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The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution (1990)

Chapter: 2. The Cosmic History of the Biogenic Elements and Compounds

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Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
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Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 22
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 23
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 24
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 25
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 26
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 27
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 28
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 29
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 30
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 31
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 32
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 33
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 34
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 35
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 36
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 37
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 38
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 39
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 40
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 41
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 42
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 43
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 44
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 45
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 46
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 47
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 48
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 49
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 50
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 51
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 52
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 53
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 54
Suggested Citation:"2. The Cosmic History of the Biogenic Elements and Compounds." National Research Council. 1990. The Search for Life's Origins: Progress and Future Directions in Planetary Biology and Chemical Evolution. Washington, DC: The National Academies Press. doi: 10.17226/1541.
×
Page 55

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The Cosmic History of the Biogenic Elements and Compounds INTRODUCTION From our terrestrial perspective it is difficult to conceive of life forms in which the elements hydrogen, carbon, oxygen, nitrogen, sulfur, and phos- phorus do not play a predominant role. That they do indeed play such a role throughout the universe seems highly probable, in part because (apart from phosphorus) these are the most abundant elements throughout the cos- mos and they occur in significant quantities among the building blocks of terrestrial planets as represented by the primitive chondrites and comets. Moreover, their chemistry is particularly well suited to the development of the complex structures and functions characteristic of living systems. Since the Sun and planets formed only some 4.6 billion years ago in a universe whose age is perhaps 15 billion years, it is clear that these "biogenic ele- ments" experienced a long and complex chemical history before being in- corporated into terrestrial biochemistry. At present it is not known whether this prior history played a direct role in the origin of life on Earth. What is clear is that astrochemistry is to a large extent the chemistry of the biogenic elements and that understanding the nature and evolution of chemical com- plexity throughout the universe is crucial to understanding both the early chemical state of our own solar system and the frequency with which simi- lar or related conditions exist elsewhere in our galaxy and other galaxies. There is, in addition, increasingly suggestive evidence for the survival of interstellar molecular material within objects present in the solar system today. Such evidence comes from studies of the isotopic compositions of the carbonaceous components of certain meteorites and from the inferred chemical composition of cometary nuclei, the latter supported by models derived from recent spacecraft encounters. Moreover, some current models 21

22 THE SEARCH FOR LIFE'S ORIGINS of the solar nebula suggest that the bulk of the Earth's volatiles would not have condensed at 1 AU from the Sun, implying that they were provided by a bombardment of the Earth by volatile-rich cometary and meteoroidal de- bris, which may well have contained interstellar components. At the least, these ideas imply links between the chemistry of primitive objects in the solar system and the interstellar environment in which the Sun and planets formed and that such links involve the chemistry of the elements necessary for the origin of life on Earth. Certainly, a knowledge of the chemistry and physics of both interstellar clouds and the solar nebula will provide crucial information on how and from what materials the solar system was formed. The cosmic history of the biogenic elements and their compounds thus becomes a critical field of study for exobiologists. Apart from hydrogen, which is for all essential purposes primordial, these elements are formed in the interiors of stars and returned to the interstellar medium either in the violent events accompanying the late stages of evolution of a massive star (supernova explosions) or in the even larger amounts of processed material expelled continuously or episodically from stars in late stages of their life cycles. The subsequent of chemical complexity is a complicated and still poorly understood story, involving condensation of particulate material ("dust") in the outflowing envelopes around evolved stars, gas-phase reac- tions that build complex organic molecules in dense interstellar clouds of gas and dust, and interaction of the particulate and gaseous phases with the interstellar radiation field and cosmic rays. In circumstellar and interstellar regions, astronomers have unequivocally identified gaseous organic molecules with up to 13 atoms and molecular weights twice that of glycine, the simplest amino acid. Although the pres- ence of an interstellar "dust" component has been known for more than 50 years, its composition, structure, and special variations are still subjects of heated controversy. Evidence is accumulating, however, that the size of these dust particles may well overlap that of large molecules, and their composition, in terms of biogenic compounds, quite likely ranges from water and amorphous carbon or graphite to complex, heterocyclic organic poly- mers. It is within the denser interstellar clouds that new stars and planetary systems form. The details of this process are not well understood. None- theless, it is generally accepted that the physical and chemical properties of the biogenic compounds play a crucial role in the thermodynamics of star formation, because radiative energy loss from these molecules allows the cloud to cool and hence to collapse. Moreover, the trace biogenic constitu- ents provide critical probes of the physical, chemical, and kinematic states of both interstellar clouds and protostellar systems, by way of their rotational and vibrational transitions observable at radio and infrared wavelengths.

