Low energy neutral atom imaging on the Moon with the SARA instrument aboard Chandrayaan-1 mission

This paper reports on the Sub-keV Atom Reflecting Analyzer (SARA) experiment that will be flown on the first Indian lunar mission Chandrayaan-1. The SARA is a low energy neutral atom (LENA) imaging mass spectrometer, which will perform remote sensing of the lunar surface via detection of neutral atoms in the energy range from 10 eV to 3 keV from a 100km polar orbit. In this report we present the basic design of the SARA experiment and discuss various scientific issues that will be addressed. The SARA instrument consists of three major subsystems: a LENA sensor (CENA), a solar wind monitor (SWIM), and a digital processing unit (DPU). SARA will be used to image the solar wind-surface interaction to study primarily the surface composition and surface magnetic anomalies and associated mini-magnetospheres. Studies of lunar exosphere sources and space weathering on the Moon will also be attempted. SARA is the first LENA imaging mass spectrometer of its kind to be flown on a space mission. A replica of SARA is planned to fly to Mercury onboard the BepiColombo mission.     

Ion flow and momentum transfer in the Venus plasma environment

An analysis of ion data from 390 Venus Express, VEX, orbits demonstrates that the flow of solar wind- and ionospheric ions near Venus is characterized by a marked asymmetry. The flow asymmetry of solar wind H⁺ and ionospheric O⁺ points steadily in the opposite direction to the planet’s orbital motion, and is most pronounced near the Pole and in the tail/nightside region. The flow asymmetry is consistent with aberration forcing, here defined as lateral forcing induced by the planet’s orbital motion. In addition to solar wind forcing by the radial solar wind expansion, Venus is also subject a lateral/aberration forcing induced by the planet’s orbital motion transverse to the solar wind flow.The ionospheric response to lateral solar wind forcing is analyzed from altitude profiles of the ion density, ion velocity and ion mass-flux. The close connection between decreasing solar wind H⁺ mass-flux and increasing ionospheric O⁺ mass-flux, is suggestive of a direct/local solar wind energy and momentum transfer to ionospheric plasma. The bulk O⁺ ion flow is accelerated to velocities less than 10 km/s inside the dayside/flank Ionopause, and up to 6000 km in the tail. Consequently, the bulk O⁺ outflow does not escape, but remains near Venus as a fast (km/s) O⁺ zonal wind in the Venus polar and nightside upper ionosphere. Furthermore, the total O⁺ mass-flux in the Venus induced magnetosphere, increases steadily downward to a maximum of 2 × 10⁻¹⁴ kg/(m² s) at ≈400 km altitude, suggesting a downward transport of energy and momentum. The O⁺, and total mass-flux, decay rapidly below 400 km. With no other plasma mass-flux as replacement, we argue that the reduction of ion mass-flux is caused by ion-neutral drag, a transfer of ion energy and momentum to neutrals, implying that the O⁺ plasma wind is converted to a neutral (thermosphere) wind at Venus. Incidentally, such a neutral wind would go in the same direction as the Venus atmosphere superrotation.     

Electrochemical Evidence for Pentasulfide Complexes with Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+

A series of stable pentasulfide complexes of the common base metals, Mn, Fe, Co, Ni, Cu and Zn exist in aqueous solutions at ambient temperatures. Pure sodium pentasulfide was prepared and reacted with the divalent cations of Mn, Fe, Co, Ni, Cu and Zn in aqueous solution at ambient temperature. The S52- complexes were found to exist as determined by voltammetric methods.Pentasulfide complexes with compositions assigned as [M(1-S5)] and [M2(- S5)]2+ occur for Mn, Fe, Co and Ni where only one terminal S atom in the S52- binds to one metal (1 = mono-dentate ligand or M-S-S-S-S-S, = ligand bridging two metal centers or M-S-S-S-S-S-M). Conditional stability constants are similar for all four metals with log 1 between 5.3 and 5.7 and log 2 between 11.0 and 11.6. The constants for these pentasulfide complexes are similar to the tetrasulfide complexes and are approximately 0.4–0.8 log units higher than for comparable bisulfide complexes [M(SH)]+ as expected based on the higher nucleophilicity of S52- compared to HS-. Voltammetric results indicate that these are labile complexes.As with the bisulfide and tetrasulfide complexes, Zn(II) and Cu(II) are chemically distinct from the other metals. Zn(II) reacts with pentasulfide to form a stable monomeric pentasulfide chelate, [Zn(1-S5)] with log = 8.7. Cu(II) reacts with pentasulfide to form a complex with the probable stoichiometry [Cu(S5)]2 with log estimated to be 20.2. As with the other four metals, these complexes are comparable with the tetrasulfide complexes. Discrete voltammetric peaks are observed for these complexes and indicate they are electrochemically inert to dissociation. Reactions of Zn(II) and Cu(II) also lead to significant breakup of the polysulfide.The relative strength of the complexes is Cu > Zn > Mn, Fe, Co, Ni. Cu displaces Zn from [Zn(1- S5)] and both Cu and Zn displace Mn, Fe, Co and Ni from their pentasulfide complexes.     

