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Comets are considered the most primitive planetary bodies in our Solar System. ESA's Rosetta mission to Jupiter family comet 67P/Churyumov-Gerasimenko (67P/CG) has provided a wealth of isotope data which expanded the existing data sets on isotopic compositions of comets considerably. In a previous paper (Hoppe et al. in Space Sci. Rev. 214:106, 2018) we reviewed the results for comet 67P/CG from the first four years of data reduction after arrival of Rosetta at the comet in August 2014 and discussed them in the context of respective meteorite data. Since then important new isotope data of several elements, among them the biogenic elements H, C, N, and O, for comet 67P/CG, the Tagish Lake meteorite, and C-type asteroid Ryugu became available which provide new insights into the formation conditions of small planetary bodies in the Solar System's earliest history. To complement the picture on comet 67P/CG and its context to other primitive Solar System materials, especially meteorites, that emerged from our previous paper, we review here the isotopic compositions of H, C, and N in various volatile molecules, of O in water and a suite of other molecules, of the halogens Cl and Br, and of the noble gas Kr in comet 67P/CG. Furthermore, we also review the H isotope data obtained in the refractory organics of the dust grains collected in the coma of 67P/CG. These data are compared with the respective meteoritic and Ryugu data and spectroscopic observations of other comets and extra-solar environments; Cl, Br, and Kr data are also evaluated in the context of a potential late supernova contribution, as suggested by the Si- and S-isotopic data of 67P/CG., Competing Interests: Competing InterestsThe authors declare that they have no conflict of interest., (© The Author(s) 2023.)

In-situ study of comet 1P/Halley during its 1986 apparition revealed a surprising abundance of organic coma species. It remained unclear, whether or not these species originated from polymeric matter. Now, high-resolution mass-spectrometric data collected at comet 67P/Churyumov-Gerasimenko by ESA's Rosetta mission unveil the chemical structure of complex cometary organics. Here, we identify an ensemble of individual molecules with masses up to 140 Da while demonstrating inconsistency of the data with relevant amounts of polymeric matter. The ensemble has an average composition of C 1 H 1.56 O 0.134 N 0.046 S 0.017 , identical to meteoritic soluble organic matter, and includes a plethora of chain-based, cyclic, and aromatic hydrocarbons at an approximate ratio of 6:3:1. Its compositional and structural properties, except for the H/C ratio, resemble those of other Solar System reservoirs of organics-from organic material in the Saturnian ring rain to meteoritic soluble and insoluble organic matter -, which is compatible with a shared prestellar history., (© 2022. The Author(s).)

Primitive objects like comets hold important information on the material that formed our solar system. Several comets have been visited by spacecraft and many more have been observed through Earth- and space-based telescopes. Still our understanding remains limited. Molecular abundances in comets have been shown to be similar to interstellar ices and thus indicate that common processes and conditions were involved in their formation. The samples returned by the Stardust mission to comet Wild 2 showed that the bulk refractory material was processed by high temperatures in the vicinity of the early sun. The recent Rosetta mission acquired a wealth of new data on the composition of comet 67P/Churyumov-Gerasimenko (hereafter 67P/C-G) and complemented earlier observations of other comets. The isotopic, elemental, and molecular abundances of the volatile, semi-volatile, and refractory phases brought many new insights into the origin and processing of the incorporated material. The emerging picture after Rosetta is that at least part of the volatile material was formed before the solar system and that cometary nuclei agglomerated over a wide range of heliocentric distances, different from where they are found today. Deviations from bulk solar system abundances indicate that the material was not fully homogenized at the location of comet formation, despite the radial mixing implied by the Stardust results. Post-formation evolution of the material might play an important role, which further complicates the picture. This paper discusses these major findings of the Rosetta mission with respect to the origin of the material and puts them in the context of what we know from other comets and solar system objects., (© The Author(s) 2020.)