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AD COMPOUNDS 23 How much of this interstellar chemistry is preserved as the parent mo- lecular cloud collapses to yield the protosun, as the accretion disk develops into the solar nebula, and as the building blocks of the planets accrete, is uncertain. The investigation of possible links between the chemistries of these stages in solar-system formation, and the determination of physical and chemical conditions during this process by studying both primitive objects and molecular clouds, are fascinating and crucial areas to be ex- plored in coming years. It is clear that the solar nebula was not in chemical equilibrium. Can local kinetic processes mimic those that occurred under interstellar conditions? What new organic compounds might have formed in the solar nebula or on the primitive bodies of the solar system? Can the processes operating on primitive bodies give insight into chemical evolu- tion on Earth? Detailed analysis of the chemistry and structure of com- pounds and phases containing the biogenic elements in surviving primitive material, including comets, can probe such questions. The single overriding goal of this phase of evolutionary history is stated below. Five major objectives contributing to the achievement of this goal follow. GOAL: To understand the history of physical and chemical transforma- tions undergone by the biogenic elements and compounds, from nucleosyn- thesis to their incorporation and subsequent modification in preplanetary bodies. OBJECTIVE 1: To determine the extent and the evolution of molecular complexity in interstellar and circumstellar environments. Almost 20 years have passed since the first gaseous polyatomic mole- cules ammonia (NH3) and water (H2O) were discovered in the interstel- lar medium via the technique of radio astronomy. Since that time, more than 80 different molecular species and numerous isotopic modifications have been identified unambiguously in the gas phase. Most of these species have been detected through their rotational transition frequencies at radio wavelengths (the term "radio" is often used to apply to wavelengths of 1 mm or less), although a few molecules, especially in circumstellar sources, have been characterized by their vibrational spectra in the infrared. The detected molecules range in complexity from diatomics such as hydrogen (H2) and carbon monoxide (CO) to a 13-atom unsaturated linear nitrite HEWN and include many simple organic molecules (Table 2.1~. Typically, molecules involving the biogenic elements carbon, nitrogen, and oxygen are trace constituents of a gas dominated by molecular hydrogen. Nevertheless, the large mass of "dense" interstellar clouds implies that there is substan- tially more organic matter in a typical cloud than on the Earth. In addition to the existence of organic molecules, dense interstellar clouds have other

24 TABLE 2.1 Identified Interstellar Molecules THE SEARCH FOR LIFE'S ORIGINS Simple Hydrides, Oxides, Sulfides, Halides, and Related Molecules H2 CO NH3 CS HC1 SiO SiH4X SiS H2O so2 CC H2S OCS CH4X PN HNO (?) SiCX Naclx Alclx KClx AlFX Nitrites, Acetylene Derivatives, and Related Molecules HCN HC_C CN H3C C_C CN H3C CH2 CN H2C=CH2X H3CCN H(C_C)2 CN H3C C-CH H2C=CH CN HC_CHX CCO(?) H(C-C)3 CN H3C- (C_C)2 H HNC CCCO H(C_C)4 CN H3C (C_C)2—CN? HN=C=0 CCCS H(C_C)s CN HN=C=S HC_CCHO H3CNC Aldehydes, Alcohols, Ethers, Ketones, Amides, and Related Molecules H2C=0 H3COH HO CH=0 H2C=S H3C—CH2 OH H3C O CH=0 H3C CH=0 H3CSH H3C O CH3 NH2 CH=0 (CH312CO (?) H2C=C=0 Cyclic Molecules C3H2 SiC2 C3H ions CH+ HCO+ H3O+ (?) H2D+ (?) HOCO+ HCNH+ HN2+ HCS+ SO+ HOC+ (?) Radicals CH C3H CN HCO C2S OH C4H C3N NO SO C2H CsH H2CCN NS C6H H2CNH H3CNH2 H2NCN NOTE: The superscript x indicates detection only in the envelopes around evolved stars. A question mark (?) indicates molecules claimed but not yet confirmed. features in common, such as a preponderance of gas-phase matter (with perhaps 1 percent of the material in the form of solid dust grains), tempera- tures well below those on Earth (10 to 100 K), gas densities quite low by terrestrial standards (103 to 106 molecules/cm3), and chemically "reducing" environments in which H2 is the dominant molecular species but in which oxygenated molecules also exist. The most massive objects, "giant" mo- lecular clouds, are larger, hotter (100 K versus 10 K), and show more evidence of past and present massive star formations than the much smaller

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 25 "dark clouds." Circumstellar sources appear to exhibit a significant organic chemistry only if, unlike most objects, they are carbon- rather than oxygen- rich. In such stellar envelopes, the gas density and temperature are severe functions of the distance from the center of the star. Although the spectra of many gaseous molecules have been detected in interstellar and circumstellar sources, most astronomers have been less inter- ested in the chemical composition of these sources than in utilizing the spectra of abundant species such as CO and NH3 to probe the prevailing physical conditions. High priority in the next decade should therefore be accorded to a systematic study of the chemical composition of interstellar and circumstellar clouds. Of particular interest in the context of exobiology are studies of the degree of molecular complexity that can be attained and of the diversity of chemical compositions that are produced as a result of evolutionary effects and different physical conditions. SYSTEMATIC STUDIES OF INTERSTELLAR CLOUDS Although much has been learned about individual interstellar and cir- cumstellar sources, a systematic study of the gas-phase chemistry of any of these sources has not yet been achieved, even though portions of such studies are available. A systematic study would entail determination of the following: the chemical state of the major elements, including the biogenic ones; isotopic abundances and isotopic fractionation effects; the way in which abundances of major constituents vary as functions of position and physical conditions within the cloud and possible cloud history; and the extent of molecular complexity (see below). Consider oxygen as an example of how little is known about the domi- nant repositories of the major elements. It is argued indirectly that oxygen (O2) and water (H2O) are probably the most abundant oxygen-containing species after CO in the gas phase of interstellar and circumstellar clouds, and yet it is difficult to study these species from the ground or even from aircraft because of atmospheric absorption. A strategy for determining the abundances of these important gas-phase species via their millimeter and submillimeter transitions requires space-based instrumentation, perhaps ini- tially of the Explorer class, but ultimately employing the higher angular resolution of the proposed Large Deployable Reflector (LDR) and the Space Infrared Telescope Facility (SIRTF) spacecraft (Space Science in the Twenty- First Century, SSB, 1988a,c). Consider, as a second example, the case of carbon. A significant fraction of carbon abundance in the gas phase is in the form of CO. However, it is unclear how much is in the form of carbon dioxide (CO2) or simple hydrocarbons such as methane (CH4) and acetylene (C2H2), because these nonpolar species do not possess strong rotational spectra. To determine their importance, infrared techniques will have to be

