¹Damanveer S.Grewal,¹Paul D.Asimow
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2023.01.012]
¹Division of Geological and Planetary Sciences, California Institute of Technology, 1200 E California Blvd, Pasadena, CA 91125, USA
Copyright Elsevier

Disagreement regarding the origin of the bulk silicate Earth’s (BSE) superchondritic carbon/nitrogen (C/N) ratio is due, in part, to the unknown C/N ratios of differentiated planetesimals − the building blocks of Earth-like rocky planets. In this study we report solid-liquid metal partitioning experiments for C and N that allow us to reconstruct, from the C and N contents of iron meteorites, the C/N ratios of the cores of the earliest formed planetesimals. Due to their siderophile character, most of the C and N retained in these bodies after differentiation resides in their cores. Therefore, estimates of the bulk C and N contents and C/N ratios of the cores yield confident estimates of these quantities in the complete parent bodies of iron meteorites. Our experimental data, at 1 GPa and 1200-1400 °C, show that C and N are incompatible in solid metal relative to S-poor liquids but compatible in solid metal relative to S-rich liquids. Crucially, N is approximately an order of magnitude more compatible than C in S-rich systems. S itself is incompatible in solid metal and so the late-crystallizing liquids persisting at the end of core freezing were S-rich for most cores. Although these late-crystallizing liquids are unsampled by iron meteorites, we infer that their N contents and C/N ratios were generally lower and higher, respectively, than those in iron meteorites. Depending upon the fraction of unsampled late-crystallizing liquids as well as their S contents, the C/N ratios of the bulk cores and complete parent bodies are either similar to or higher than those measured in iron meteorites. The reconstructed C/N ratios of most of the parent bodies of iron meteorites are chondritic, except that the volatile-rich IC and IIC groups have superchondritic C/N ratios. Importantly, the C/N ratio of the parent body of the IC iron meteorite group lies within the estimated range of the BSE, whereas the C/N ratios of all other groups are distinctly lower. Correlated depletion of moderately volatile elements like Ge and Ga with C and N, variations in metallographic cooling rates, and Pd-Ag isotope systematics suggest that the parent cores of the volatile-depleted iron meteorite groups were likely affected by volatile degassing. If volatile-rich iron meteorites like the IC group better capture the C and N inventories of the parent cores of the earliest formed planetesimals, then delivery of C and N via such planetesimals makes the superchondritic C/N ratio of the BSE a natural consequence of the Earth’s accretion history. Otherwise, poorly constrained processes like atmospheric erosion or C and N delivery by exotic materials are required to explain the superchondritic C/N ratio of the BSE.

^1,2Alessandro Bragagni,¹Frank Wombacher,^1,3Maria Kirchenbaur,^1,4Ninja Braukmüller,¹Carsten Münker
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2023.01.014]
¹Institut für Geologie und Mineralogie, Universität zu Köln, Zülpicher Str. 49b, 50674 Köln, Germany
²Dipartimento di Scienze della Terra, Università degli studi di Firenze, via La Pira 4, 50121 Firenze, Italy
³Institut für Mineralogie, Leibniz Universität Hannover, Callinstraße 3, 30167 Hannover, Germany
⁴Institut für Geologische Wissenschaften, Freie Universität, Malteserstr. 74-100, 12249, Berlin, Germany
Copyright Elsevier

Tin has ten stable isotopes, providing the opportunity to investigate and discriminate nucleosynthetic isotope anomalies from mass-dependent and mass-independent isotope fractionation. Novel protocols for chemical separation (based on TBP-resin) and MC-ICP-MS analyses are reported here for high precision Sn isotope measurements on terrestrial rocks and chondrites. Relative to the Sn reference standard (NIST SRM 3161a), terrestrial basalts and chondrites show isotope patterns that are consistent with mass-dependent and mass-independent isotope fractionation processes as well as with 115Sn radiogenic ingrowth from 115In.

Two different mass-independent isotope effects are identified, namely the nuclear volume (or nuclear field shift) and the magnetic isotope effect. The magnetic isotope effect dominates in the two measured ordinary chondrites, while repeated analyses of the carbonaceous chondrite Murchison (CM2) display a pattern consistent with a nuclear volume effect. Terrestrial basalts show patterns that are compatible with a mixture of nuclear volume and magnetic isotope effects. The ultimate origin of the isotope fractionation is unclear but a fractionation induced during sample preparation seems unlikely because different groups of chondrites show distinctly different patterns, hence pointing towards natural geo/cosmochemical processes. Only the carbonaceous chondrite Murchison (CM2) shows a Sn isotope pattern similar to what expected for nucleosynthetic variations. However, this pattern is better reproduced by nuclear volume effects. Thus, after considering mass-independent and mass-dependent effects, we find no evidence of residual nucleosynthetic anomalies, in agreement with observations for most other elements with similar half-mass condensation temperatures.

Most chondrites show a deficit in 115Sn/120Sn (typically -150 to -200 ppm) relative to terrestrial samples, with the exception of one ordinary chondrite that displays an excess of about +250 ppm. The 115Sn/120Sn data correlate with In/Sn, being consistent with the β- decay of 115In over the age of the solar system. This represents the first evidence of the 115In-115Sn decay system in natural samples. The radiogenic 115Sn signature of the BSE derives from a suprachondritic In/SnBSE, which reflects preferential partitioning of Sn into the Earth’s core.