Abstract
The nature of the organic matter in interplanetary samples is central to elucidating the formation and early evolution of the Solar System. Although most meteorites derive from asteroids, micrometeorites mainly sample more remote objects. Ultra-carbonaceous Antarctic micrometeorites (UCAMMs), which have the highest carbon content among interplanetary samples, offer a unique window into cometary organics. Here we report a survey of the H, C and N isotopes in four UCAMMs, of which two are 15N-poor (δ15N ≃ −120‰), which suggests that their formation involved primordial N2 (δ15N ≃ −380‰). Such a composition could be the result of Galactic cosmic ray irradiation of N2 ices at the surface of cold small bodies in the outermost parts of the Solar System, possibly the Oort cloud. The two other UCAMMs exhibit higher δ15N (75‰ and 282‰), like those reported for carbonaceous chondrites and interplanetary dust particles. They may originate from parent bodies initially on lower heliocentric orbits in the Kuiper belt that have surfaces cold enough to retain N-bearing species, such as cyanides (δ15N ≥ 200‰), that are richer in 15N than primordial N2. According to their elemental and isotopic composition, UCAMMs constitute a unique probe into the coldest objects of the Solar System, namely those in the Kuiper Belt and the Oort cloud, which are largely out of reach of current space exploration.
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Data availability
The data presented in the paper are provided in Supplementary Table 1 and are available via Zenodo at https://doi.org/10.5281/zenodo.12626220 (ref. 55).
References
Alexander, C. M. O'D., Fogel, M., Yabuta, H. & Cody, G. D. The origin and evolution of chondrites recorded in the elemental and isotopic compositions of their macromolecular organic matter. Geochim. Cosmochim. Acta 71, 4380–4403 (2007).
Busemann, H. et al. Interstellar chemistry recorded in organic matter from primitive meteorites. Science 312, 727–730 (2006).
De Gregorio, B. T. et al. Isotopic and chemical variation of organic nanoglobules in primitive meteorites. Meteorit. Planet. Sci. 48, 904–928 (2013).
Nittler, L. R. et al. A cometary building block in a primitive asteroidal meteorite. Nat. Astron. 3, 659–666 (2019).
Floss, C. & Stadermann, F. J. High abundances of circumstellar and interstellar C-anomalous phases in the primitive CR3 chondrites QUE 99177 and MET 00426. Astrophys. J. 697, 1242 (2009).
Nittler, L. R. et al. High abundances of presolar grains and 15N-rich organic matter in CO3.0 chondrite Dominion Range 08006. Geochim. Cosmochim. Acta 226, 107–131 (2018).
Vollmer, C. et al. Isotopic compositions, nitrogen functional chemistry, and low-loss electron spectroscopy of complex organic aggregates at the nanometer scale in the carbonaceous chondrite Renazzo. Meteorit. Planet. Sci. 55, 1293–1319 (2020).
Vollmer, C. et al. A primordial 15N-depleted organic component detected within the carbonaceous chondrite Maribo. Sci. Rep. 10, 20251 (2020).
Floss, C., Le Guillou, C. & Brearley, A. Coordinated NanoSIMS and FIB-TEM analyses of organic matter and associated matrix materials in CR3 chondrites. Geochim. Cosmochim. Acta 139, 1–25 (2014).
Messenger, S. Identification of molecular-cloud material in interplanetary dust particles. Nature 404, 968–971 (2000).
Floss, C. et al. Identification of isotopically primitive interplanetary dust particles: a NanoSIMS isotopic imaging study. Geochim. Cosmochim. Acta 70, 2371–2399 (2006).
Floss, C., Stadermann, F. J., Mertz, A. F. & Bernatowicz, T. J. A NanoSIMS and Auger nanoprobe investigation of an isotopically primitive interplanetary dust particle from the 55P/Tempel-Tuttle targeted stratospheric dust collector. Meteorit. Planet. Sci. 45, 1889–1905 (2010).