26 THE SEARCH FOR LIFE'S ORIGINS utilized to observe vibrational transitions. It is clear from atmospheric ab- sorption at these wavelengths and from the currently limited sensitivity of ground-based infrared telescopes that significant progress will be made by high-spectral-resolution detectors in space, including those employing hetero- dyne techniques. Another subject of considerable interest is that of isotopic fractionation, which may provide the most accurate "fingerprints" of interstellar processes that are preserved in comets and primitive asteroids. Low-temperature inter- stellar clouds lead to strong fractionation effects, especially with regard to deuterium/hydrogen (HD/H2) abundance ratios in trace species. For ex- ample, although the interstellar abundance ratio HD/H2 is approximately 1-2 x 10-5, the abundance ratio between other deuterated species and their hydrogen analog can be higher than 0.01 in cold clouds. This effect is un- derstood theoretically and occurs because the reactions between molecular ions and neutral molecules that dominate the chemistry at low temperature (ion-molecule reactions) can only proceed rapidly in exothermic directions. More systematic observations of selected fractionation ratios as functions of cloud temperature and density are required to refine current theories fur- ther. Once these theories have become more quantitative, theoretical treat- ments of how these isotopic ratios can be preserved as the interstellar cloud becomes a protosolar nebula will be most useful. Some studies of the variations in abundance of selected species as func- tions of position and physical conditions within clouds are under way. For example, radio astronomers have begun to probe selected regions in the Orion nebula, a prototype giant molecular cloud. A variety of chemically unusual regions, associated to a greater or lesser extent with star formation, have already been delineated. It would be of interest to devote similar attention to lower-mass clouds such as TMC-1 and L183, because such smaller and colder regions may lead upon collapse to solar-type stars. Complementary to the studies discussed above are broad surveys of the radio line spectra of interstellar sources: knowledge of the radio frequency spectra of most molecular clouds is extremely patchy. Systematic maps of the spectra have thus far been partially accomplished for only two giant interstellar clouds, that in Orion and one near the galactic center. These surveys, which detected on the order of 1000 emission lines, have resulted in a significant increase in the amount of chemical information available (see Figure 2.1~. A similar survey of the dark cloud TMC-1 would be most worthwhile because it is a precursor of solar-type stars. Because clouds such as TMC-1 are so cool (10 K) and have little turbulence, spectral line widths are very narrow, making a survey much more difficult than in the giant clouds. To survey TMC-1 over a wide range of frequencies, a broad- band high-resolution spectroscopic capability is required. Some of the in- strumentation being developed in the SETI program may be useful here

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS ED COMPOUNDS 27 1 1 1 1 1 1 1 1 1 1 1 Orion Molecular Cloud 2.0 1.0 - ~: o.o 0.6 0.4 0.2 0.0 SOo _ CH3OH ~ CH3OH _~` _c ~ ~ 1 IRC + 1 0216 C4H C3H w~,/~ 1 1 1 1 1 1 1 1 1 1 1 76000 76100 76200 76300 Frequency (MHz) 76400 76500 FIGURE 2.1 Portions of the millimeter wavelength spectra of a dense interstellar cloud (Orion) and the envelope around an evolved star (IRC+10216~. (Astronomy and Astrophysics for the 1980s, National Research Council, 1982, 1983a,b). In the long run it is essential to broaden such studies to include a large sample of clouds. Will other abundance patterns be found? Will evolution- ary effects on chemical composition emerge? Then, eventually, can the analogous chemistry be probed in external galaxies? COMPLEX MOLECULES Biochemistry is clearly the chemistry of large, complex, organic mole- cules. The largest molecule unambiguously observed in the gas phase of interstellar and circumstellar clouds is PECAN. Although infrared spectra provide evidence for far larger species (such as polycyclic aromatic hydro- carbons; see discussion following objective 2), specific molecules have not been identified from the existing low-resolution spectra. To extend gas- phase high-resolution radio astronomical methods to search for molecules considerably larger than 13 atoms will require continually improving elec- tronics and a strategy involving laboratory studies. The laboratory work is necessary because many species more complex than 13 atoms have not been

28 TlIE SEARCH FOR LIFE'S ORIGINS studied spectroscopically in the gas phase, especially in the radio and milli- meter wave regions where their characteristic rotational transitions lie. The larger a molecule, the higher is its density of rotational levels, so that the intensity available in a single transition diminishes. Thus, to observe single rotational transitions of complex molecules in interstellar sources will re- quire more sensitive instrumentation and large amounts of searching time. In addition, as molecules grow in complexity, their most intense spectral lines shift toward lower frequencies. Current plans to enhance the capabili- ties of the large (300 m), low-frequency radio telescope at Arecibo to in- clude the 1- to 8-GHz frequency range would seem to be a boon for com- plex molecule studies. Another important component of a strategy for determining the extent of molecular complexity in interstellar and circumstellar sources involves chemi- cal modeling. Such modeling can tell astronomers what likely molecules may be found in a given environment and what intensities can be expected. From successful models involving smaller molecules, it is safe to say that much of the chemistry of the cold interstellar gas is accounted for by schemes based on gas-phase ion-molecule reactions which, because they typically possess no activation energy, can occur rapidly even at low temperature. Although models of interstellar clouds involving small gas-phase mole- cules are in good agreement among themselves and with observation, they differ significantly in their predictions of complex molecule abundances. These differences derive at least in part from lack of laboratory data on important ion-molecule reactions. Thus, an additional component of the strategy emerges the need for laboratory work on important ion-molecule reactions to aid modelers in calculating the expected abundances of com- plex molecules. Nor is this the final element of such a strategy: chemical models cannot be based entirely on laboratory studies of relevant reaction rates. Reaction systems with rate coefficients that are highly temperature dependent, which have only been studied in the laboratory at approximately room temperature, may occur at unsuspected rates under interstellar condi- tions. In addition, some classes of reactions are not easily studied in the laboratory. An example is the low-pressure process called radiative asso- ciation, which is thought to be critical in gas-phase syntheses of complex molecules. To examine this and other processes requires theoretical studies of rate coefficients. Such studies are then another integral part of a strategy aimed at determining the limits of molecular complexity in interstellar and circumstellar sources. Although the tenor of the discussion on interstellar chemistry has been concentrated on gas-phase processes, the influence of dust particles cannot be ignored. These particles are sites of molecular adsorption, Resorption, and possible reactions, and they can protect complex molecules from stellar ultraviolet radiation. Further discussion of particulate matter is given after objective 2 (see below).

