Scott A. Sandford

Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues

The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites—over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.

Organics captured from comet 81P/Wild 2 by the Stardust spacecraft

Organics found in comet 81P/Wild 2 samples show a heterogeneous and unequilibrated distribution in abundance and composition. Some organics are similar, but not identical, to those in interplanetary dust particles and carbonaceous meteorites. A class of aromatic-poor organic material is also present. The organics are rich in oxygen and nitrogen compared with meteoritic organics. Aromatic compounds are present, but the samples tend to be relatively poorer in aromatics than are meteorites and interplanetary dust particles. The presence of deuterium and nitrogen-15 excesses suggest that some organics have an interstellar/protostellar heritage. Although the variable extent of modification of these materials by impact capture is not yet fully constrained, a diverse suite of organic compounds is present and identifiable within the returned samples.

Mid- and far-infrared spectroscopy of ices: optical constants and integrated absorbances.

Laboratory spectra through the mid-infrared (4000 to 500 cm-1 [2.5-20 micrometers]) have been used to calculate the optical constants (n and k) and integrated absorption coefficients (A) for a variety of pure and mixed molecular ices of relevance to astrophysics. The ices studied were H2O, CH3OH, CO2, OCS, CH4, CO2 + CH4, CO2 + OCS, CO + CH4, CO + OCS, O2 + CH4, O2 + OCS, N2 + CH4, N2 + OCS, H2O + CH4, H2O + OCS, and H2O + CH3OH + CO + NH3. In addition, the measurements have been extended through the far-infrared (500 to 50 cm-1 [20-200 micrometers]) for the H2O, CH3OH, and H2O + CH3OH + CO + NH3 ices.

Photochemical and thermal evolution of interstellar/precometary ice analogs

An experimental investigation of the photochemical and thermal evolution of ices deposited at 10 K which contain primarily H2O, CH3OH, NH3, and CO mixed in relative proportions consistent with the proposed composition of interstellar ices is presented. These experiments, which are relevant to both interstellar and cometary ices, are the first described in which CH3OH (methanol) is a major constituent of the ice. Ultraviolet photolysis of these ice analogs invariably produces H2CO, CO2, CO, CH4, and HCO, largely at the expense of photofragmented CH3OH. In addition, photolysis produces a mixture of more complex molecules, some of which contain nitrile or isonitrile (CN or CN) and carbonyl (CO) groups. Most of the CO and CH4 leaves the sample upon warm-up to 100 K. Most of the parent ice molecules sublime away by 200 K leaving behind a mixture of more refractory substances. Warm-up to 250 K removes a component rich in CH3 groups which may correlate with the carrier(s) of the CO and CN bonds. A residue rich in CH2 groups remains even after warm-up to 300 K. The relevance of these results to questions concerning the composition of interstellar and cometary ices, and the scale heights of photofragments in cometary comae is discussed. The results may have some bearing on the recent suggestion that polyoxymethylene is present in Comet Halley.

Near-infrared absorption spectroscopy of interstellar hydrocarbon grains

We present new 3600 - 2700/cm (2.8 - 3.7 micrometer) spectra of objects whose extinction is dominated by dust in the diffuse interstellar medium. The observations presented here augment an ongoing study of the organic component of the diffuse interstellar medium. These spectra contain a broad feature centered near 3300/cm (3.0 micrometers) and/or a feature with a more complex profile near 2950/cm (3.4 micrometers), the latter of which is attributed to saturated aliphatic hydrocarbons in interstellar grains and is the primary interest of this paper. As in our earlier work, the similarity of the absorption bands near 2950/cm (3.4 micrometers) along different lines of sight and the correlation of these features with interstellar extinction reveal that the carrier of this band lies in the dust in the diffuse interstellar medium (DISM). At least 2.5% of the cosmic carbon in the local interstellar medium and 4% toward the Galactic center is tied up in the carrier of the 2950/cm (3.4 micrometer) band. The spectral structure of the diffuse dust hydrocarbon C-H stretch absorption features is reasonably similar to UV photolyzed laboratory ice residues and is quite similar to the carbonaceous component of the Murchison meteorite. The similarity between the DISM and the meteoritic spectrum suggests that some of the interstellar material originally incorporated into the solar nebula may have survived relatively untouched in primitive solar system bodies. Comparisons of the DISM spectrum to hydrogenated amorphous carbon and quenched carbonaceous composite are also presented. The A(sub V)/tau ratio for the 2950/cm (3.4 micrometer) feature is lower toward the Galactic center than toward sources in the local solar neighborhood (approximately 150 for the Galactic center sources vs. approximately 250 for the local ISM sources). A similar trend has been observed previously for silicates in the diffuse medium by Roche & Aitken, suggesting that (1) the silicate and carbonaceous materials in the DISM may be physically correlated and (2) there is either dust compositional variation in the galaxy or galactic variation in the grain population density distribution. We also note a possible absorption feature near 3050/cm (3.28 micrometers), a wavelength position that is characteristic of polycyclic aromatic hydrocarbons (PAHs).

