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.

Formation of a Single-Crystal Aluminum-Based MOF Nanowire with Graphene Oxide Nanoscrolls as Structure-Directing Agents.

An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al3+ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 µm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.

The growth of lithospheric diamonds.

Natural diamonds contain mineral and fluid inclusions that record diamond growth conditions. Replicating the growth of inclusion-bearing diamonds in a laboratory is therefore a novel diagnostic tool to constrain the conditions of diamond formation in Earth's lithosphere. By determining the carbon isotopic fractionation during diamond growth in fluids or melts, our laboratory experiments revealed that lithospheric monocrystalline and fibrous and coated diamonds grow similarly from redox reactions at isotopic equilibrium in water and carbonate-rich fluids or melts, and not from native carbon. These new results explain why most of the lithospheric diamonds are characterized by a common carbon isotopic fingerprint, inherited from their common parent fluids and not from the mantle assemblage.

Massive production of abiotic methane during subduction evidenced in metamorphosed ophicarbonates from the Italian Alps.

Alteration of ultramafic rocks plays a major role in the production of hydrocarbons and organic compounds via abiotic processes on Earth and beyond and contributes to the redistribution of C between solid and fluid reservoirs over geological cycles. Abiotic methanogenesis in ultramafic rocks is well documented at shallow conditions, whereas natural evidence at greater depths is scarce. Here we provide evidence for intense high-pressure abiotic methanogenesis by reduction of subducted ophicarbonates. Protracted (≥0.5-1 Ma), probably episodic infiltration of reduced fluids in the ophicarbonates and methanogenesis occurred from at least ∼40 km depth to ∼15-20 km depth. Textural, petrological and isotopic data indicate that methane reached saturation triggering the precipitation of graphitic C accompanied by dissolution of the precursor antigorite. Continuous infiltration of external reducing fluids caused additional methane production by interaction with the newly formed graphite. Alteration of high-pressure carbonate-bearing ultramafic rocks may represent an important source of abiotic methane, with strong implications for the mobility of deep C reservoirs.

Arsenic(V) Incorporation in Vivianite during Microbial Reduction of Arsenic(V)-Bearing Biogenic Fe(III) (Oxyhydr)oxides.

The dissolution of arsenic-bearing iron(III) (oxyhydr)oxides during combined microbial iron(III) and arsenate(V) reduction is thought to be the main mechanism responsible for arsenic mobilization in reducing environments. Besides its mobilization during bioreduction, arsenic is often resequestered by newly forming secondary iron(II)-bearing mineral phases. In phosphate-bearing environments, iron(II) inputs generally lead to vivianite precipitation. In fact, in a previous study we observed that during bioreduction of arsenate(V)-bearing biogenic iron(III) (oxyhydr)oxides in phosphate-containing growth media, arsenate(V) was immobilized by the newly forming secondary iron(II) and iron(II)/iron(III)mineral phases, including vivianite. In the present study, changes in arsenic redox state and binding environment in these experiments were analyzed. We found that arsenate(V) partly replaced phosphate in vivianite, thus forming a vivianite-symplesite solid solution identified as Fe3(PO4)1.7(AsO4)0.3·8H2O. Our data suggests that in order to predict the fate of arsenic during the bioreduction of abiogenic and biogenic iron(III) (oxyhydr)oxides in arsenic-contaminated environments, the formation of symplesite-vivianite minerals needs to be considered. Indeed, such mineral phases could contribute to a delayed and slow release of arsenic in phosphate-bearing surface and groundwater environments.