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 29 In general, modeling of circumstellar sources has lagged somewhat be- hind that of interstellar ones. However, within the last few years, several circumstellar models have become available. The picture of carbon-rich circumstellar sources such as IRC+10216 that emerges is one in which chemical equilibrium at high temperature is achieved as material is ejected from the star, only to be reprocessed by an active photochemistry and ion- molecule reactions as the material proceeds further from the stellar photo- sphere. Significant amounts of complex molecules may be produced by these processes. STAR-FORMING REGIONS AND THE SUBMILLIMETER SPECTRAL RANGE How is the chemistry of an interstellar cloud affected by the process of star formation? Virtually nothing is known in this regard for isolated solar- mass stars. For more massive stars, however, some evidence has been obtained from study of the Orion nebula. Astronomers have thus far de- tected at least three unusual regions in which the abundances of gas-phase molecules are quite different from more normal values. Suggested causes include chemical reactions driven by shock waves, molecules desorbed from the interstellar grains by temperatures exceeding 100 K, and interactions between species so produced and the "normal" constituents of the ambient cloud. As more information becomes available concerning the unique chem- istry of star-forming regions, it should be possible to develop models of their chemistries with some predictive power. Indeed, primitive models of the star-forming regions in Orion are currently being formulated. Detailed observational studies of small regions warmer than the ambient interstellar medium will require very high angular resolution, which must be obtained by interferometric techniques. Expansion of existing facilities and eventual construction of instruments such as the Millimeter Array and the Submillimeter Array Telescope being discussed by the National Radio Astronomy Observatory (NRAO) and the Smithsonian Astrophysical Obser- vatory (SAO), respectively, will be required. In addition, frequencies higher than those normally used, particularly in the submillimeter region, are im- portant. Because, as the temperature rises, the dominant rotational line emission of most smaller molecules shifts into this wavelength region. Moreover, some light molecules such as simple hydrides can be observed only in the submillimeter spectral region; some of these species are critical to a quantitative understanding of chemical processes in interstellar clouds (e.g., the ion H3+ and metal hydrides such as MgH). Unfortunately, severe problems are associated with submillimeter observations. Ground-based observation is extremely difficult because of atmospheric water. Although a first generation of ground-based submillimeter telescopes is currently being constructed in high, dry locations, the advantages to observing this spectral

30 THE SEARCH FOR LIFE'S ORIGINS region from space are enormous (e.g., with LDR and SIRTF). An equally important problem, however, is the small laboratory data base on which submillimeter astronomy can draw. Very few gas-phase molecules have been examined in the submillimeter region; many more studies are needed. Thus, a necessary component of a strategy aimed at using this spectral range to study star-forming regions involves laboratory spectroscopy. To achieve the recommendations listed below, it will be necessary for exobiologists to interact closely with the astronomical and planetary science communities. The committee supports the major recommendations of the Astronomy Survey Committee (Astronomy and Astrophysics for the 1980s, Volume 1, National Research Council, 1982) to construct an LDR in space to carry out spectroscopic and imaging observations in the far-infrared and submillimeter wavelength regions of the spectrum that are inaccessible to study from the ground. Such an instrument, in the 10-m class, will offer unprecedented opportunities for studying the molecular and atomic pro- cesses that accompany the formation of stars and planetary systems. The committee also concurs with the recommendation from A Strategy for Space Astronomy and Astrophysics for the 1980s (SSB, 1979) that development of a meter-class, cryogenically cooled, infrared telescope be actively contin- ued, with the option of its construction as a free-flying spacecraft being retained until the Shuttle environment has been demonstrated to be suffi- ciently free of contaminants (SIRTF). OBJECTIVE 2: To determine the composition, structure, and interrela- tionships among circumstellar, interstellar, and interplanetary dust. Interstellar grains constitute an important component of the interstellar medium. They play a crucial role in the heating and cooling of interstellar clouds through the absorption of visible and ultraviolet photons and the ejection of energetic photoelectrons. They also influence the gas-phase composition of molecular clouds directly by providing surfaces for reac- tions and indirectly by locking up some elements, as well as by shielding molecules from the dissociative ultraviolet interstellar radiation field. Ob- servations have shown that these dust grains have a size distribution rang- ing from approximately 3000 ~ down to perhaps molecular sizes and that they lock up a large fraction (290 percent) of some heavier elements such as silicon, iron, calcium, and aluminum, as well as a substantial fraction of the available carbon, nitrogen, and oxygen. The life history of interstellar grains is a complex interplay of many different competing processes, including nucleation and condensation around stars and accretion, chemical modification, and shock processing in the interstellar medium. Some interstellar grains ("star dust") originally con- densed in the high-density, high-temperature environment (n ~ 108 cm~3; To 1000 K) of the circumstellar envelopes of red giants, planetary nebulae, and