The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) suite of instruments operated throughout the over two years of the Rosetta mission operations in the vicinity of comet 67P/Churyumov-Gerasimenko. It measured gas densities and composition throughout the comet's atmosphere, or coma. Here we present two-years' worth of measurements of the relative densities of the four major volatile species in the coma of the comet, H 2 O, CO 2 , CO and O 2 , by one of the ROSINA sub-systems called the Double Focusing Mass Spectrometer (DFMS). The absolute total gas densities were provided by the Comet Pressure Sensor (COPS), another ROSINA sub-system. DFMS is a very high mass resolution and high sensitivity mass spectrometer able to resolve at a tiny fraction of an atomic mass unit. We have analyzed the combined DFMS and COPS measurements using an inversion scheme based on spherical harmonics that solves for the distribution of potential surface activity of each species as the comet rotates, changing solar illumination, over short time intervals and as the comet changes distance from the sun and orientation of its spin axis over long time intervals. We also use the surface boundary conditions derived from the inversion scheme to simulate the whole coma with our fully kinetic Direct Simulation Monte Carlo model and calculate the production rates of the four major species throughout the mission. We compare the derived production rates with revised remote sensing observations by the Visible and Infrared Thermal Imaging Spectrometer (VIRTIS) as well as with published observations from the Microwave Instrument for the Rosetta Orbiter (MIRO). Finally we use the variation of the surface production of the major species to calculate the total mass loss over the mission and, for different estimates of the dust/gas ratio, calculate the variation of surface loss all over the nucleus.

Context: Pre-equinox measurements of comet 67P/Churyumov-Gerasimenko with the mass spectrometer ROSINA/DFMS on board the Rosetta spacecraft revealed a strongly heterogeneous coma. The abundances of major and various minor volatile species were found to depend on the latitude and longitude of the nadir point of the spacecraft. The observed time variability of coma species remained consistent for about three months up to equinox. The chemical variability could be generally interpreted in terms of surface temperature and seasonal effects superposed on some kind of chemical heterogeneity of the nucleus., Aims: We compare here pre-equinox (inbound) ROSINA/DFMS measurements from 2014 to measurements taken after the outbound equinox in 2016, both at heliocentric distances larger than 3 AU. For a direct comparison we limit our observations to the southern hemisphere., Methods: We report the similarities and differences in the concentrations and time variability of neutral species under similar insolation conditions (heliocentric distance and season) pre- and post-equinox, and interpret them in light of the previously published observations. In addition, we extend both the pre- and post-equinox analysis by comparing species concentrations with a mixture of CO 2 and H 2 O., Results: Our results show significant changes in the abundances of neutral species in the coma from pre- to post-equinox that are indicative of seasonally driven nucleus heterogeneity., Conclusions: The observed pre- and post-equinox patterns can generally be explained by the strong erosion in the southern hemisphere that moves volatile-rich layers near the surface.

Recent high-resolution in situ mass spectrometry at comet 67P/Churyumov-Gerasimenko visited by European Space Agency's Rosetta spacecraft raised the question, if sublimating ammonium salts can unequivocally be detected in the cometary coma. In laboratory experiments with the twin model of the space instrument, two prototypic ammonium salts NH 4 B, namely, ammonium chloride (B = Cl - ) and ammonium formate (B = HCOO - ) (as well as methodologically relevant isotopologues), were allowed to sublimate in vacuum while mass spectra were collected. High-resolution electron-impact ionization mass spectrometry provides an outstanding experimental tool to investigate the complex physicochemical processes occurring during the sublimation of ammonium salts. Sublimation of ammonium chloride led to the observation of the ammonium cation NH 4 + and the chloramide molecule NH 2 Cl in the neutral gas mode of the instrument. These observations could be jointly interpreted as indirect evidence for the existence of a neutral gaseous parent species (either as the molecular complex NH 3 ···HB or the double-ionic species NH 4 + ···B - ). However, the qualitative fragmentation pattern we present for 13 C 15 N-ammonium formate suggests an alternative route of NH 4 + production within the ionization region of the instrument, namely, by protonation/hydrogenation. Besides NH 4 + , other species were observed that were formed in protonation/hydrogenation reactions. Moreover, together with the two major species from the decomposition of the salt, ammonia and formic acid, three minor species also contributed to the fragmentation pattern: HCN/HNC, HOCN/HNCO, and CH 3 NO. Like chloramide, formamide (CH 3 NO) also is a secondary species probably formed in a pseudo-intramolecular chemical reaction while ammonia and the respective acid are in a state of association. HCN/HNC and HOCN/HNCO are ternary products coming out of formamide decomposition reactions. We discuss our experimental findings, summarized in a tentative chemical reaction network, in light of the available theoretical literature and highlight their relevance for the interpretation of in situ measurements in space research.

The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis mass spectrometer Double Focusing Mass Spectrometer on board the European Space Agency's Rosetta spacecraft detected the major isotopes of the noble gases argon, krypton, and xenon in the coma of comet 67P/Churyumov-Gerasimenko. Earlier, it was found that xenon exhibits an isotopic composition distinct from anywhere else in the solar system. However, argon isotopes, within error, were shown to be consistent with solar isotope abundances. This discrepancy suggested an additional exotic component of xenon in comet 67P/Churyumov-Gerasimenko. We show that krypton also exhibits an isotopic composition close to solar. Furthermore, we found the argon to krypton and the krypton to xenon ratios in the comet to be lower than solar, which is a necessity to postulate an addition of exotic xenon in the comet.

