Formation and transformations of Fe-rich serpentines by asteroidal aqueous alteration processes: A nanoscale study of the Murray chondrite

Fe-rich serpentines are an abundant product of the early aqueous alteration events that affected the parent bodies of CM carbonaceous chondrites. Alteration assemblages in these meteorites show a large chemical variability and although water-rock interactions occurred under anoxic conditions, serpentines contain high amounts of ferric iron. To date very few studies have documented Fe valence variations in alteration assemblages of carbonaceous chondrites, limiting the understanding of the oxidation mechanisms. Here, we report results from a nanoscale study of a calcium-aluminum-rich inclusion (CAI) from the Murray chondrite, in which alteration resulted in Fe import and Ca export by the fluid phase and in massive Fe-rich serpentines formation. We combined scanning and transmission electron microscopies and scanning transmission X-ray microscopy for characterizing the crystal chemistry of Fe-serpentines. We used reference minerals with known crystallographic orientations to quantify the Fe valence state in Fe-rich serpentines using X-ray absorption spectroscopy at the Fe L2,3-edges, yielding a robust methodology that would prove valuable for studying oxidation processes in other terrestrial or extra-terrestrial cases of serpentinization. We suggest that aqueous Fe2+ was transported to the initially Fe-depleted CAI, where local changes in pH conditions, and possibly mineral catalysis by spinel promoted the partial oxidation of Fe2+ into Fe3+ by water and the formation of Fe-rich serpentines close to the cronstedtite endmember. Such mechanisms produce H2, which opens interesting perspectives as hydrogen may have reacted with carbon species, or escaped and yield increasingly oxidizing conditions in the parent asteroid. From the results of this nanoscale study, we also propose transformations of the initial cronstedtite, destabilized by later input of Al- and Mg-rich solutions, leading to Fe2+ leaching from serpentines, as well as to random serpentine-chlorite interstratifications. Such transformations towards polysomatic assemblages that are un-equilibrated from the structural, chemical and redox point of views are probably controlled by the various rates of alteration of primary minerals, but also by porosity gradients, as in terrestrial hydrothermal systems. We suggest that the proposed mechanisms may have played a role in the early formation of (Fe2+,Fe3+)-rich serpentines documented in CM chondrites, as well as in their transformation with on-going alteration towards Fe-poorer compositions inferred from previous petrologic, mineralogical and magnetic studies of CM chondrites.