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 31 novae and have subsequently been expelled into the interstellar medium along with gaseous species. Other possible dust components may originate in the interstellar medium itself by accretion, reaction, and photolysis of gaseous species on preexisting grain cores. Laboratory experiments suggest that a C60 spherical molecular species "fullerene" may also be a component of interstellar dust. Table 2.2 contains a summary of current knowledge of the composition of interstellar dust. There is at least some evidence for all of the dust components shown in circumstellar or interstellar environments, mainly through low-resolution infrared spectroscopy (see below). Silicate grains are a ubiquitous component of the dust in the diffuse (n < 102 cm~3) interstellar medium, and this star dust component may actually make up about half the interstellar dust volume (cf. Table 2.2~. On the basis of elemental abundances and stability, the remainder of the dust vol- ume has to consist of species containing predominantly carbon. However, it is still an open question whether this carbon is in the form of graphite, which would likely be a star dust component, or in the form of refractory organic grain mantles, which might form via processes in the interstellar medium. Although small graphite particles (~200 A' may be the carriers of the ubiquitous 2200-A bump in the ultraviolet spectra seen toward stars, large graphite grains (1000 ~) do not possess any currently detectable infra- red or ultraviolet absorption features; thus, we can only guess at their con- tribution to the interstellar dust volume. Icy grain mantles, consisting of simple molecules such as H2O, CO, and perhaps NH3 and CH3OH (methanol), are an important component of inter- stellar dust inside dense molecular clouds, but they have never been ob- served in the diffuse interstellar medium. Traces of more complex organic molecules (e.g., aldehydes, ketones, and nitrites) have also been reported in some objects. Icy grain mantles are presumably formed by the accretion of gas-phase species onto preexisting cores inside molecular clouds. In the less dense interstellar medium, these volatile materials would be efficiently destroyed by photodesorption and subsequent photodestruction in the inter- stellar ultraviolet radiation field and by shock waves. Inside dense molecu- lar clouds the much lower ultraviolet flux from embedded newly formed stars or from cosmic-ray excitation of molecular hydrogen may be suffi- ciently high to transform the simple icy molecules into more complex mole- cules, which are more refractory. This process may also be the source of the more refractory grain mantles possibly observed in the diffuse interstel- lar medium. GRAIN INTERRELATIONSHIPS The evolution of biogenic elements in the interstellar medium prior to the formation of the solar system has gained additional interest with the

32 CO an o o V Cat sat en - Cat - D ._ Cat U: o ~¢ sit - Ct ._ V' - C) an > ·— c: ~~ 3 _ _ ~ O _ ~ ~ .D Hi ~ ._ A ._ m - o o C ED ~ ~ 5 _, ,, At, ~ = A, - } t— 00 ~ ~ ~ ~ 0 00 00 of O . . . ~- O C`. o ~ O O—c`I ~ 0 ~ ~ I I ~ Al ~ ~ Vl ~ C =) ~ o E ~ ~ 20 C c c ~ ~ ? ~ ~ o ~ ~ ~ ~ c D D D o C O V V V ~ C V V ._ C~ — U: C~0 E ~; ~ o E E ~ ~ ~ ;^ Cq o o C) _l ~ ~ ~: c~ ~ ca ~ ~ Ct c, ,, ~ ~ c E ~ >` E ~ "V _ ( ¢L, ~ ~ O - o C~ ._ ._ ._ - ._ ~: ._ c: ~ E E Do ~ .D ~ _ ~ U. ( e~ O O C) ,,= Ct ~4 g ~ ~V ·— O ~ 3 ~ 3= o ct O ~ —o O O ~ ~ '40 O ~ .,= ~ O O .~ · - c: :~ .— ~D ~ CO ._ ~ ~ _ ._ ,~, s~ Ct - U, C~ C~ U, ._ ~ 3 ~ o o~ .D s ._ ._ ~: ._ C) o Cd — C.) ~ . _ ~ ~o au — 4— Ct Oo C) ._ :, ~ ~: o ·E ~ C~ ~ 8 8 o ~ ~ E E E C) ~ o ~ ~ _ c~ (U ~ ~ _t ca ~ o ~ ·C ·~ ~D - 4_ o ~: U,

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AD COMPOUNDS 33 (a) Activated Carbon-Raman ~1 f . . l r I ~ _' (b) Orion Bar-Emission f 1000 1200 1400 1600 1800 Frequency (cm~1 ) (c) Murchison- ~ Raman Jam Ji . , I , , , ~ I I I _ a__ ~ ~ 1000 1200 1400 1600 1800 FIGURE 2.2 Infrared spectra of (a) soot derived from automobile exhaust, (b) the Orion molecular cloud, (c) a carbonaceous chrondritic meteorite, and (d) an inter- planetary dust particle. discovery in recent years that presolar grains have apparently been incorpo- rated into meteorites without totally losing their identity (see discussion following objective 4 below). An interrelationship among circumstellar, inter- stellar, and interplanetary dust is supported by a comparison of infrared and Raman spectra from such sources. For example, Figure 2.2 shows the mid- infrared spectrum observed toward the prominent ionization bar in the Orion nebula (interstellar cloud), in which the emission has been ascribed to infra- red fluorescence of interstellar polycyclic aromatic hydrocarbon molecules (hereafter PAHs) pumped by the absorption of energetic ultraviolet photons from nearby embedded stars. Similar midinfrared spectra have been ob- served toward reflection nebulae, carbon-rich planetary nebulae, and some galactic nuclei. Presumably, these PAHs are the extension of the size dis- tribution of interstellar carbon grains into the molecular domain, and these large molecules are formed as the condensation nuclei of carbon grains in the circumstellar outflow of carbon-rich planetary nebulae and red giants. The observed interstellar infrared spectrum is compared in Figure 2.2 to the laboratory-measured Raman spectra of carbonaceous grains in interplane- tary dust particles, carbonaceous chondrites, and auto exhaust. The striking