Asteroids and comets are the remnants of the swarm of planetesimals from which the planets ultimately formed, and they retain records of processes that operated prior to and during planet formation. They are also likely the sources of most of the water and other volatiles accreted by Earth. In this review, we discuss the nature and probable origins of asteroids and comets based on data from remote observations, in situ measurements by spacecraft, and laboratory analyses of meteorites derived from asteroids. The asteroidal parent bodies of meteorites formed ≤4 Ma after Solar System formation while there was still a gas disk present. It seems increasingly likely that the parent bodies of meteorites spectroscopically linked with the E-, S-, M- and V-type asteroids formed sunward of Jupiter's orbit, while those associated with C- and, possibly, D-type asteroids formed further out, beyond Jupiter but probably not beyond Saturn's orbit. Comets formed further from the Sun than any of the meteorite parent bodies, and retain much higher abundances of interstellar material. CI and CM group meteorites are probably related to the most common C-type asteroids, and based on isotopic evidence they, rather than comets, are the most likely sources of the H and N accreted by the terrestrial planets. However, comets may have been major sources of the noble gases accreted by Earth and Venus. Possible constraints that these observations can place on models of giant planet formation and migration are explored.

Comets are considered the most primitive planetary bodies in our Solar System, i.e., they should have best preserved the solid components of the matter from which our Solar System formed. ESA's recent Rosetta mission to Jupiter family comet 67P/Churyumov-Gerasimenko (67P/CG) has provided a wealth of isotope data which expanded the existing data sets on isotopic compositions of comets considerably. In this paper we review our current knowledge on the isotopic compositions of H, C, N, O, Si, S, Ar, and Xe in primitive Solar System materials studied in terrestrial laboratories and how the Rosetta data acquired with the ROSINA (Rosetta Orbiter Sensor for Ion and Neutral Analysis) and COSIMA (COmetary Secondary Ion Mass Analyzer) mass spectrometer fit into this picture. The H, Si, S, and Xe isotope data of comet 67P/CG suggest that this comet might be particularly primitive and might have preserved large amounts of unprocessed presolar matter. We address the question whether the refractory Si component of 67P/CG contains a presolar isotopic fingerprint from a nearby Type II supernova (SN) and discuss to which extent C and O isotope anomalies originating from presolar grains should be observable in dust from 67P/CG. Finally, we explore whether the isotopic fingerprint of a potential late SN contribution to the formation site of 67P/CG in the solar nebula can be seen in the volatile component of 67P/CG., (© The Author(s) 2018.)

The European Rosetta mission has been following comet 67P/Churyumov-Gerasimenko for 2 years, studying the nucleus and coma in great detail. For most of these 2 years the Rosetta Orbiter Sensor for Ion and Neutral Analysis (ROSINA) has analysed the volatile part of the coma. With its high mass resolution and sensitivity it was able to not only detect deuterated water HDO, but also doubly deuterated water, D 2 O and deuterated hydrogen sulfide HDS. The ratios for [HDO]/[H 2 O], [D 2 O]/[HDO] and [HDS]/[H 2 S] derived from our measurements are (1.05 ± 0.14) × 10 -3 , (1.80 ± 0.9) × 10 -2 and (1.2 ± 0.3) × 10 -3 , respectively. These results yield a very high ratio of 17 for [D 2 O]/[HDO] relative to [HDO]/[H 2 O]. Statistically one would expect just 1/4. Such a high value can be explained by cometary water coming unprocessed from the presolar cloud, where water is formed on grains, leading to high deuterium fractionation. The high [HDS]/[H 2 S] ratio is compatible with upper limits determined in low-mass star-forming regions and also points to a direct correlation of cometary H 2 S with presolar grain surface chemistry.This article is part of the themed issue 'Cometary science after Rosetta'., (© 2017 The Author(s).)

The origin of cometary matter and the potential contribution of comets to inner-planet atmospheres are long-standing problems. During a series of dedicated low-altitude orbits, the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) on the Rosetta spacecraft analyzed the isotopes of xenon in the coma of comet 67P/Churyumov-Gerasimenko. The xenon isotopic composition shows deficits in heavy xenon isotopes and matches that of a primordial atmospheric component. The present-day Earth atmosphere contains 22 ± 5% cometary xenon, in addition to chondritic (or solar) xenon., (Copyright © 2017, American Association for the Advancement of Science.)

