Petrology of chromite in ureilites: Deconvolution of primary oxidation states and secondary reduction processes

Abstract

Ureilites are ultramafic achondrites thought to be residues of partial melting on a carbon-rich asteroid. They show a trend of FeO-variation (olivine Fo from ∼74 to 95) that suggests variation in oxidation state. Whether this variation was established during high-temperature igneous processing on the ureilite parent body (UPB), or preserved from nebular precursors, is a subject of debate. The behavior of chromium in ureilites offers a way to assess redox conditions during their formation and address this issue, independent of Fo. We conducted a petrographic and mineral compositional study of occurrences of chromite (Cr-rich spinel) in ureilites, aimed at determining the origin of the chromite in each occurrence and using primary occurrences to constrain models of ureilite petrogenesis. Chromite was studied in LEW 88774 (Fo 74.2), NWA 766 (Fo 76.7), NWA 3109 (Fo 76.3), HaH 064 (Fo 77.5), LAP 03587 (Fo 74.9), CMS 04048 (Fo 76.4), LAP 02382 (Fo 78.6) and EET 96328 (Fo 85.2).Chromite occurs in LEW 88774 (∼5vol.%), NWA 766 (<1vol.%), NWA 3109 (<1vol.%) and HaH 064 (<1vol.%) as subhedral to anhedral grains comparable in size (∼30μm to 1mm) and/or textural setting to the major silicates (olivine and pyroxenes[s]) in each rock, indicating that it is a primary phase. The most FeO-rich chromites in these sample (rare grain cores or chadocrysts in silicates) are the most primitive compositions preserved (fe#=0.55–0.6; Cr# varying from 0.65 to 0.72 among samples). They record olivine–chromite equilibration temperatures of ∼1040–1050°C, reflecting subsolidus Fe/Mg reequilibration during slow cooling from ∼1200 to 1300°C. All other chromite in these samples is reduced. Three types of zones are observed. (1) Inclusion-free interior zones showing reduction of FeO (fe# ∼0.4→0.28); (2) Outer zones showing further reduction of FeO (fe# ∼0.28→0.15) and containing abundant laths of eskolaite–corundum (Cr2O3–Al2O3); (3) Outermost zones showing extreme reduction of both FeO (fe# <0.15) and Cr2O3 (Cr# as low as 0.2). The grains are surrounded by rims of Si-Al-rich glass, graphite, Fe, Cr-carbides ([Fe,Cr]3C and [Fe,Cr]7C3), Cr-rich sulfides (daubréelite and brezinaite) and Cr-rich symplectic bands on adjacent silicates. Chromite is inferred to have been reduced by graphite, forming eskolaite–corundum and carbides as byproducts, during impact excavation. This event involved initial elevation of T (to 1300–1400°C), followed by rapid decompression and drop in T (to <700°C) at 1–20°C/h. The kinetics of reduction of chromite is consistent with this scenario. The reduction was facilitated by silicate melt surrounding the chromites, which was partly generated by shock-melting of pyroxenes. Symplectic bands, consisting of fine-scale intergrowths of Ca-pyroxene, chromite and glass, formed by reaction between the Cr-enriched melt and adjacent silicates.Early chromite also occurs in a melt inclusion in olivine in HaH 064 and in a metallic spherule in olivine in LAP 02382. LAP 03587 and CMS 04048 contain ⩽μm-sized chromite+pyroxene symplectic exsolutions in olivine, indicating high Cr valence in the primary olivine. EET 96328 contains a round grain of chromite that could be a late-crystallizing phase. Tiny chromite grains in melt inclusions in EET 96328 formed in late, closed-system reactions.For 7 of the 8 ureilites we conclude that the relatively oxidizing conditions evidenced by the presence of primary or early chromite pertain to the period of high-T igneous processing. The observation that such conditions are recorded almost exclusively in low-Fo samples supports the interpretation that the ureilite FeO-variation was established during igneous processing on the UPB.