34 THE SEARCH FOR LIFE'S ORIGINS similarities among these spectra illustrate the structural similarities in these different types of cosmic grains. In addition, the discovery both of anomal- ously low 12C/I3C ratios in a refractory carbon phase in meteorites, and of isotope ratios attributable to discrete nucleosynthetic (stellar) sources for noble gases trapped within meteoritic carbonaceous grains, suggests an ori- gin in red giants for these grains. This means that some interstellar carbon grains have been carried into the solar system and incorporated into larger bodies. Similar evidence from the deuterium-to-hydrogen ratio in some components of carbonaceous meteorites is discussed following objective 4 below. Strengthening and extending the possible interrelationships among circumstellar, interstellar, and interplanetary dust should be an important goal for the near future. Because other interstellar dust components may also have survived incorporation into the presolar nebula, it is important that searches be conducted for interstellar or circumstellar signatures for the biogenic elements in other primitive interplanetary, meteoritic, or cometary dust components such as silicates, carbides, and ices. INFRARED SPECTROSCOPY AND ASTRONOMY As already demonstrated, infrared spectroscopy is a useful tool for study- ing the composition of cosmic dust. Broad emission and absorption fea- tures often appear superimposed on the midinfrared thermal continua of interstellar and circumstellar emission regions. These features are due to vibrational transitions in solid materials or large molecules and can be used to identify the functional groups present. Infrared spectroscopy has already been used to infer, to varying degrees of certainty, the presence of silicates, icy grain mantles (e.g., solid H2O, NH3, CO, and CH3OH), PAHs, silicon carbide (SiC), magnesium sulfide (MgS), organic refractory grain mantles, and possibly amorphous carbon in interstellar and circumstellar objects (cf. Table 2.2~. Future work should concentrate on characterizing the molecular complexity of icy grain mantles inside dense molecular clouds and the pos- sible organic refractory grain mantles in the diffuse interstellar medium. In this respect it is particularly important to investigate further any evolution- ary relationship. Another line of research should be the search for deuter- ated molecules in these dust components, because this information may confirm the possible link between interstellar grains and components of meteoritic and interplanetary dust. Such studies, down to a D/H enrichment of 103 over cosmic levels, are possible with present or near-future instru- mentation for the most abundant molecules. Special emphasis should be given to regions with evidence for proto- or postplanetary disks (e.g., Vega and ~ Pictoris). Except for interplanetary particles, little is presently known about the isotopic and biogenic element composition of dust in protostellar nebulae. Emission by warm silicate

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 35 grains is commonly observed around newly formed stars. In addition, ice absorption features are also observed toward embedded infrared sources (protostars?), but they are generally caused by very cool (10 to 50 K) dust in the intervening parental molecular cloud rather than by dust in the puta- tive collapsing protostellar envelope or the protoplanetary disk. This is partly because of the large beam size of existing observations (~1', corre- sponding to 104 AU at the distance of the nearest sources of star formation). Infrared Astronomical Satellite (IRAS) and Kuiper Airborne Observatory (KAO) studies have shown the usefulness of far infrared for the detection of protostellar and protoplanetary disks around protostars and main sequence stars; nevertheless, higher angular resolution is an important goal. Because important parts of the 2- to 1000-,um spectral region are blocked by atmospheric absorption, even from airborne altitudes, space-based obser- vations are required. These have the added advantage of cryogenic cooling and thus of lower background. The resulting higher sensitivity will permit observations of weaker infrared sources. Given the expected width of ab- sorption and emission features, a resolution (~//~) of about 3000 is neces- sary to study the grains, whereas even higher resolution is required for observations of the gas phase. The composition of interstellar, circumstel- lar, and protostellar dust is very complex and probably varies from object to object. Observations of many different objects and correlation of their observed absorption or emission features, supported by theoretical and labo- ratory studies, will be required to unravel this complexity and to identify the molecular constituents responsible. Although in the long-term, space- based infrared observations (as would be provided by SIRTF) are called for and efforts should be directed at preparing for such endeavors, in the short term, characterization of the dust through ground-based as well as airborne infrared observations should continue. Higher resolution (~//~\ > 200) than presently used for such studies is an important near-term goal. Further improvements in sensitivity will be possible when larger ground-based or airborne telescopes become available. Continued analysis of the IRAS data base is also important. Despite the rather poor spectral resolution (~/~\ = 10 to 40), the 8- to 22-,um spectra obtained with IRAS have already yielded valuable new insights into the properties of interstellar and circumstellar dust. The electronic transitions that dominate the visible and ultraviolet spec- tra of solid materials are very characteristic of their chemical composition and structure. However, it should be noted that the sizes of interstellar and circumstellar grains are comparable to wavelengths in the visible and ultra- violet spectral regions. Size and shape effects will then influence the ob- served spectra. In particular, the presence of a grain size distribution will tend to smear out spectral structure and, therefore, hamper the characteriza- tion of grains. Nevertheless, because of the possible unique interpretation,