Davidson, J., Busemann, H. & Franchi, I. A. A NanoSIMS and Raman spectroscopic comparison of interplanetary dust particles from comet Grigg–Skjellerup and non-Grigg Skjellerup collections. Meteorit. Planet. Sci. 47, 1748–1771 (2012).
Matrajt, G., Messenger, S., Brownlee, D. & Joswiak, D. Diverse forms of primordial organic matter identified in interplanetary dust particles. Meteorit. Planet. Sci. 47, 525–549 (2012).
Busemann, H. et al. Ultra-primitive interplanetary dust particles from the comet 26P/Grigg/Skjellerup dust stream collection. Earth Planet. Sci. Lett. 288, 44–57 (2009).
Aléon, J., Engrand, C., Robert, F. & Chaussidon, M. Clues on the origin of interplanetary dust particles from the isotopic study of their hydrogen-bearing phases. Geochim. Cosmochim. Acta 65, 4399–4412 (2001).
McKeegan, K. D. et al. Isotopic compositions of cometary matter returned by Stardust. Science 314, 1724–1728 (2006).
Yabuta, H. et al. Macromolecular organic matter in samples of the asteroid (162173) Ryugu. Science 379, eabn9057 (2023).
Aikawa, Y., Wakelam, V., Hersant, F., Garrod, R. T. & Herbst, E. From prestellar to protostellar cores. II. Time dependence and deuterium fractionation. Astrophys. J. 760, 55 (2012).
Visser, R. et al. Nitrogen isotope fractionation in protoplanetary disks. Astron. Astrophys. 615, A75 (2018).
Müller, D. R. et al. High D/H ratios in water and alkanes in comet 67P/Churyumov-Gerasimenko measured with Rosetta/ROSINA DFMS. Astron. Astrophys. 662, A69 (2022).
Manfroid, J. et al. The CN isotopic ratios in comets. Astron. Astrophys. 503, 613–624 (2009).
Bockelée-Morvan, D. et al. Large excess of heavy nitrogen in both hydrogen cyanide and cyanogen from comet 17P/Holmes. Astrophys. J. 679, L49–L52 (2008).
Duprat, J. et al. Extreme deuterium excesses in ultracarbonaceous micrometeorites from central Antarctic snow. Science 328, 742–745 (2010).
Yabuta, H. et al. Formation of an ultracarbonaceous Antarctic micrometeorite through minimal aqueous alteration in a small porous icy body. Geochim. Cosmochim. Acta 214, 172–190 (2017).
Dartois, E. et al. Ultracarbonaceous Antarctic micrometeorites, probing the Solar System beyond the nitrogen snow-line. Icarus 224, 243–252 (2013).
Dartois, E. et al. Dome C ultracarbonaceous Antarctic micrometeorites. Infrared and Raman fingerprints. Astron. Astrophys. 609, 27 (2018).
Duprat, J. et al. Micrometeorites from central Antarctic snow: the CONCORDIA collection. Adv. Space Res. 39, 605–611 (2007).
Yada, T. et al. The global accretion rate of extraterrestrial materials in the last glacial period estimated from the abundance of micrometeorites in Antarctic glacier ice. Earth Planets Space 56, 67–79 (2004).
Dobrică, E., Engrand, C., Leroux, H., Rouzaud, J.-N. & Duprat, J. Transmission electron microscopy of CONCORDIA ultracarbonaceous Antarctic micrometeorites (UCAMMs): mineralogical properties. Geochim. Cosmochim. Acta 76, 68–82 (2012).
Remusat, L., Guan, Y., Wang, Y. & Eiler, J. M. Accretion and preservation of D-rich organic particles in carbonaceous chondrites: evidence for important transport in the early Solar System nebula. Astrophys. J. 713, 1048–1058 (2010).
Krueger, F. R. & Kissel, J. The organic component in dust from comet Halley as measured by the PUMA mass spectrometer on board Vega 1. Nature 326, 755–760 (1987).
Fray, N. et al. Nitrogen-to-carbon atomic ratio measured by COSIMA in the particles of comet 67P/Churyumov–Gerasimenko. Mon. Not. R. Astron. Soc. 469, S506–S516 (2017).
