Thermal behavior of astrophysical amorphous molecular ices.

Ice is a major component of astrophysical environments - from interstellar molecular clouds through protoplanetary disks to evolved solar systems. Ice and complex organic matter coexist in these environments as well, and it is thought primordial ice brought the molecules of life to Earth four billion years ago, which could have kickstarted the origin of life on Earth. To understand the journey of ice and organics from their origins to becoming a part of evolved planetary systems, it is important to complement high spatial and spectral resolution telescopes such as JWST with laboratory experimental studies that provide deeper insight into the processes that occur in these astrophysical environments. Our laboratory studies are aimed at providing this knowledge. In this article we present simultaneous mass spectrometric and infrared spectroscopic investigation on how molecular ice mixtures behave at different temperatures and how this information is critical to interpret observational data from protoplanetary disks as well as comets. We find that amorphous to crystalline water ice transformation is the most critical phenomenon that differentiates between outgassing of trapped volatiles such as CO2vs. outgassing of pure molecular ice domains of the same in a mixed molecular ice. Crystalline water ice is found to trap only a small fraction of other volatiles (<5%), indicating ice grain composition in astrophysical and planetary environments must be different depending on whether the ice is in amorphous phase or transformed into crystalline phase, even if the crystalline ice undergoes radiation-induced amorphization subsequently. Crystallization of water ice is a key differentiator for many ices in astronomical environments as well as in our Solar System.

Ammonium Salts as a Source of Small Molecules Observed with High-Resolution Electron-Impact Ionization Mass Spectrometry.

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 NH4B, 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 NH4+ and the chloramide molecule NH2Cl 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 NH3···HB or the double-ionic species NH4+···B-). However, the qualitative fragmentation pattern we present for 13C15N-ammonium formate suggests an alternative route of NH4+ production within the ionization region of the instrument, namely, by protonation/hydrogenation. Besides NH4+, 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 CH3NO. Like chloramide, formamide (CH3NO) 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.

A Comparison of Presolar Isotopic Signatures in Laboratory-Studied Primitive Solar System Materials and Comet 67P/Churyumov-Gerasimenko: New Insights from Light Elements, Halogens, and Noble Gases.

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.

Complex organosulfur molecules on comet 67P: Evidence from the ROSINA measurements and insights from laboratory simulations.

The ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument aboard the Rosetta mission revolutionized our understanding of cometary material composition. One of Rosetta's key findings is the complexity of the composition of comet 67P/Churyumov-Gerasimenko. Here, we used ROSINA data to analyze dust particles that were volatilized during a dust event in September 2016 and report the detection of large organosulfur species and an increase in the abundances of sulfurous species previously detected in the coma. Our data support the presence of complex sulfur-bearing organics on the surface of the comet. In addition, we conducted laboratory simulations that show that this material may have formed from chemical reactions that were initiated by the irradiation of mixed ices containing H2S. Our findings highlight the importance of sulfur chemistry in cometary and precometary materials and the possibility of characterizing organosulfur materials in other comets and small icy bodies using the James Webb Space Telescope.

The Plasma Environment of Comet 67P/Churyumov-Gerasimenko.

The environment of a comet is a fascinating and unique laboratory to study plasma processes and the formation of structures such as shocks and discontinuities from electron scales to ion scales and above. The European Space Agency's Rosetta mission collected data for more than two years, from the rendezvous with comet 67P/Churyumov-Gerasimenko in August 2014 until the final touch-down of the spacecraft end of September 2016. This escort phase spanned a large arc of the comet's orbit around the Sun, including its perihelion and corresponding to heliocentric distances between 3.8 AU and 1.24 AU. The length of the active mission together with this span in heliocentric and cometocentric distances make the Rosetta data set unique and much richer than sets obtained with previous cometary probes. Here, we review the results from the Rosetta mission that pertain to the plasma environment. We detail all known sources and losses of the plasma and typical processes within it. The findings from in-situ plasma measurements are complemented by remote observations of emissions from the plasma. Overviews of the methods and instruments used in the study are given as well as a short review of the Rosetta mission. The long duration of the Rosetta mission provides the opportunity to better understand how the importance of these processes changes depending on parameters like the outgassing rate and the solar wind conditions. We discuss how the shape and existence of large scale structures depend on these parameters and how the plasma within different regions of the plasma environment can be characterised. We end with a non-exhaustive list of still open questions, as well as suggestions on how to answer them in the future.

On the Origin and Evolution of the Material in 67P/Churyumov-Gerasimenko.

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 Surface Distributions of the Production of the Major Volatile Species, H2O, CO2, CO and O2, from the Nucleus of Comet 67P/Churyumov-Gerasimenko throughout the Rosetta Mission as Measured by the ROSINA Double Focusing Mass Spectrometer.

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, H2O, CO2, CO and O2, 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.

Presolar Isotopic Signatures in Meteorites and Comets: New Insights from the Rosetta Mission to Comet 67P/Churyumov-Gerasimenko.

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.

Krypton isotopes and noble gas abundances in the coma of comet 67P/Churyumov-Gerasimenko.

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.

The presence of clathrates in comet 67P/Churyumov-Gerasimenko.

Cometary nuclei are considered to most closely reflect the composition of the building blocks of our solar system. As such, comets carry important information about the prevalent conditions in the solar nebula before and after planet formation. Recent measurements of the time variation of major and minor volatile species in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko (67P) by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument onboard Rosetta provide insight into the possible origin of this comet. The observed outgassing pattern indicates that the nucleus of 67P contains crystalline ice, clathrates, and other ices. The observed outgassing is not consistent with gas release from an amorphous ice phase with trapped volatile gases. If the building blocks of 67P were formed from crystalline ices and clathrates, then 67P would have agglomerated from ices that were condensed and altered in the protosolar nebula closer to the Sun instead of more pristine ices originating from the interstellar medium or the outskirts of the disc, where amorphous ice may dominate.

