Acoustic monitoring of laser-induced phase transitions in minerals: implication for Mars exploration with SuperCam.

The SuperCam instrument suite onboard the Mars 2020 Perseverance rover uses the laser-induced breakdown spectroscopy (LIBS) technique to determine the elemental composition of rocks and soils of the Mars surface. It is associated with a microphone to retrieve the physical properties of the ablated targets when listening to the laser-induced acoustic signal. In this study, we report the monitoring of laser-induced mineral phase transitions in acoustic data. Sound data recorded during the laser ablation of hematite, goethite and diamond showed a sharp increase of the acoustic signal amplitude over the first laser shots. Analyses of the laser-induced craters with Raman spectroscopy and scanning electron microscopy indicate that both hematite and goethite have been transformed into magnetite and that diamond has been transformed into amorphous-like carbon over the first laser shots. It is shown that these transitions are the root cause of the increase in acoustic signal, likely due to a change in target's physical properties as the material is transformed. These results give insights into the influence of the target's optical and thermal properties over the acoustic signal. But most importantly, in the context of the Mars surface exploration with SuperCam, as this behavior occurs only for specific phases, it demonstrates that the microphone data may help discriminating mineral phases whereas LIBS data only have limited capabilities.

Arsenic Incorporation in Pyrite at Ambient Temperature at Both Tetrahedral S-I and Octahedral FeII Sites: Evidence from EXAFS-DFT Analysis.

Pyrite is a ubiquitous mineral in reducing environments and is well-known to incorporate trace elements such as Co, Ni, Se, Au, and commonly As. Indeed, As-bearing pyrite is observed in a wide variety of sedimentary environments, making it a major sink for this toxic metalloid. Based on the observation of natural hydrothermal pyrites, As-I is usually assigned to the occupation of tetrahedral S-I sites, with the same oxidation state as in arsenopyrite (FeAsS), although rare occurrences of AsIII and AsII have been reported. However, the modes of As incorporation into pyrite during its crystallization under low-temperature diagenetic conditions have not yet been elucidated because arsenic acts as an inhibitor for pyrite nucleation at ambient temperature. Here, we provide evidence from X-ray absorption spectroscopy for AsII,III incorporation into pyrite at octahedral FeII sites and for As-I at tetrahedral S-I sites during crystallization at ambient temperature. Extended X-ray absorption fine structure (EXAFS) spectra of these As-bearing pyrites are explained by local structure models obtained using density functional theory (DFT), assuming incorporation of As at the Fe and S sites, as well as local clustering of arsenic. Such observations of As-I incorporation at ambient temperature can aid in the understanding of the early formation of authigenic arsenian pyrite in subsurface sediments. Moreover, evidence for substitution of AsII,III for Fe in our synthetic samples raises questions about both the possible occurrence and the geochemical reactivity of such As-bearing pyrites in low-temperature subsurface environments.

Structure of Pb-rich chabournéite from Jas Roux, France.

The crystal structure of a specimen of `Pb-rich' chabournéite from Jas Roux, Hautes-Alpes, France, with the chemical formula obtained by electron microprobe analysis of Ag(0.04 (1))Tl(2.15 (2))Pb(0.64 (1))Sb(5.12 (1))As(5.05 (1))S(17.32 (5)), has been solved by X-ray single-crystal diffraction on the basis of 36,550 observed reflections (with F(o) > 4σF(o)) with a final R1 = 0.074. Pb-rich chabournéite is triclinic P1, with unit-cell parameters a = 8.5197 (4), b = 42.461 (2), c = 16.293 (8) Å, α = 83.351 (2), ß = 90.958 (2), γ = 84.275 (2)°, V = 5823 (3) Å(3). Its structural formula is close to [Tl2(Pb(0.8)Tl(0.1)Sb(1.1))](Sb(4.1)As(4.9))S17, with Z = 8. Its crystal structure is formed by the alternation of two pairs of slabs along the b axis, deriving from the SnS and PbS archetypes, respectively. 104 independent cation sites and 136 S sites occur in the unit cell. Slab interfaces show the alternation, along c, of Tl sites, ninefold coordinated, with Pb, Sb or mixed/split (Pb,Sb) and (Pb,Tl) sites. Within the slabs, 72 independent M(3+) sites (M(3+) = As, Sb) occur. Considering M(3+)-S bond distances shorter than 2.70 Å, MS3 triangular pyramidal groups are condensed according to various M(m)S(n) chain fragments (`polymers'). The solution of the crystal structure of chabournéite allows its comparison with the closely related homeotypes protochabournéite and dalnegroite.