Geochemical Journal, Vol. 48, pp. 511 to 518, 2014
doi:10.2343/geochemj.2.0330
Interstellar and interplanetary carbonaceous solids in the laboratory
EMMANUEL DARTOIS,1,2* CECILE E NGRAND,3 ROSARIO BRUNETTO,1,2 JEAN DUPRAT,3 THOMAS PINO,4
ERIC QUIRICO,5 LAURENT REMUSAT,6 NOEMIE BARDIN ,3 G IACOMO BRIANI ,3 SMAIL MOSTEFAOUI,6
GILLES MORINAUD,1,2 B RUNO C RANE,1,2 NICOLAS SZWEC ,1,2 LUCIE D ELAUCHE,3 FREDERIC JAMME,7
CHRISTOPHE SAND7 and PAUL DUMAS7
1
CNRS-INSU, Institut d’Astrophysique Spatiale, UMR 8617, 91405 Orsay, France
Université Paris Sud, Institut d’Astrophysique Spatiale, UMR 8617, bâtiment 121, 91405 Orsay, France
3
Centre de Spectrométrie Nucléaire et de Spectrométrie de Masse (CSNSM), Université Paris-Sud,
UMR 8609-CNRS/IN2P3, F-91405 Orsay, France
4
Institut des Sciences Moléculaires d’Orsay (ISMO), UMR 8214-CNRS Université Paris Sud,
bât.210, F-91405 Orsay Cedex, France
5
UJF-Grenoble 1/CNRS-INSU, Institut de Planétologie et dAstrophysique de Grenoble (IPAG),
UMR 5274-CNRS INSU, F-38041 Grenoble, France
6
Institut de Minéralogie, de Physique des Matériaux, et de Cosmochimie (IMPMC) - Sorbonne Universités - UMR 7590 CNRS,
UPMC, IRD, Muséum National d’Histoire Naturelle, 61 rue Buffon, F-75005 Paris, France
7
Synchrotron SOLEIL, L’orme des Merisiers, BP 48, Saint Aubin, F-91192 Gif sur Yvette, France
2
(Received January 10, 2014; Accepted September 1, 2014)
The interstellar medium (ISM) is a physico-chemical laboratory where extreme conditions are encountered and where
particular environmental parameters (e.g., density, reactant nature, radiation, temperature, time scales) define the composition of matter. With present observational possibilities, the fundamental question regarding the possible link between
ISM and solar system samples can be addressed by astrophysicists, planetologists, and cosmochemists. This article focuses on observations of diffuse ISM and dust components of molecular clouds, setting constraints on the composition of
organic solids and large molecules associated with matter cycling in the Galaxy. This study aims at drawing some
commonalities and differences between the materials found in the Solar System and those found in interstellar dust.
Keywords: interstellar dust, Solar System, interplanetary dust, cosmochemistry, astrochemistry, organic chemistry
stellar medium (DISM), and molecular clouds (MC).
These observations give essential access to the molecular functionality of these solids, rarely strong constraints
related to their elemental composition, and their isotopic
fractionation, mostly in the gas phase. Astrochemists can
bring in additional information from the study of analogues produced in the laboratory and placed in simulated space environments.
In the interstellar dust lifecycle, interstellar matter
bounces back and forth between various phases. During
this process, stellar mass loss by old stars contributes significantly to dust production and injection in the diffuse
medium, adding to the mass fraction injected by supernova and young star jets, which is debated (Jones, 2001;
Dartois, 2005b; Tielens et al., 2005; Robitaille and
Whitney, 2010; Matsuura et al., 2011). The solid interstellar materials observed between these phases are typically divided in three main categories, including minerals (among which the silicates play an important role);
“carbonaceous matter,” comprising almost any organic
matter; and ices, which are encountered in the densest
INTRODUCTION
While cosmochemists interested in studying
(micro-)meteorites chemical composition can
spectroscopically examine any collected extraterrestrial
material in the laboratory (Orthous-Daunay et al., 2013;
Dartois et al., 2013; Brunetto et al., 2011; Kebukawa et
al., 2011; Sandford et al., 2006; Flynn et al., 2003, and
references therein), astrochemists must rely on interstellar medium (ISM) investigations based on remote observations to monitor and analyze the physico-chemical composition of interstellar solids (Spoon et al., 2007; Dartois
and Muñoz-Caro, 2007; Van Diedenhoven et al., 2004;
Chiar et al., 2002; Pendleton et al., 1994; and reference
therein). The composition of solid state matter can be
deduced by observing infrared dust absorption and emission from stellar winds, recently born stars, diffuse inter*Corresponding author (e-mail: [email protected])
Copyright © 2014 by The Geochemical Society of Japan.
