock HSE abundance and 187Os/188Os data for seven shergottites. Sulfide grains in depleted and intermediate shergottites typically have the highest absolute abundances of the HSE, with broadly flat CI-chondrite normalized patterns. Enriched shergottite sulfide grains typically have highly variable Au, elevated Pd and Rh and are relatively depleted in Zn, Ir and Os. The new HSE whole-rock data for enriched (Northwest Africa [NWA] 7397, NWA 7755, NWA 11043), and intermediate shergottites (NWA 10961, NWA 11065, NWA 12241, and NWA 12536) are generally consistent with existing 187Os/188Os and HSE abundance data for these geochemical groupings. Enriched shergottites with > 1 ppb Os have measured 187Os/188Os ranging between 0.1296 and 0.1471, with variable Pd and Pt contents. Intermediate shergottites with > 1 ppb Os have chondrite-relative proportions of the HSE at ∼ 0.01 to 0.001 × CI chondrites and 187Os/188Os from 0.1284 and 0.1295. Sulfides are the major host of the HSE, and they control the behavior of the HSE during petrogenetic processes in shergottite magmas, enabling the determination of HSE compatibility for martian magmatism in the order: Os > Ir ≥ Ru ≥≥ Rh ≥ Pd ≥ Re ≥ Pt ≥ Au. Fractionation models of removal of an olivine-dominated cumulate recreate HSE patterns for the whole-rock shergottites. Enriched shergottites are best reproduced by 25 to 30% of fractionation from a degassed parent melt (250 ± 50 ppm of S), whereas depleted and intermediate shergottites can be explained by slightly lower fractionation (10 to 15%) from higher S content parent melts (350 ± 100 ppm of S). Sulfur contents in the melt ∼ 50% higher than these estimates yield earlier S-saturation during fractional crystallization, leading to an abrupt decrease of the more compatible HSE (Ru, Ir, Os), which is not observed. These results indicate that the martian mantle and partial melts from it, are probably not anomalously enriched in S, and instead are similar to slightly higher than those of the terrestrial mantle and its partial melts.