Cody, G. D. et al. Quantitative organic and light-element analysis of comet 81P/Wild 2 particles using C-, N-, and O-μ-XANES. Meteorit. Planet. Sci. 43, 353–365 (2008).
Remusat, L., Bonnet, J.-Y., Bernard, S., Buch, A. & Quirico, E. Molecular and isotopic behavior of insoluble organic matter of the Orgueil meteorite upon heating. Geochim. Cosmochim. Acta 263, 235–247 (2019).
Owen, T., Mahaffy, P. R., Niemann, H. B., Atreya, S. & Wong, M. Protosolar nitrogen. Astrophys. J. 553, L77–L79 (2001).
Marty, B., Chaussidon, M., Wiens, R. C., Jurewicz, A. J. G. & Burnett, D. S. A 15N-poor isotopic composition for the Solar System as shown by Genesis solar wind samples. Science 332, 1533 (2011).
Meibom, A. et al. Nitrogen and carbon isotopic composition of the Sun inferred from a high-temperature solar nebular condensate. Astrophys. J. 656, L33–L36 (2007).
Hashizume, K., Chaussidon, M., Marty, B. & Terada, K. Protosolar carbon isotopic composition: implications for the origin of meteoritic organics. Astrophys. J. 600, 480 (2004).
Wimmer-Schweingruber, R. F., Berger, L., Köten, M., Bochsler, P. & Gloeckler, G. The 13C/12C Isotopic Ratio in the Solar Wind. Lunar Planet. Sci. XLV, 1114 (2014).
Lyons, J. R., Gharib-Nezhad, E. & Ayres, T. R. A light carbon isotope composition for the Sun. Nat. Commun. 9, 908 (2018).
Biver, N. et al. Isotopic ratios of H, C, N, O, and S in comets C/2012 F6 (Lemmon) and C/2014 Q2 (Lovejoy). Astron. Astrophys. 589, A78 (2016).
Brown, M. E., Schaller, E. L. & Fraser, W. C. A hypothesis for the color diversity of the Kuiper belt. Astrophys. J. 739, L60 (2011).
Parhi, A. & Prialnik, D. Sublimation of ices during the early evolution of Kuiper belt objects. Mon. Not. R. Astron. Soc. 522, 2081–2088 (2023).
Augé, B. et al. Irradiation of nitrogen-rich ices by swift heavy ions. Clues for the formation of ultracarbonaceous micrometeorites. Astron. Astrophys. 592, A99 (2016).
Cooper, J. F., Christian, E. R., Richardson, J. D. & Wang, C. Proton irradiation of Centaur, Kuiper belt, and Oort cloud objects at plasma to cosmic ray energy. Earth Moon Planets 92, 261–277 (2003).
Grundy, W. M. et al. Color, composition, and thermal environment of Kuiper belt object (486958) Arrokoth. Science 367, eaay3705 (2020).
Augé, B. et al. Hydrogen isotopic anomalies in extraterrestrial organic matter: role of cosmic ray irradiation and implications for UCAMMs. Astron. Astrophys. 627, A122 (2019).
Rojas, J. et al. Isotopic Analyses of Ion Irradiation-Induced Organic Residues, Clues on the Formation of Organics from UCAMMs. Lunar Planet. Sci. LI, 1630 (2020).
Keller, L. P. & Flynn, G. J. Evidence for a significant Kuiper belt dust contribution to the zodiacal cloud. Nat. Astron. 6, 731–735 (2022).
Rojas, J. et al. The micrometeorite flux at Dome C (Antarctica), monitoring the accretion of extraterrestrial dust on Earth. Earth Planet. Sci. Lett. 560, 116794 (2021).
Dobricǎ, E., Engrand, C., Quirico, E., Montagnac, G. & Duprat, J. Raman characterization of carbonaceous matter in CONCORDIA Antarctic micrometeorites. Meteorit. Planet. Sci. 46, 1363–1375 (2011).