511
places such as molecular clouds and protoplanetary disks.
The first two compose the so-called “refractory solids,”
whereas the ice mantles are the volatile solids.
Although this article concentrates on carbonaceous
dust, the observations of silicates in the interstellar dust
cycle are considered instructive, as they possess sharp
crystalline phases that provide well-identified spectral
features, raising important questions. Silicates have been
observed in emission during the late phases of stellar evolution, like the stars in the Asymptotic Giant Branch and
Red Giant phases, when copious amount of matter is
ejected by stellar winds. The observed silicates in these
environments are significantly crystalline. By contrast,
the silicates injected in the diffuse interstellar medium
are observed to be fully amorphous (e.g., Kemper et al.,
2004). The amorphization in this medium occurs due to
the processing by energetic cosmic rays, as demonstrated
in the laboratory (Carrez et al., 2002; Demyk et al., 2004;
Bringa et al., 2007). In a later evolutionary stage, these
silicates, present into dense clouds, are incorporated in
the eventual formation of protostellar objects. The spectra of disks around T Tauri stars harbor large fractions of
crystalline silicates. The observations in these disks lead
to a so-called “crystallinity paradox” (e.g., Olofsson et
al., 2009), as more crystalline silicates are observed in
regions that are colder, rather than warmer, and closer to
the star, and therefore far from their presumed (trans-)formation regions.
Careful investigations are still needed to conclude
about the origin of crystalline silicate in the cold regions
of T Tauri stars, as alternative silicates crystallization
mechanisms have been invoked at temperatures lower than
the classical condensation temperatures (Molster and
Kemper, 2005), such as by intense electron bombardment
(Carrez et al., 2001; Kimura et al., 2008) and exothermic
reactions (Tanaka et al., 2010). This implies that silicate
crystallization occurs under a wider range of astrophysical
conditions. However, the radial distributions observed in
these crystalline silicates are still associated with efficient outward radial transport mechanisms in the disks
around T Tauri stars, with the silicates incorporated from
the protostellar phase being amorphous. The constraints
suggested through the observation of these minerals raises
similar questions on our understanding of the interstellar
organic matter.
THE CARBONACEOUS “ALLOTROPES ”
OF THE INTERSTELLAR MEDIUM
Several forms of carbonaceous solids are observed in
the Galaxy’s ISM: nanodiamonds, fullerenes,
polyaromatic hydrocarbons, amorphous carbons, hydrogenated amorphous carbons, and ices that can form organic residues. Nanodiamonds are best observed around
512 E. Dartois et al.
young stars through two specific infrared emission bands
at 3.43 and 3.53 microns. They are attributed to vibrational modes of hydrogen-terminated nanodiamonds, typically a few nanometers in size, and containing hundreds
of C atoms (Chang et al., 1995; Guillois et al., 1999; Pirali
et al., 2007) in equilibrium with the stellar radiation field.
They are observed around very few objects and are close
to stars (Habart et al., 2004; Acke et al., 2006; Goto et
al., 2009).
Space fullerenes have been observed more recently,
after long searches of upper limits (e.g., Foing and
Ehrenfreund, 1994; Fulara et al., 1993; Moutou et al.,
1999; Herbig, 2000). C60 was first spatially resolved in a
reflection nebula by Sellgren et al. (2009, 2010), and then
C60 and C70 in a planetary nebula (Cami et al., 2010).
The fullerenes observed consume a low percentage of the
available cosmic carbon, with C 60/C ratios typically
<0.1%. However, recent observations report the presence
of mid-infrared features that are expected to arise from
C60 in the surroundings of many objects with different
physical conditions such as Asymptotic Giant Branch,
Post-AGB, Protoplanetary Nebulae, and Herbig Ae/Be
stars (Garcia-Hernandez et al., 2012; Roberts et al., 2012).