36 TlIE SEARCH FOR LIFE'S ORIGINS studies of structure in the visible and ultraviolet spectral regions are very important and should be pursued further. Of particular importance is the search for spectral structure in the ultraviolet region, which will become possible with the launch of the Hubble Space Telescope. Visible and ultra- violet studies can also give indirect information on the composition of inter- stellar dust through studies of gas-phase depletion of the biogenic elements. These observational projects require much supporting laboratory and theoretical effort. For successful interpretation of interstellar spectra, labo- ratory studies should include infrared spectroscopy of candidate molecules (e.g., PAHs) and molecular ice mixtures. Also important are experimental studies on interstellar grain chemistry, including grain surface chemistry as well as the effects of ultraviolet photolysis and transient heating on the composition of interstellar grain mantles. Studies of the condensation pro- cess in the outflow from late-type giants, planetary nebulae, novae, and supernovae should be undertaken. Special emphasis should be given to isotopic enrichments during the condensation process, including those of trace noble gases trapped in the solid phase. Correlation studies with grains identified in primitive solar-system materials, including carbonaceous chon- drites, interplanetary dust particles, and cometary materials, will be able to elucidate the possible interrelationships among interstellar, circumstellar, and interplanetary grains. Finally, the possibility of cosmic dust collection in earth orbit should be mentioned. This is, of course, of primary concern for the collection of meteoritic and cometary debris, but if such instrumentation were able to measure the orbital elements of collected dust particles, then interstellar dust particles could be separated from interplanetary ones. The possibility of studying actual interstellar grains in the laboratory rather than by remote sensing is an exciting prospect and would undoubtedly revolutionize our knowledge of interstellar grains and their connection with primitive inter- planetary particles. OBJECTIVE 3: To assess the efficacy of chemical and physical pro- cesses in the solar nebula for altering preexisting materials and producing new compounds and phases containing the biogenic elements. The collapse of one particular interstellar cloud led to the formation of a flattened disk of dust and gas that is referred to as the solar nebula, in which the Sun and planets formed. In currently accepted models of the solar nebula, radial temperature gradients are presumed to be a major influ- ence on the composition of the gas and dust grains. These models indicate that as the interstellar gas and dust were accreted by the solar nebula, they were thermally and chemically equilibrated to varying degrees. Accreting gases may have been only partially equilibrated (or not at all) as they were warmed and compressed. The extent to which this occurred would be de-

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 37 pendent on the distance of the gas parcel from the protosun and the rate of radial transport in the nebula relative to the rate of equilibrating reactions in the gas parcel. Similar considerations apply to the accreted interstellar dust grains. Recent theoretical work suggests that accreting dust grains may have evaporated totally, partially, or not at all, depending on the type of grain, the strength of radial mixing in the nebula, and the distance from the protosun. Isotopic data for the primitive calcium- and aluminum-rich inclu- sions (CAIs) in the Allende carbonaceous chondrite imply that the CAIs formed by a complex sequence involving condensation, partial evapora- tion, and recondensation. Such observations and theoretical models strongly suggest that evaporation and recondensation leading to thermal and chemi- cal equilibration were very probable in the inner regions of the solar nebula. The net result of these processes would have been the alteration and repro- cessing of any existing compounds and phases containing the biogenic ele- ments (except possibly for very refractory "graphitic" phases). However, these arguments become less and less convincing with increas- ing radial distance (and thus lower temperature) in the solar nebula. Again, inferences from meteorites are instructive. The observed isotopic anoma- lies in several biogenic elements (e.g., H. C, N. O) in the volatile-rich carbonaceous chondrites imply that interstellar material (or at least its chemi- cal and physical signature) is preserved in these meteorites. This result contrasts with the "standard" chemical model of the solar nebula, which assumes complete evaporation and recondensation of the grains and com- plete chemical equilibration of the gas and dust. The two most important conclusions of such a standard model are (1) that the solid grains that equilibrated at lower temperatures (i.e., farther from the protosun) are predicted to contain more biogenic element-bearing phases and to be more rich in volatiles than the solid grains equilibrated closer to the protosun, and (2) that the biogenic element-bearing phases are predicted to be simple molecular compounds such as H2O (either as water ice or as bound water in hydrated silicates), NH3 or NH3 hydrates, and CH4 or CH4 clathrate hydrate. Other biogenic elements such as sulfur or phos- phorus are predicted to be retained in the solid grains in the form of solu- tions in iron-nickel (Fe-Ni) alloys, as sulfides or phosphides of Fe-Ni, or as phosphate minerals. Although the major predictions of this equilibrium model for the bulk composition of planetary-forming materials are consistent with observations of the terrestrial planets and the asteroids, several important facets of the chemistry of the biogenic elements (in addition to isotopic anomalies) can- not be accommodated within the framework of this model. In particular, the atmospheric inventories of CO2 on Venus and Earth, and of N2 (gaseous nitrogen) on Venus, Earth, and Mars, are larger (substantially so in the case of N2) than the inventories predicted by the complete equilibrium model.