Itokawa Dust Particles: A Direct Link Between S-Type Asteroids and Ordinary Chondrites

Laboratory analysis of samples returned from an asteroid establishes a direct link between asteroids and meteorites and provides clues to the complex history of the asteroid and its surface. The Hayabusa spacecraft successfully recovered dust particles from the surface of near-Earth asteroid 25143 Itokawa. Synchrotron-radiation x-ray diffraction and transmission and scanning electron microscope analyses indicate that the mineralogy and mineral chemistry of the Itokawa dust particles are identical to those of thermally metamorphosed LL chondrites, consistent with spectroscopic observations made from Earth and by the Hayabusa spacecraft. Our results directly demonstrate that ordinary chondrites, the most abundant meteorites found on Earth, come from S-type asteroids. Mineral chemistry indicates that the majority of regolith surface particles suffered long-term thermal annealing and subsequent impact shock, suggesting that Itokawa is an asteroid made of reassembled pieces of the interior portions of a once larger asteroid.

MODELING THE UNIDENTIFIED INFRARED EMISSION WITH COMBINATIONS OF POLYCYCLIC AROMATIC HYDROCARBONS

The infrared emission band spectrum associated with many different interstellar objects can be modeled successfully by using combined laboratory spectra of neutral and positively charged polycyclic aromatic hydrocarbons (PAHs). These model spectra, shown here for the first time, alleviate the principal spectroscopic criticisms previously leveled at the PAH hypothesis and demonstrate that mixtures of free molecular PAHs can indeed account for the overall appearance of the widespread interstellar infrared emission spectrum. Furthermore, these models give us insight into the structures, stabilities, abundances, and ionization balance of the interstellar PAH population. These, in turn, reflect conditions in the emission zones and shed light on the microscopic processes involved in the carbon nucleation, growth, and evolution in circumstellar shells and the interstellar medium.

The impact and recovery of asteroid 2008 TC 3

In the absence of a firm link between individual meteorites and their asteroidal parent bodies, asteroids are typically characterized only by their light reflection properties, and grouped accordingly into classes. On 6 October 2008, a small asteroid was discovered with a flat reflectance spectrum in the 554–995 nm wavelength range, and designated 2008 TC3 (refs 4–6). It subsequently hit the Earth. Because it exploded at 37 km altitude, no macroscopic fragments were expected to survive. Here we report that a dedicated search along the approach trajectory recovered 47 meteorites, fragments of a single body named Almahata Sitta, with a total mass of 3.95 kg. Analysis of one of these meteorites shows it to be an achondrite, a polymict ureilite, anomalous in its class: ultra-fine-grained and porous, with large carbonaceous grains. The combined asteroid and meteorite reflectance spectra identify the asteroid as F class, now firmly linked to dark carbon-rich anomalous ureilites, a material so fragile it was not previously represented in meteorite collections.

Condensation and vaporization studies of CH3OH and NH3 ices: major implications for astrochemistry.

In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecules observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

Laboratory studies of the infrared spectral propertries of CO in astrophysical ices

Analysis of laboratory spectra of numerous astrophysical ice analogs demonstrates that the exact band position, width, and profile of the solid state CO fundamental near 2137 cm-1 (4.679 microns) can provide important information on the physical conditions present during the ice accretion phase as well as during any subsequent thermal processes and radiation exposure. In the ices studied, the CO peak position varies from 2134 to 2144 cm-1 (4.686 to 4.664 microns) and the band width from 2.1 to over 20 cm-1 depending on the composition of the ice. In an ice matrix dominated by H2O, the CO peak falls at 2136.7 cm-1, has a full width at half-maximum of about 9 cm-1, and shows a prominent sideband at 2152 cm-1. This sideband and minor structure superposed on the main band arise from CO trapped in different matrix sites. These features provide information concerning the thermal and radiation history of the ice. The solid CO band in interstellar spectra often has contributions from broad (12 cm-1) and narrow (5 cm-1) components. We identify the broad component with CO intimately mixed in matrices dominated by polar molecules, of which H2O is likely to be the major component. Examination of the interstellar and laboratory band profiles shows that either the abundance of nonpoplar impurities in these ices must be less than 10% or the ices have been thermally annealed or processed by ultraviolet radiation. The narrow component is likely to originate from grain mantles dominated by nonpolar molecules such as CO2. These components reflect differences in the physical and chemical conditions in regions of the cloud along the line of sight. Laboratory determination of the absorption strength of the CO fundamental in H2O-rich ices showed that the value used in the past was approximately 60% too low and that most previously determined solid-state CO column densities have been systematically overestimated. The rich spectral behavior of the CO band observed in the laboratory studies clearly indicates that future high-quality astronomical spectra in the 2200-2100 cm-1 range can produce a wealth of new information and provide deeper insights into the nature of astrophysical ices.