Aromatic Infrared Bands (AIB), with emission bands
observed at around 3.3, 6.2, 7.7, 8.6, and 11.3 microns,
are characteristic of a polyaromatic material and are observed ubiquitously in the ISM. They have led to the socalled “Polycyclic Aromatic Hydrocarbons” (PAHs) hypothesis. Under this hypothesis, AIB bands are associated with the infrared fluorescence of large PAHs molecules upon absorption of energetic UV photons (Leger
and Puget, 1984; Allamandola et al., 1985). AIB astronomical spectra are variable in their band profiles, and
the observed sources are classified as A, B or C, based on
the phenomenological decomposition of the bands’ positions (Peeters et al., 2002; Van Diedenhoven et al., 2004).
The class A spectra are observed the most in terms of
numbers, followed by class B, and class C. The evolution
among the profiles is primarily linked to differences in
the chemical composition of the emitting molecules or
particles. The ones in class A are probably the most aromatic ones. The ones in class B show an evolution of the
band that can be attributed to several factors, including
the possible presence of heteroatoms or structural changes
at the nanoscale in the carbonaceous network. And the
ones in class C display additional features attributed to a
more aliphatic character, both observationally (Sloan et
al., 2007; Boersma et al., 2008; Keller et al., 2008; Acke
et al., 2010) and experimentally (Pino et al., 2008;
Carpentier et al., 2012; Gadallah et al., 2013).
Amorphous carbon dust is also observed around carbon(-phase) stars, mainly through a blackbody emission
from the amorphous carbon particles (Volk et al., 2001;
Gauba and Parthasarathy, 2004; Chen et al., 2010). This
interstellar dust component is very difficult to detect elsewhere, as it possesses neither specific nor strong infrared
features. However, it probably contributes to the extinction in the UV-visible part of the DISM spectrum.
Hydrogenated amorphous carbons (HAC), also called
by physicists a-C:H after amorphous material made of C
and H, are another major component of interstellar dust.
Observed for the first time in an absorption band at 3.4
µ m against a Galactic center source (Allen and
Wickramasinghe, 1981), the features contributing to this
absorption band are associated with sp3 CH3 and CH2
stretching modes (Duley and Williams, 1983). Numerous
experiments and observations have been performed to
identify its origin. The a-C:H Galactic abundance has been
estimated from the observed CH stretching modes in many
lines of sight (e.g., Sandford et al., 1991, 1995; Pendleton
et al., 1994; Duley, 1994; Duley et al., 1998; Dartois and
Muñoz-Caro, 2007), and varies from a few percent up to
35% (laboratory HAC) of the cosmic C abundance.
In the densest phases of the interstellar dust cycle, or
molecular clouds, the dust grains are covered by volatile
molecules that are frozen at low temperature (about 10
K, Bottinelli et al., 2010, Boogert et al., 2008;
Pontoppidan et al., 2008; Öberg et al., 2008; Bergin et
al., 2005; Dartois, 2005a; van Dishoeck, 2004; Boogert
and Ehrenfreund, 2004; Gibb et al., 2000). These simple
ice mantles may act as chemical sites for surface processes (e.g., Hama and Watanabe, 2013; and reference
therein) and are simultaneously processed in bulk by cosmic rays and UV photons. The radiolysis and photolysis
products recombine, leading to the formation of
macromolecular residues that are stable upon sublimation of the ice mantles (e.g., Muñoz Caro and Schutte,
2003; Nuevo et al., 2006) and could be incorporated into
later stages of dust evolution.
