Insights into the origin of carbonaceous chondrite organics from their triple oxygen isotope composition Romain Tartèsea,1, Marc Chaussidonb, Andrey Gurenkoc, Frédéric Delarued, and François Roberte aSchool of Earth and Environmental Sciences, The University of Manchester, Manchester M13 9PL, United Kingdom; bInstitut de Physique du Globe de Paris, Université Sorbonne-Paris-Cité, Université Paris Diderot, CNRS UMR 7154, F-75238 Paris, France; cCentre de Recherches Pétrographiques et Géochimiques, UMR 7358, Université de Lorraine, F-54501 Vandoeuvre-lès-Nancy, France; dSorbonne Université, Université Pierre-et-Marie-Curie, CNRS, École Pratique des Hautes Etudes, Paris Sciences et Lettres, UMR 7619 Milieux Environnementaux, Transferts et Interactions dans les Hydrosystèmes et les Sols, F-75005 Paris, France; and eInstitut de Minéralogie, de Physique des Matériaux et de Cosmochimie, Muséum National d’Histoire Naturelle, Sorbonne Universités, CNRS, Université Pierre-et-Marie-Curie, and Institut de Recherche pour le Développement, F-75005 Paris, France Edited by Mark H. Thiemens, University of California, San Diego, La Jolla, CA, and approved July 12, 2018 (received for review May 10, 2018) Dust grains of organic matter were the main reservoir of C and N studies of meteoritic materials (e.g., refs. 16 and 17), and this should in the forming Solar System and are thus considered to be an apply to CC OM since it contains ∼10–25 wt% O (11, 12). essential ingredient for the emergence of life. However, the physical However, determining the O isotope composition of OM is environment and the chemical mechanisms at the origin of these challenging since it tends to be intimately mixed with O-rich organic grains are still highly debated. In this study, we report high- silicates and oxides at nanoscale to microscale in carbonaceous precision triple oxygen isotope composition for insoluble organic chondrites (e.g., ref. 18). Acid maceration used to isolate the matter isolated from three emblematic carbonaceous chondrites, insoluble OM (IOM) fraction from whole-rock samples removes Orgueil, Murchison, and Cold Bokkeveld. These results suggest that most of the silicates but is less effective at dissolving sulfides and the O isotope composition of carbonaceous chondrite insoluble or- some refractory O-bearing oxides such as chromite, spinel, ganic matter falls on a slope 1 correlation line in the triple oxygen hibonite, or corundum. Bulk pyrolysis O isotope analysis of IOM isotope diagram. The lack of detectable mass-dependent O iso- is thus susceptible to contamination by residual mineral inclu- topic fractionation, indicated by the slope 1 line, suggests that the sions. To constrain the triple O isotope composition of CC bulk of carbonaceous chondrite organics did not form on asteroi- IOM, we integrate here high spatial resolution secondary ion dal parent bodies during low-temperature hydrothermal events. mass spectrometry (SIMS) data obtained using NanoSIMS with On the other hand, these O isotope data, together with the H and high-precision 17,18O/16O isotope ratios obtained using large N isotope characteristics of insoluble organic matter, may indicate geometry multicollector IMS 1270/80 ion probes (referred to as that parent bodies of different carbonaceous chondrite types largely L-SIMS in the following). For each L-SIMS O isotope analysis, accreted organics formed locally in the protosolar nebula, possibly by measurement of 28Si, 32S, and 56Fe16O intensities allowed a photochemical dissociation of C-rich precursors. first-order filtering of data for which the O signals were largely affected by contamination by residual silicate and/or oxide carbonaceous chondrites | organic matter | oxygen isotopes | phases (see Materials and Methods for details). The results protosolar nebula | secondary ion mass spectrometry presented here thus provide high-precision triple O isotope estimates for IOM residues isolated from two emblematic CC ype 1–2 carbonaceous chondrites (CCs) contain several falls, the Ivuna-type (CI) Orgueil meteorite and the Mighei- Tweight percent (wt%) carbon that mostly occurs as small type (CM) Murchison meteorite. patchesoforganicmatter(OM)dispersed in the fine-grained matrix (1). Because this OM possibly played a key role in the development Significance of life on the early Earth, its molecular structure and its chemical and isotopic compositions have been extensively investigated (see Refractory organic matter found in volatile-rich asteroidal ref. 2 and references therein for a recent review). Despite this materials essentially comprise the elements C, H, O, N, and S, profusion of structural, chemical, and isotopic information, the which are thought to be important building blocks for life. question of whether CC OM formed in the cold interstellar medium Characterizing the origin(s) of these organics thus