Detection of ferric iron in an exsolved lunar pyroxene using electron energy loss spectroscopy (EELS): Implications for space weathering and redox conditions on the Moon

To shed light on the mechanism of formation of nanophase iron particles (npFe) in space-weathered materials from airless bodies, we analyzed exsolved and unexsolved space-weathered lunar pyroxenes from Apollo 17 sample 71501. The exsolved pyroxene allowed for the observation of the effects of space weathering on similar mineral phases with variable composition. Using coordinated scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy (EELS), we determined that two coexisting pyroxenes in the exsolved grain showed systematic variations in response to space weathering, despite equivalent exposure conditions. The npFe in the space-weathered rim of augite lamellae were smaller and fewer than the npFe in the rim of pigeonite lamellae. EELS spectrum imaging revealed the presence and heterogeneous distribution of Fe⁰, Fe²⁺, and Fe³⁺ in the exsolved pyroxene. Metallic iron occurred in the npFe, a mixture of Fe²⁺ and Fe³⁺ occurred in the pigeonite lamellae, and the augite lamellae contained virtually all Fe³⁺. Approximately 50% of the total Fe measured in the exsolved pyroxene grain was ferric. Partitioning of Fe²⁺ and Fe³⁺ among the lamellae is invoked to explain the difference in npFe development in pigeonite and augite. The results of this study, the first to identify Fe³⁺ in a crystalline lunar ferromagnesian silicate, have implications for our understanding of how space weathering might proceed in oxidized phases. Furthermore, the discovery of an Fe³⁺-rich pyroxene also supports attribution of the 0.7 μm absorption feature observed in Galileo Solid State Imager data to oxidized Fe in clinopyroxenes.