COMPARISONS BETWEEN ISM O BSERVATIONS/LABORATORY ANALOGUES AND S OLAR SYSTEM MATTER
From the point of view of expected abundance, and
among the observed carbonaceous solids, the formation
of a protosolar nebula would mainly incorporate PAHs,
a-C:H, and/or organic residues. Early comparisons between the ISM a-C:H features and meteoritic Insoluble
Organic Matter (IOM) have been performed (e.g.,
Ehrenfreund et al., 1991; and citations therein). The relatively good match between both infrared spectra around
3.4 microns led to the conclusion that the chemical composition of interstellar matter was similar to the meteorite organic extract (Ehrenfreund et al., 1991). The observational astronomical constraint came later, when satellites gave access to the mid-infrared spectral fingerprint
region (inaccessible for ground telescopes because of atmospheric absorption), showing that the 5 to 9 microns
spectral region in IOM was neither compatible with DISM
a-C:H nor were organics expected from ice mantles processed in dense clouds.
The underlying structure proposed more than ten years
ago for a-C:H diffuse organic matter was highly
polyaromatic, fully hydrogenated at the edges of the aromatic planes, with few aliphatic bridges (Pendleton and
Allamandola, 2002), and very different from the inferred
IOM structure in Orgueil (Remusat et al., 2007; Derenne
and Robert, 2010) and the labile fraction in CM chondrites
(Kitajima et al., 2002). Recent extragalactic specific lines
of sight that cover a larger astronomical scale give us
additional information about the a-C:H structure by probing the diffuse medium at galactic scales (Dartois and
Muñoz-Caro, 2007). Galaxies are receding from us and
distant ones bring the 3 microns absorption to a more
favorable atmospheric transmission window, giving access to the aromatic CH absorption (Dartois et al., 2007).
The background reference source is now an entire galactic nucleus with a large parsec probe beam. Apart from
the strong amorphous silicate absorption, other absorptions in some lines of sight are dominated by a-C:H, while
the aromatic versus aliphatic content of DISM a-C:H
shows that the aromatic CH stretching modes are less
prominent than those suggested by the proposed former
structure.
The evolution of the schematic basic structural unit
of diffuse ISM analogues resembles more the IOM structure, but the meteoritic organics still display too many
absorptions in the mid-infrared spectral fingerprint region
(Kebukawa et al., 2011; Orthous-Daunay et al., 2013).
Comparing the interstellar a-C:H spectra to the IOM spectra in more detail, we see that the former spectra do not
display the strong infrared signatures of oxygen
heteroatoms, nor there is evidence of a large amount of
incorporated nitrogen atoms. However, this ISM dust
could be a precursor that could evolve when incorporated
into dense clouds.
Following observations of the transition from diffuse
to dense ISM when MC are formed, the a-C:H infrared
signatures disappear, while ice mantles begin to form. This
raises the question of whether the ISM hydrogenated
carbonaceous dust is destroyed or transformed. Several
experiments have investigated this modification and show
that the a-C:H are dehydrogenated either in the dense
phase (Mennella et al., 2003) and/or in the interface between diffuse and dense clouds (Godard et al., 2011), thus,
before being incorporated into a protosolar nebula.
In this dense cloud phase, an alternative organic material can be produced by the photolysis and radiolysis of
ice mantles covering the dust grains. However, the
laboratory-produced residues, which are measured at
room temperature (e.g., Muñoz Caro et al., 2004; Nuevo
et al., 2006), and the space-exposed laboratory residues
Astrophysical carbonaceous dust in the laboratory 513
Fig. 1. Comparison of the infrared spectra of some ISM, Solar System, and laboratory-produced solids. From bottom to top:
emission spectrum of the class A emission line star IRAS23133+6050 displaying the characteristic PAH features (ISO database);
laboratory-produced interstellar a-C:H analogue and diffuse interstellar absorption from interstellar a-C:H in the extragalactic
source IRAS08572+3915 (Dartois et al., 2007); OR1 (Muñoz Caro and Schutte, 2003) and OR2 (Muñoz Caro et al., 2004) are
organic residues obtained by laboratory UV irradiation of interstellar ices analogues; IOM extracted from PCA91008 and
Murchison (Orthous-Daunay et al., 2013); laboratory-produced hydrogenated amorphous carbon nitride (Ong et al., 1996);
UCAMMsDC060565 and DC060594 infrared spectra (Dartois et al., 2013). The top right spectra (i) and (ii) represent possible
forsterite and enstatite silicates contributions to the UCAMMS (see Dartois et al., 2013 for details).
