SIMS matrix effects in oxygen isotope analysis of olivine and pyroxene: Application to Acfer 094 chondrite chondrules and reconsideration of the primitive chondrule minerals (PCM) line
Mingming Zhang, Kohei Fukuda, Michael J. Spicuzza, Guillaume Siron, Adriana Heimann, Alex J. Hammerstromb, Noriko T.Kita, Takayuki Ushikubo, John W.Valley
In Press, Journal Pre-proof, Available online 11 July 2022
“The instrumental bias (here expressed as bias, the difference relative to San Carlos Olivine, SC-Ol) of oxygen isotopes in secondary ion mass spectrometry (SIMS) analyses of olivine and pyroxene were investigated. Seventeen olivine (Fo0–100), nine orthopyroxene (En70–100Wo0–3), and three clinopyroxene (En28-49Wo45–50) reference materials (RMs) were utilized. The values of bias are nearly invariant (within 0 ± 0.5‰) among magnesian olivine (Fo ≥60) RMs but decrease systematically with increasing Fe molar fraction down to ~ − 10‰ (Fo0). The session-to-session variability of bias* for Fo ≥60 olivines is ≤0.3‰ but becomes slightly larger for more Fe-rich compositions (≤1.5‰). Orthopyroxene RMs have a narrow range of bias* values (−1.7‰ to −2.6‰) that show session-to-session variability ≤0.3‰; correspondingly, the sputter rates are similarly low and resemble those of Fo ≥60 olivines. Clinopyroxene RMs bias* values (−0.2‰ to +1.2‰) are more variable and have larger session-to-session variability (≤0.8‰), which appear to be independent of sputter rates. Bias* of the same RMs change slightly from session to session with different analytical settings (≤0.6‰ for Fo ≥60 and as much as 2‰ for fayalite) so that equations of bias* as a function of Fo, En, and Wo should be determined for each SIMS session by the analyses of multiple RMs.
The new suite of olivine and pyroxene RMs with expanded composition range were used to correct the instrumental biases during oxygen three-isotope analysis of olivine and low-Ca pyroxene in chondrules of the ungrouped Acfer 094 chondrite, from which the primitive chondrule minerals (PCM, δ18O vs. δ17O) line was originally derived. The PCM line is considered to be a mixing trend of two extreme primary oxygen isotope reservoirs of solids in the early solar system. However, this new dataset, with better analytical precision and instrumental bias correction, allows two oxygen isotope trends to be clearly identified. One is represented by chondrules that plot on or above the PCM line, likely linked to ordinary chondrite (OC)-like materials. A second trend is represented by the major chondrule population in this chondrite that defines a regression line of δ17O = (0.968 ± 0.020) × δ18O − (3.45 ± 0.09) (MSWD = 1.7), consistent with recent oxygen isotope data of chondrules in carbonaceous chondrites (i.e., CV, CK, CO, and CM). We propose that this regression line represents a mixing of two oxygen isotope reservoirs (possibly 16O-rich solids and 16O-poor H2O ice) in the outer solar system and likely resulting from the separate evolutions of isotope reservoirs after the “Jupiter divide” built up.”