Mn-Cr dating of Fe- and Ca-rich olivine from ‘quenched’ and ‘plutonic’ angrite meteorites using Secondary Ion Mass Spectrometry

Angrite meteorites are suitable for Mn-Cr relative dating (53Mn decays to 53Cr with a half life of 3.7 Myr) using secondary ion mass spectrometry (SIMS) because they contain olivine and kirschsteinite with very high 55Mn/52Cr ratios arising from very low Cr concentrations. Discrepant Mn-Cr and U-Pb time intervals between the extrusive or ‘quenched’ angrite D’Orbigny and some slowly cooled or ‘plutonic’ angrites suggests that some have been affected by secondary disturbances, but this seems to have occurred in quenched rather than in slow-cooled plutonic angrites, where such disturbance or delay of isotopic closure might be expected. Using SIMS, we investigate the Mn-Cr systematics of quenched angrites to higher precision than previously achieved by this method and extend our investigation to non-quenched (plutonic or sub-volcanic) angrites. High values of 3.54 (±0.18) × 10-6 and 3.40 (±0.19) × 10-6 (2-sigma) are found for the initial 53Mn/55Mn of the quenched angrites D’Orbigny and Sahara 99555, which are preserved by Cr-poor olivine and kirschsteinite. The previously reported initial 53Mn/55Mn value of D’Orbigny obtained from bulk-rock and mineral separates is slightly lower and was probably controlled by Cr-rich olivine. Results can be interpreted in terms of the diffusivity of Cr in this mineral. Very low Cr concentrations in Ca-rich olivine and kirschsteinite are probably charge balanced by Al; this substitutes for Si and likely diffuses at a very slow rate because Si is the slowest-diffusing cation in olivine. Diffusion in Cr-rich Mg-Fe olivine is probably controlled by cation vacancies because of deficiency in charge-balancing Al and is therefore more prone to disturbance. The higher initial 53Mn/55Mn found by SIMS for extrusive angrites is more likely to reflect closure of Cr in kirschsteinite at the time of crystallisation, simultaneous with closure of U-Pb and Hf-W isotope systematics for these meteorites obtained from pyroxenes. For the younger angrites Northwest Africa (NWA) 4590 and 4801 we have found initial 53Mn/55Mn values which are consistent with more precise work, at 0.90 (±0.4) × 10-6 and 0.13 (±1.1) × 10-6 respectively. Our work shows that SIMS can usefully constrain and distinguish the ages of angrites of different petrologic groups. In reviewing the petrology of angrites, we suggest that NWA 2999, 4590, and 4801 underwent a secondary partial melting and Cr (+/-Pb) disturbance event that the sub-volcanic Lewis Cliff 86010, and perhaps the plutonic Angra dos Reis, did not. With our higher initial 53Mn/55Mn for D’Orbigny and Sahara 99555 as well as previous data, a combined quenched angrite initial 53Mn/55Mn of 3.47 (±0.12) × 10-6 (2-sigma, MSWD 1.00) yields consistent Mn-Cr and U-Pb intervals between these angrites and Lewis Cliff 86010. Discrepant Mn-Cr timescales for other plutonic and sub-volcanic angrites represents resetting during the secondary partial melting event at ∼4557.2 Ma and indicates a relative order of disturbance of isotope systems: Mn-Cr in olivine before U-Pb in pyroxene, with Hf-W in pyroxene being the most resistant.