Disequilibrium oxygen isotope distribution among aqueously altered minerals in Ryugu asteroid returned samples

Oxygen 3-isotope ratios of magnetite and carbonates in aqueously altered carbonaceous chondrites provide important clues to understanding the evolution of the fluid in the asteroidal parent bodies. We conducted oxygen 3-isotope analyses of magnetite, dolomite, and breunnerite in two sections of asteroid Ryugu returned samples, A0058 and C0002, using a secondary ion mass spectrometer (SIMS). Magnetite was analyzed by using a lower primary ion energy that reduced instrumental biases due to the crystal orientation effect. We found two groups of magnetite data identified from the SIMS pit morphologies: (1) higher delta O-18 (from 3 parts per thousand to 7 parts per thousand) and Delta O-17 (similar to 2 parts per thousand) with porous SIMS pits mostly from spherulitic magnetite, and (2) lower delta O-18 (similar to -3 parts per thousand) and variable Delta O-17 (0 parts per thousand-2 parts per thousand) mostly from euhedral magnetite. Dolomite and breunnerite analyses were conducted using multi-collection Faraday cup detectors with precisions <= 0.3 parts per thousand. The instrumental bias correction was applied based on carbonate compositions in two ways, using Fe and (Fe + Mn) contents, respectively, because Ryugu dolomite contains higher amounts of Mn than the terrestrial standard. Results of dolomite and breunnerite analyses show a narrow range of Delta O-17; 0.0 parts per thousand-0.3 parts per thousand for dolomite in A0058 and 0.2 parts per thousand-0.8 parts per thousand for dolomite and breunnerite in C0002. The majority of breunnerite, including large >= 100 mu m grains, show systematically lower delta O-18 (similar to 21 parts per thousand) than dolomite (25 parts per thousand-30 parts per thousand and 23 parts per thousand-27 parts per thousand depending on the instrumental bias corrections). The equilibrium temperatures between magnetite and dolomite from the coarse-grained lithology in A0058 are calculated to be 51 +/- 11 degrees C and 78 +/- 14 degrees C, depending on the instrumental bias correction scheme for dolomite; a reliable temperature estimate would require a Mn-bearing dolomite standard to evaluate the instrumental bias corrections, which is not currently available. These results indicate that the oxygen isotope ratios of aqueous fluids in the Ryugu parent asteroid were isotopically heterogeneous, either spatially, or temporary. Initial water ice accreted to the Ryugu parent body might have Delta O-17 > 2 parts per thousand that was melted and interacted with anhydrous solids with the initial Delta O-17 < 0 parts per thousand. In the early stage of aqueous alteration, spherulitic magnetite and calcite formed from aqueous fluid with Delta O-17 similar to 2 parts per thousand that was produced by isotope exchange between water (Delta O-17 > 2 parts per thousand) and anhydrous solids (Delta O-17 < 0 parts per thousand). Dolomite and breunnerite, along with some magnetite, formed at the later stage of aqueous alteration under higher water-to-rock ratios where the oxygen isotope ratios were nearly at equilibrium between fluid and solid phases. Including literature data, delta O-18 of carbonates decreased in the order calcite, dolomite, and breunnerite, suggesting that the temperature of alteration might have increased with the degree of aqueous alteration.