(e.g., EURECA experiment, Greenberg et al., 1995) do
not match. The same applies to the entire infrared spectra
of IOM. Therefore, they can only be seen as a potential
starting or precursor material (Muñoz Caro and Dartois,
2013), provided that the subsequent evolutionary pathways can lead to some kind of IOM.
We have previously compared ISM dust with meteorite organic matter originating from the asteroid belt region. Now is important to discuss the carbonaceous component for Interplanetary Dust Particles (IDPs) and
micrometeorites from larger distances. IR spectra are difficult to measure for IDPs, and their organic content cannot be easily separated using techniques similar to the
ones used for meteorites given their small sizes. Many of
the IDPs infrared spectra display a stretching mode region different from the Galactic center lines of sights that
display the a-C:H dust components (e.g., Keller et al.,
2004; Matrajt et al., 2005; Bradley, 2005; Muñoz Caro et
al., 2008; Brunetto et al., 2011). Micrometeorites col-
514 E. Dartois et al.
lected at the poles offer a size distribution that is more
suitable for these techniques to be applied, thus allowing
for a more direct comparison with astronomical spectra.
The remaining part of this article focuses on rare, specific, and very interesting ultracarbonaceous
micrometeorites (UCAMMs), which provide a sample of
another form of organic matter from the Solar System.
These UCAMMs were discovered as a small fraction in
various Antarctic micrometeorites collections, such as
those reported by Nakamura et al. (2005) and Yabuta et
al. (2012) from the Dome Fuji collection, and those
present in the Concordia collection of the CSNSM, from
the French-Italian Dome C station (Duprat et al., 2007).
Scanning electron micrograph and X-ray maps of two
UCAMMs, combined with Nano-SIMS measurements,
show that these are very rich in organic content, with more
than 50% and up to 95% of the whole UCAMM atoms
being organic matter, and have a high D enrichment (D/
H = 1.0 ± 0.3 × 10–3 and D/H = 7.2 ± 3.2 × 10–4, respec-
tively), suggesting formation in a low T environment
(Dartois et al., 2013). Their organic matter presents an
infrared spectrum similar to laboratory analogues of
polyaromatic hydrogenated carbon nitrides, and display
a nitrogen concentration characterized by bulk atomic N/
C ratios of 0.05 and 0.12 (locally exceeding 0.15).
N-rich materials in the Solar System are rare and no
such materials are observed in ISM. Incorporating 10–
20% of N in a carbon nitride requires a C-precursor and
energetic processes in an N-dominated environment (i.e.,
H2O ice depleted). Such nitrogen-rich carbonaceous material could possibly be formed by irradiation of N- and
C-rich ices by UV photons and/or cosmic rays in very
low temperature regions of the Solar System. These conditions are encountered at the surface of small objects
beyond the trans-Neptunian region. UCAMMs could
therefore provide unique insights into the material incorporated from the protosolar nebula and the physicochemical processes that occurred beyond the nitrogen
snow-line, revealing organic material from the extreme
outer regions of the Solar System that cannot be investigated by remote sensing methods. To summarize the comparison and emphasize the differences between many of
the above-discussed materials, their infrared spectra are
displayed in Fig. 1.
CONCLUSION
In view of the comparisons made above, there seems
to be no strong evidence for interstellar materials being
directly imported and incorporated at a large scale in the
Solar System. When incorporated, the interstellar dust
provides at most a precursor, and laboratory studies are
important to decipher the future evolution of these solids
as observed in the previous phases of the ISM cycle. Apart
from very specific particles, such as the extremely resistant presolar grains (highly refractory SiC, Diamonds), the
materials observed, collected, and analyzed are more often probing nebular processes or physico-chemical mechanisms occurring inside the Solar System during its youth
rather than genuine fully preserved ISM material.
Acknowledgments—The Goldschmidt conference fees and part
of the work presented here were supported by the ANR projects
COSMISME (Grant ANR-2010-BLAN-0502) and OGRESSE
(Grant ANR2011-BS56-026-01) of the French Agence Nationale
de la Recherche. We thank Dr. Shogo Tachibana, Dr. Itsuki
Sakon and an anonymous reviewer for thoroughly reviewing
and providing comments, as well as a language editor, that
helped improve the manuscript.
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