Prebiotic chemicals-amino acid and phosphorus-in the coma of comet 67P/Churyumov-Gerasimenko.

The importance of comets for the origin of life on Earth has been advocated for many decades. Amino acids are key ingredients in chemistry, leading to life as we know it. Many primitive meteorites contain amino acids, and it is generally believed that these are formed by aqueous alterations. In the collector aerogel and foil samples of the Stardust mission after the flyby at comet Wild 2, the simplest form of amino acids, glycine, has been found together with precursor molecules methylamine and ethylamine. Because of contamination issues of the samples, a cometary origin was deduced from the (13)C isotopic signature. We report the presence of volatile glycine accompanied by methylamine and ethylamine in the coma of 67P/Churyumov-Gerasimenko measured by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) mass spectrometer, confirming the Stardust results. Together with the detection of phosphorus and a multitude of organic molecules, this result demonstrates that comets could have played a crucial role in the emergence of life on Earth.

Cometary science. Birth of a comet magnetosphere: a spring of water ions.

The Rosetta mission shall accompany comet 67P/Churyumov-Gerasimenko from a heliocentric distance of >3.6 astronomical units through perihelion passage at 1.25 astronomical units, spanning low and maximum activity levels. Initially, the solar wind permeates the thin comet atmosphere formed from sublimation, until the size and plasma pressure of the ionized atmosphere define its boundaries: A magnetosphere is born. Using the Rosetta Plasma Consortium ion composition analyzer, we trace the evolution from the first detection of water ions to when the atmosphere begins repelling the solar wind (~3.3 astronomical units), and we report the spatial structure of this early interaction. The near-comet water population comprises accelerated ions (<800 electron volts), produced upstream of Rosetta, and lower energy locally produced ions; we estimate the fluxes of both ion species and energetic neutral atoms.

Detection of argon in the coma of comet 67P/Churyumov-Gerasimenko.

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.

Nitrilotriacetate therapy of alkaline earth urinary calculi

Los mecanismos por los cuales la administración oral de nitrilotriacetato (NTA) previene y disuelve cálculos urinarios compuestos por brushita, CaH804 . 2HZ0 y struvita, MgNH4PO4 . 6 H2O, han sido estudiados en ratas por administración intravenosa del quelato a dosis bajas, 14 micronmol/kg, intermedias, 41 micronmol/kg y la dosis máxima tolerada de 82 micronmol/kg. Con todas las dosis se observó una rápida fosfaturia. El Ca y NTA urinario variaron con la dosis y el tiempo. En la primera hora posinyección, para todas las dosis de NTA, el calcio urinario presentó valores mayores o iguales que el control. En la segunda hora la excreción fue igual o más baja que los controles y fue uniformemente bajo en la tercera hora. La variable excreción de NTA y calcio tuvo una relación máxima NTA/Ca = 5,9 en la segunda hora después de la administración de 82 micronmol/kg. Los datos sugieren que el NTA en plasma establece un buffer de calcio hipocalcémico, el cual provoca un estímulo para la secreción de PTH. El aumento resultante de la reabsorción renal de Ca y CaNTA, a partir del filtrado glomerular, establece la relación variable NTA/Ca en orina. Los límites del proceso están establecidos por la hipocalcemia relacionada a la dosis de NTA, la máxima capacidad de reabsorción del Ca por el riñón y la solubilidad del CaNTA en orina. Además de la potencial utilidad terapéutica, la inusual capacidad del NTA para imponer una sobrecarga de calcio al riñón, simultáneamente con hipocalcemia, sugiere su utilización como una prueba funcional paratiroidea y renal en el metabolismo del calcio

Nitrilotriacetate therapy of alkaline earth urinary calculi

Los mecanismos por los cuales la administración oral de nitrilotriacetato (NTA) previene y disuelve cálculos urinarios compuestos por brushita, CaH804 . 2HZ0 y struvita, MgNH4PO4 . 6 H2O, han sido estudiados en ratas por administración intravenosa del quelato a dosis bajas, 14 micronmol/kg, intermedias, 41 micronmol/kg y la dosis máxima tolerada de 82 micronmol/kg. Con todas las dosis se observó una rápida fosfaturia. El Ca y NTA urinario variaron con la dosis y el tiempo. En la primera hora posinyección, para todas las dosis de NTA, el calcio urinario presentó valores mayores o iguales que el control. En la segunda hora la excreción fue igual o más baja que los controles y fue uniformemente bajo en la tercera hora. La variable excreción de NTA y calcio tuvo una relación máxima NTA/Ca = 5,9 en la segunda hora después de la administración de 82 micronmol/kg. Los datos sugieren que el NTA en plasma establece un buffer de calcio hipocalcémico, el cual provoca un estímulo para la secreción de PTH. El aumento resultante de la reabsorción renal de Ca y CaNTA, a partir del filtrado glomerular, establece la relación variable NTA/Ca en orina. Los límites del proceso están establecidos por la hipocalcemia relacionada a la dosis de NTA, la máxima capacidad de reabsorción del Ca por el riñón y la solubilidad del CaNTA en orina. Además de la potencial utilidad terapéutica, la inusual capacidad del NTA para imponer una sobrecarga de calcio al riñón, simultáneamente con hipocalcemia, sugiere su utilización como una prueba funcional paratiroidea y renal en el metabolismo del calcio (AU)