Mathurin, J. et al. Nanometre-scale infrared chemical imaging of organic matter in ultra-carbonaceous Antarctic micrometeorites (UCAMMs). Astron. Astrophys. 622, A160 (2019).
Bardin, N. et al. Hydrogen isotopic fractionation in secondary ion mass spectrometry using polyatomic ions. Int. J. Mass Spectrometr. 393, 17–24 (2015).
Rojas, J. A. et al. Raw NanoSIMS data - DC06-05-94, DC06-07-18, DC06-04-43, DC16-14-309. Zenodo https://doi.org/10.5281/zenodo.12626220 (2024).
Schneider, C. A., Rasband, W. S. & Eliceiri, K. W. NIH Image to ImageJ: 25 years of image analysis. Nat. Methods 9, 671–675 (2012).
MessaoudiI, C., Boudier, T., Sorzano, C. O. S. & Marco, S. TomoJ: tomography software for three-dimensional reconstruction in transmission electron microscopy. BMC Bioinform. 8, 288 (2007).
Slodzian, G., Hillion, F., Stadermann, F. J. & Zinner, E. QSA influences on isotopic ratio measurements. Appl. Surf. Sci. 231–232, 874–877 (2004).
Geiss, J. & Gloeckler, G. Abundances of deuterium and helium-3 in the protosolar cloud. Space Sci. Rev. 84, 239–250 (1998).
Ceccarelli, C. et al. in Protostars and Planets VI (eds Beuther, H. et al.) 859–882 (Univ. of Arizona Press, 2014).
Crovisier, J. et al. The composition of ices in comet C/1995 O1 (Hale–Bopp) from radio spectroscopy. Further results and upper limits on undetected species. Astron. Astrophys. 418, 1141–1157 (2004).
Paquette, J. A. et al. D/H in the refractory organics of comet 67P/Churyumov-Gerasimenko measured by Rosetta/COSIMA. Mon. Not. R. Astron. Soc. 504, 4940–4951 (2021).
Brown, P. D. & Millar, T. J. Models of the gas–grain interaction – deuterium chemistry. Mon. Not. R. Astron. Soc. 237, 661–671 (1989).
Acknowledgements
The micrometeorites were collected at Concordia Station (Project No. 1120), and their collection was supported by the French Polar Institute (IPEV). We are grateful to IPEV for financial support and to IPEV and National Antarctic Research Program staff for logistical help. This work was financially supported by the French National Agency for Research (Project COMETOR 18-CE31-0011), Région Île-de-France (Major Interest Area ACAV+ under Project C3E), the French National Centre for Space Studies and the French National Centre for Scientific Research (French National Institute for Earth Sciences and Astronomy, the Physics and Chemistry of the Interstellar Medium Program, the National Institute of Nuclear and Particle Physics and the Laboratory of Excellence for Physics of the Two Infinite and of Origins). L.R. thanks the European Research Council for funding (Project HYDROMA under Grant Agreement No. 819587). The NanoSIMS facility in Paris was established by funds from the French National Centre for Scientific Research, Région Île-de-France, Ministère délégué à l’Enseignement Supérieur et à la Recherche, and the Muséum National d’Histoire Naturelle. We acknowledge the CurieCore Tech for the use of Curie-NanoSIMS. J.R. thanks G. Slodzian for his help and precious insights on the NanoSIMS instrument and data treatment.
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J.D., E.D. and C.E. conceived and designed the study. J.D., E.D., C.E. and L.D. participated in the fieldwork and the selection of samples. L.D., J.R. and B.G. performed the scanning electron microscopy of the samples. L.R.N., T.-D.W., L.R. and S.M. conceived and performed the NanoSIMS experiments. L.R.N., L.R. and J.D. provided the standards. J.R., N.B. and J.D. participated in the NanoSIMS experiments. R.M.S. performed the focused ion beam microscopy of the samples. J.R. analysed and interpreted the data. J.R., J.D., E.D., C.E., L.R.N., R.M.S. and L.R. wrote the paper.
