Raman spectroscopy of high salinity brines and ices

1Daniel P.Mason,1Megan E.Elwood Madden
Icarus (in Press) Link to Article [https://doi.org/10.1016/j.icarus.2021.114759]
1School of Geosciences, University of Oklahoma, 100 E Boyd St., Norman, OK, USA
Copyright Elsevier

Raman spectroscopy is an ideal tool to analyze the geochemistry and mineralogy of heterogenous mixtures of solids, liquid, and gases in situ, while maintaining planetary protection protocols. Here we characterize saturated CaCl2, MgCl2, MgSO4, Na2SO4, NaCl, and NaClO4 brines, as well as ultrapure water, and mixed MgSO4-NaCl, MgSO4-NaClO4, Na2SO4-NaCl, Na2SO4-NaClO4, and NaCl-NaClO4 brines from 200 K to 295 K to determine how changes in temperature affect spectral signatures of planetary analogue brines. The resulting reference dataset can be used to interpret spectra from future samples analyzed in situ on planetary bodies. Sulfate and perchlorate brines produced clear, distinct peaks associated with each polyatomic anion. While chloride brines did not produce anion peaks, subtle changes were observed in the OH-stretching region, suggesting changes to the molecular water vibration states due to complexation. Solid-liquid phase transitions were clearly observed in each of the solutions using both 785 nm (red) and 532 nm (green) excitation lasers, particularly in the OH-stretching region between 3000 and 4000 cm−1 with the 532 nm laser. Differences observed in the spectra of frozen sulfate brines suggest that cooling rates may influence the hydration state and/or crystallinity of the solid magnesium and sodium- sulfate salts. These experiments and the resulting spectral library will allow future researchers to use Raman spectroscopy to look for in situ melting, freezing, evaporation, and deliquescence as well as identify the composition of high salinity brines and their frozen products in a range of planetary environments, including permafrost and recurring slope lineae on Mars, potential ice and salt-rich regolith on asteroids such as Ceres, and ice shells and possible seeps or geysers on icy moons and other bodies.

Origin of the non-carbonaceous–carbonaceous meteorite dichotomy

1Josefine A.M.Nanne,2Francis Nimmo,3Jeffrey N.Cuzzi,1Thorsten Kleine
Earth and Planetary Science Letters 511, 44-54 Link to Article [https://doi.org/10.1016/j.epsl.2019.01.027]
1Institut für Planetologie, University of Münster, Wilhelm-Klemm-Straße 10, 48149 Münster, Germany
2Department of Earth and Planetary Sciences, University of California Santa Cruz, Santa Cruz, CA 95064, USA
3Space Science Division, Ames Research Center, Moffett Field, CA 94035, USA
Copyright Elsevier

The isotopic composition of meteorites reveals a fundamental dichotomy between non-carbonaceous (NC) and carbonaceous (CC) meteorites. However, the origin of this dichotomy—whether it results from processes within the solar protoplanetary disk or is an inherited heterogeneity from the solar system’s parental molecular cloud—is not known. To evaluate the origin of the NC–CC dichotomy, we report Ni isotopic data for a comprehensive set of iron meteorites, with a special focus on groups that have not been analyzed before and belong to the CC group. The new Ni isotopic data demonstrate that the NC–CC dichotomy extends to Ni isotopes, and that CC meteorites are characterized by a ubiquitous 58Ni excess over NC meteorites. These data combined with prior observations reveal that, in general, the CC reservoir is characterized by an excess in nuclides produced in neutron-rich stellar environments, such as 50Ti, 54Cr, 58Ni, and r-process Mo isotopes. Because the NC–CC dichotomy exists for refractory (Ti, Mo) and non-refractory (Ni, Cr) elements, and is only evident for nuclides produced in specific, neutron-rich stellar environments, it neither reflects thermal processing of presolar carriers in the disk, nor the heterogeneous distribution of isotopically anomalous Ca–Al-rich inclusions (CAI). Instead, the NC–CC dichotomy reflects the distinct isotopic composition of later infalling material from the solar system’s parental molecular cloud, which affected the inner and outer regions of the disk differently. Simple models of the infall process by themselves can support either infall of increasingly NC-like material onto an initially CC-like disk, or infall of increasingly CC-like material in the absence of disk evolution by spreading. However, provided that CAIs formed close to the Sun, followed by rapid outward transport, their isotopic composition likely reflects that of the earliest infalling material, implying that the composition of the inner disk (i.e., the NC reservoir) is dominated by later infalling material, whereas the outer disk (i.e., the CC reservoir) preserved a compositional signature of the earliest disk. The isotopic difference between the inner and outer disk was likely maintained through the rapid formation of Jupiter, which prevented complete homogenization between material from inside (NC reservoir) and outside (CC reservoir) its orbit.