Mechanism of chalcopyrite formation from iron monosulphides in aqueous solutions (< 100°C, pH 2–4.5)

In low-temperature aqueous solutions (< 100°C, pH 2–4.5), chalcopyrite (CuFeS₂) does not form through direct precipitation from solution. The pathway is exclusively via precursor iron sulphides and dissolved Cu salts. The reaction of dissolved Cu (II) salts with natural hexagonal pyrrhotite (Fe_0.9S) is diffusion controlled. The initial stage has an apparent activation energy of 11.4 ± 1.8 kJ mol⁻¹ and the rate (in units of mol dm⁻³s⁻¹ cm⁻²) is independent of the solid reactant surface area. The reaction proceeds through a series of metastable Cu-Fe-sulphide intermediaries. These phases form a series of ephemeral layers penetrating into the pyrrhotite surface. The first phase formed has the stoichiometry Cu_0.1Fe_0.9S. No Fe is released into the solution during its formation and this, together with the extremely low apparent activation energy and the stoichiometry, suggest that it is formed by stuffing of electron holes in the pyrrhotite structure with Cu ions. The transformation from the hexagonal close-packed arrangement of the pyrrhotite structure to the essentially cubic packing in chalcopyrite proceeds through a series of intermediaries, approximating in composition to members of the cubanite group. The rate of formation of these phases is controlled by the coupled diffusion of Fe (II), Fe (III), Cu (I) and Cu (II) species through the surface reaction zone, although the process as a whole can be approximated by steady-state diffusion of total Cu into a semi-infinite medium. Experiments with metastable precursor iron monosulphide phases, including amorphous FeS and synthetic mackinawite indicate similar reaction pathways.

The results suggest that chalcopyrite formation in low-temperature natural systems may be significantly constrained by kinetic factors. Chalcopyrite is, at least, a diagenetic mineral since its formation requires the prior formation of iron sulphides. However, at ambient temperatures its formation is probably limited to very early diagenesis.     

Trace-element heterogeneity in rutile linked to dislocation structures: Implications for Zr-in-rutile geothermometry

The trace-element composition of rutile is commonly used to constrain P–T–t conditions for a wide range of metamorphic systems. However, recent studies have demonstrated the redistribution of trace elements in rutile via high-diffusivity pathways and dislocation-impurity associations related to the formation and evolution of microstructures. Here, we investigate trace-element migration in low-angle boundaries formed by dislocation creep in rutile within an omphacite vein of the Lago di Cignana unit (Western Alps, Italy). Zr-in-rutile thermometry and inclusions of quartz in rutile and of coesite in omphacite constrain the conditions of rutile deformation to around the prograde boundary from high pressure to ultra-high pressure (~2.7 GPa) at temperatures of 500–565°C. Crystal-plastic deformation of a large rutile grain results in low-angle boundaries that generate a total misorientation of ~25°. Dislocations constituting one of these low-angle boundaries are enriched in common and uncommon trace elements, including Fe and Ca, providing evidence for the diffusion and trapping of trace elements along the dislocation cores. The role of dislocation microstructures as fast-diffusion pathways must be evaluated when applying high-resolution analytical procedures as compositional disturbances might lead to erroneous interpretations for Ca and Fe. In contrast, our results indicate a trapping mechanism for Zr.