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Extended data
Extended Data Fig. 1 Isotopic maps of DC06-18.
(a, b, c) δD, δ15N and δ13C maps of the first fragment of DC06-18. (d, e, f) δD, δ15N and δ13C maps of the second fragment of DC06-18. (g, h, i) δD, δ15N and δ13C maps of the third fragment of DC06-18. The white scale bar is 5 µm.
Extended Data Fig. 2 Isotopic maps of DC06-43.
(a, b, c) δD, δ15N and δ13C maps. The white scale bar is 2 µm.
Extended Data Fig. 3 Isotopic maps of DC16-309.
(a, b, c) δD, δ15N and δ13C maps. The white scale bar is 1 µm.
Extended Data Fig. 4 δ13C versus δD isotopic composition of the 4 UCAMMs presented in this paper.
DC06-94, DC06-43, DC06-18 and DC16-309 are plotted in gray, blue, green, and red, respectively. Histograms in the margins indicate the analyzed area in µm² (in log scale). Data points are the mean isotopic ratios measured in individual regions of interest +/- one standard deviation (Methods-Data reduction and Supplementary Table). Isodensity contours of the density functions at 5% (threshold), 33% and 66% are displayed by the solid lines.
Extended Data Fig. 5 Comparison of the H and N isotopic compositions measured in UCAMMs with literature data.
DC06-94, DC06-43, DC06-18 and DC16-309 are displayed with gray, blue, green, and red contours, respectively. Literature data for IDPs10,14,15 are plotted with gray dots. IOM of CR, CM, CI and CO chondrites1 are plotted with orange, red, yellow and pink diamonds, respectively. The bulk Ryugu composition18 is displayed by the yellow star. Error bars are one standard deviation.
Extended Data Fig. 6 Comparison of the C and N isotopic composition of the 4 analyzed UCAMMs with literature data.
(a, b) DC06-94, DC06-43, DC06-18 and DC16-309 are in gray, blue, green and red contours. Literature data for IDPs (a) and carbonaceous matter from meteorites (b) are superimposed. Bulk IDPs10,11,12,13,14,15 and hotspots in IDPs11,12,13,14 are indicated in the panel a) as dark gray dots and yellow dots with one standard deviation error bars. Bulk IOM data are indicated as large diamonds in orange (CR), red (CM), yellow (CI) and pink (CO)1. Carbonaceous grains in CR, CM, CI and CO3,5,6,7,8,9 are indicated as small diamonds with the same color code. The average composition of carbonaceous asteroid Ryugu grains18 from the Hayabusa2 JAXA return sample mission is reported as a yellow star. The shaded area and the ellipse represent the range of variation of the solar δ15N and δ13C value.
Extended Data Fig. 7 H (left), N (middle) and C (right) isotopic compositions of the 4 UCAMMs plotted against their analyzed surfaces.
Red: DC16-309; blue: DC06-43; green: DC06-18; gray: DC06-94.
Extended Data Fig. 8 Comparison of the H, C and N isotopic composition of UCAMMs and Ryugu grains.
(a) N and H isotopic compositions. (b) N and C isotopic compositions. UCAMMs are displayed with grey, red, blue, and green circles. Ryugu samples18 are plotted with yellow circles. The size of the circles indicates the size of the measured ROIs in UCAMMs and Ryugu grains. The bulk composition of the C-rich particles in Ryugu grains is displayed by a star. The distinct N and C isotopic compositions evidenced in UCAMMs are observed at small scale in Ryugu grains.
Supplementary information
Supplementary Table 1
Ion counts and H, C and N isotopic ratios measured in the ROIs defined on the four UCAMMs.
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Rojas, J., Duprat, J., Dartois, E. et al. Nitrogen-rich organics from comets probed by ultra-carbonaceous Antarctic micrometeorites. Nat Astron (2024). https://doi.org/10.1038/s41550-024-02364-y
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DOI: https://doi.org/10.1038/s41550-024-02364-y