constitutes a (e.g., refs. 3–5), formed in the protosolar nebula (PSN) (e.g., refs. 6– key step to constrain the origin of life on Earth and appraise 9), or is a product of organic synthesis during hydrothermalism on the habitability potential of other worlds. However, how and CC parent bodies (e.g., ref. 10) remains highly debated, notably where these organics formed are still highly debated. In this because the extent of chemical and isotopic alteration of OM during – study, we have determined the oxygen isotope composition of secondary processes on CC parent bodies is unclear (11 15). refractory organics from two families of carbonaceous chon- Oxygen is the third most abundant element in the Solar Sys- 16 17 18 drites. These data suggest that these organics formed in the tem and has three stable isotopes, O, O, and O. Because nascent Solar System, possibly through chemical reactions oc- different fractionation laws govern interplanetary and intra- curring in the disk surrounding the young Sun. planetary processes (e.g., ref. 16), the oxygen three-isotope sys- tem can provide information that cannot be accessed using other Author contributions: R.T., M.C., and F.R. designed research; R.T. performed research; R.T., two-isotope systems of light elements such as H, C, and N. In M.C., A.G., and F.D. contributed new reagents/analytic tools; R.T. analyzed data; and R.T., planetary bodies, variations of the 17O/16O and 18O/16O ratios M.C., A.G., F.D., and F.R. wrote the paper. 17 almost always obey the mass-dependent relationship δ O ∼ The authors declare no conflict of interest. EARTH, ATMOSPHERIC, 18 AND PLANETARY SCIENCES 0.52 × δ O, while oxygen isotope abundance variations between This article is a PNAS Direct Submission. Solar System gas and solids are primarily governed by the mass- Published under the PNAS license. 17 18 independent relationship δ O ∼ 1.0 × δ O (15). [This Data deposition: Raw data from this manuscript have been deposited in the Mendeley δ-notation represents deviations in parts per 1,000 (‰)ofthe Data repository (dx.doi.org/10.17632/hwwsdz8997.1). 17,18 16 O/ O ratios relative to those of the standard mean ocean water 1To whom correspondence should be addressed. Email: [email protected]. 17,18 17,18 16 (SMOW), according to the equation δ O = [( O/ O)sample/ This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10. 17,18 16 ( O/ O)SMOW − 1] × 1,000.] Much of our understanding of how 1073/pnas.1808101115/-/DCSupplemental. our Solar System formed and evolved is thus based on O isotope Published online August 6, 2018. www.pnas.org/cgi/doi/10.1073/pnas.1808101115 PNAS | August 21, 2018 | vol. 115 | no. 34 | 8535–8540 Downloaded by guest on September 23, 2021 Results Discussion The δ17O and δ18O values measured by L-SIMS in the Orgueil, Assessing the Level of Contamination from Residuals Microinclusions Murchison, and Cold Bokkeveld IOM residues range between in IOM. The main challenge in determining the O isotope com- −23.3 ± 2.4‰ and +18.9 ± 2.4‰ and −18.0 ± 2.3‰ and +16.9 ± position of IOM isolated from carbonaceous chondrites is related 2.3‰ (uncertainties reported at 2σ), respectively (Fig. 1 and SI to the presence of residual nanoinclusions to microinclusions that Appendix, Table S1). Least-square regression through all of the have resisted acid maceration, as shown here by NanoSIMS im- data yields a line defined by δ17O = 1.00 (±0.14) × δ18O − 3.78 aging. The consistency between O isotope values estimated for (±1.35) (95% confidence level, n = 36, r2 = 0.86), which is indis- pure IOM based on high-resolution NanoSIMS analyses and the tinguishable from the relationship known as the carbonaceous most 17,18O-rich compositions obtained by L-SIMS for Murchison chondrite anhydrous mineral (CCAM) line (δ17O = 0.95 × δ18O − and Orgueil acid residues, respectively, suggest that the latter 4.18) (Fig. 1). provide an accurate estimate for the O isotope composition of The NanoSIMS data allow determining O isotope ratios with Murchison and Orgueil IOM. We thus consider here that the larger uncertainties than those obtained by L-SIMS, but with average values calculated from the two most 17,18O-rich compo- higher spatial resolution, that is, over region of interests (ROI) sitions measured by L-SIMS on both Murchison and Orgueil that can be selected from ion imaging to minimize the effect of provide us with the best estimates for the O isotope compositions 18 residual oxides and/or silicates, located through analysis of 28Si of pure IOM end-members in these samples. This yields δ O = 17 and 56Fe16O simultaneously with O isotopes. The NanoSIMS +4.7 ± 7.7‰ (2 SD) and δ O =+2.9 ± 10.3‰ (2 SD) for 18 17 analyses obtained over 40-μm2 areas in Murchison and Orgueil Murchison IOM and δ O =+16.6 ± 0.8‰ (2 SD) and δ O = IOM residues show little 28Si hot spots but more abundant +17.0 ± 5.2‰ (2 SD) for Orgueil IOM.