The presence of solid carbonaceous matter in cometary dust was established by the detection of elements such as carbon, hydrogen, oxygen and nitrogen in particles from comet 1P/Halley. Such matter is generally thought to have originated in the interstellar medium, but it might have formed in the solar nebula-the cloud of gas and dust that was left over after the Sun formed. This solid carbonaceous material cannot be observed from Earth, so it has eluded unambiguous characterization. Many gaseous organic molecules, however, have been observed; they come mostly from the sublimation of ices at the surface or in the subsurface of cometary nuclei. These ices could have been formed from material inherited from the interstellar medium that suffered little processing in the solar nebula. Here we report the in situ detection of solid organic matter in the dust particles emitted by comet 67P/Churyumov-Gerasimenko; the carbon in this organic material is bound in very large macromolecular compounds, analogous to the insoluble organic matter found in the carbonaceous chondrite meteorites. The organic matter in meteorites might have formed in the interstellar medium and/or the solar nebula, but was almost certainly modified in the meteorites' parent bodies. We conclude that the observed cometary carbonaceous solid matter could have the same origin as the meteoritic insoluble organic matter, but suffered less modification before and/or after being incorporated into the comet.

Comets have been considered to be representative of icy planetesimals that may have contributed a significant fraction of the volatile inventory of the terrestrial planets. For example, comets must have brought some water to Earth. However, the magnitude of their contribution is still debated. We report the detection of argon and its relation to the water abundance in the Jupiter family comet 67P/Churyumov-Gerasimenko by in situ measurement of the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) mass spectrometer aboard the Rosetta spacecraft. Despite the very low intensity of the signal, argon is clearly identified by the exact determination of the mass of the isotope (36)Ar and by the (36)Ar/(38)Ar ratio. Because of time variability and spatial heterogeneity of the coma, only a range of the relative abundance of argon to water can be given. Nevertheless, this range confirms that comets of the type 67P/Churyumov-Gerasimenko cannot be the major source of Earth's major volatiles.

The provenance of water and organic compounds on Earth and other terrestrial planets has been discussed for a long time without reaching a consensus. One of the best means to distinguish between different scenarios is by determining the deuterium-to-hydrogen (D/H) ratios in the reservoirs for comets and Earth's oceans. Here, we report the direct in situ measurement of the D/H ratio in the Jupiter family comet 67P/Churyumov-Gerasimenko by the ROSINA mass spectrometer aboard the European Space Agency's Rosetta spacecraft, which is found to be (5.3 ± 0.7) × 10(-4)—that is, approximately three times the terrestrial value. Previous cometary measurements and our new finding suggest a wide range of D/H ratios in the water within Jupiter family objects and preclude the idea that this reservoir is solely composed of Earth ocean-like water., (Copyright © 2015, American Association for the Advancement of Science.)

Life Investigation For Enceladus (LIFE) presents a low-cost sample return mission to Enceladus, a body with high astrobiological potential. There is ample evidence that liquid water exists under ice coverage in the form of active geysers in the "tiger stripes" area of the southern Enceladus hemisphere. This active plume consists of gas and ice particles and enables the sampling of fresh materials from the interior that may originate from a liquid water source. The particles consist mostly of water ice and are 1-10 μ in diameter. The plume composition shows H(2)O, CO(2), CH(4), NH(3), Ar, and evidence that more complex organic species might be present. Since life on Earth exists whenever liquid water, organics, and energy coexist, understanding the chemical components of the emanating ice particles could indicate whether life is potentially present on Enceladus. The icy worlds of the outer planets are testing grounds for some of the theories for the origin of life on Earth. The LIFE mission concept is envisioned in two parts: first, to orbit Saturn (in order to achieve lower sampling speeds, approaching 2 km/s, and thus enable a softer sample collection impact than Stardust, and to make possible multiple flybys of Enceladus); second, to sample Enceladus' plume, the E ring of Saturn, and the Titan upper atmosphere. With new findings from these samples, NASA could provide detailed chemical and isotopic and, potentially, biological compositional context of the plume. Since the duration of the Enceladus plume is unpredictable, it is imperative that these samples are captured at the earliest flight opportunity. If LIFE is launched before 2019, it could take advantage of a Jupiter gravity assist, which would thus reduce mission lifetimes and launch vehicle costs. The LIFE concept offers science returns comparable to those of a Flagship mission but at the measurably lower sample return costs of a Discovery-class mission.