38 THE SEARCH FOR LIFE'S ORIGINS Likewise, carbonaceous chondrites may contain several percent (by mass) of organic material, which is the dominant reservoir of carbon and nitrogen in these meteorites. Neither the relatively large abundance nor the complex molecular structure of the carbon- and nitrogen-bearing phases can be ac- counted for by the complete equilibrium model. Indeed, the occurrence of oxidized carbon molecules such as CO and CO2, which have been observed in comets, also cannot be explained by this model. It is therefore necessary to explore nonequilibrium effects on the chemistry of the biogenic elements and compounds in the solar nebula. Among the various nonequilibrium processes pertinent to the solar neb- ula, more research has been done on thermal effects associated with cooling than on other processes such as shock heating, ultraviolet irradiation, solar flares, and lightning. Understanding the effects of these latter processes on the chemistry of the biogenic elements and compounds is important, and much more effort should be devoted to their investigation. Nonequilibrium thermal effects in a cooling parcel of gas and dust in the solar nebula will be favored when the characteristic cooling time (or the characteristic radial mixing time) is less than the characteristic chemical time scales for the gas-phase (tg), gas-solid (tgs), and solid-solid (tSs) reac- tions that may occur inside this parcel. If the characteristic cooling time is tc, this condition can be expressed by the inequalities tc < tg, tc < tgs, and tc < tSs. These inequalities will be favored by low temperatures, fast nebular cooling rates, and fast radial mixing times; for reactions involving solids, the inequalities will also be favored by large grain sizes and fast accretion rates for these grains. How will nonequilibrium thermal effects influence biogenic element chemistry? Some insight into this question can be achieved by considering two reactions that exemplify biogenic element retention by solid grains in a cooling parcel of gas and dust in the solar nebula. First, consider solid- solid reactions: these are likely to be the most sluggish and hence the most susceptible to nonequilibrium effects. The retention of H2O as the hydrous mineral serpentine proceeds by the reaction Mg2SiO4(s) + MgSiO3(s) + 2H2O(g) = Mg3Si2O5(OH)4(s), which, because it requires the transport and reaction of elements between two minerals, may proceed very slowly at low temperatures (400 K) where serpentine is thermodynamically stable in the solar nebula. If this is the case, then tc << tSs may hold, and in the absence of "fast" pathways for forming equal amounts of other hydrated phases, H2O may not be retained in solid grains until below 200 K, when H2O ice becomes stable. This has significant consequences for H2O retention by the terrestrial planets and implies that H2O must be delivered to these planets by icy planetesimals and comets gravitationally scattered in the inner solar system during the

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 39 later stages of planetary accretion. It may be shown that a similar conclu- sion applies to these planets' sulfur inventories. An exemplary gas-gas reaction is the conversion of CO to CH4: CO(g) + 3H2(g) = CH4(g) + H2O(g). Kinetic inhibition of the conversion of CO to CH4 has in fact been studied quantitatively; for estimates of the nebular cooling time tc consistent with estimates of the nebular lifetime, and for estimates of the nebular radial mixing time tm consistent with subsonic radial mixing, only a few percent of the available CO can be converted to CH4 before this reaction is quenched. However, in this instance the failure to achieve equilibrium may make the retention of carbon by planetary-forming materials in the inner regions of the nebula easier instead of more difficult. The homogeneous gas-phase conversions between CO and CO2 can continue down to relatively low tem- peratures, leading to the presence of several percent of carbon as CO2 in fact, more carbon can be present as CO2 than as CH4. In turn, the CO2 can condense as a solid or it can undergo further reactions with H2O leading to the formation of a clathrate hydrate or reactions with NH3 leading to the formation of either ammonium bicarbonate (NH4HCO3) or ammonium car- bamate (NH4CO2NH2~. The latter two species would be readily incorpo- rated into the first H2O-ice-rich condensate, providing four major biogenic elements (H. C, N. O) and the presence of an aqueous phase in small bodies such as comets and asteroids. Also, the presence of metastable CO inside the CH4 stability field leads to supersaturation of elemental carbon in the gas phase, which can be relieved by the formation of organic material, as in the Fischer-Tropsch reaction, or by shock heating from lightning. In fact, the implications of the failure to achieve chemical equilibrium between nebular gas and grains are important in a much broader context. For example, if the accreting interstellar gas is not chemically equilibrated before the condensable components of this gas are incorporated into solid grains, then the chemical and isotopic diversity present in this fraction of the gas will be preserved until some point in the future—perhaps until a volatile-rich cometary body impacts the Earth. Given the relative rapidity of gas-solid condensation reactions (especially when "rocky" condensation nuclei may already be present in the outer regions of the solar nebula) and the sluggishness of molecule-molecule and molecule-radical reactions at the low temperature (<100 K) predicted, in the outer solar nebula, nonequilib- rium effects may be the rule rather than the exception. Other inherently nonequilibrium processes, such as photochemistry, so- lar flares, lightning, coronal discharges, and planetesimal impacts, must also be considered for their influences on biogenic element chemistry in the solar nebula. In general, the net effect of such processes will be to increase molecular complexity and diversity over that expected if the chemistry of

40 THE SEARCH FOR LIFE'S ORIGINS the biogenic elements were allowed to approach equilibrium. For example, observations of young (T Tauri) stars suggest that the early Sun's ultravio- let flux may have been enhanced by a factor of 104 relative to the present- day flux. If this enhancement factor and a nebular lifetime of 106 years are assumed, then the potential number of molecular dissociations produced by this early enhanced ultraviolet flux would be equal to the number of mole- cules in a solar composition nebula of approximately 10 solar masses. The ultraviolet flux from nearby stars is also a potential nonequilibrating mechanism in the solar nebula. Although the corresponding flux from the early Sun is orders of magnitude greater and may lead to a larger number of molecular dissociations, subsequent pyrolysis of the product molecules in the hot inner regions of the solar nebula may lead to a very small overall net yield of nonequilibrium species (e.g., both simple and complex organic compounds). On the other hand, the relatively smaller number of photo- chemically pumped molecular dissociations in the outer regions of the solar nebula that are shielded from the Sun by particulate matter in the nebula itself may give a larger net yield of nonequilibrium species due to the absence of efficient thermochemical loss mechanisms for the product mole- cules. The production of nonequilibrium species by solar flare irradiation and rapidly quenched high-temperature shocks, such as those associated with lightning and with planetesimal impacts, will also increase the molecular complexity and diversity of biogenic-element compounds present in the solar nebula. Little quantitative modeling or laboratory simulation has been done for these potentially important processes. However, the modeling and simulation that have been done for lightning, coronal discharges, and im- pacts on the primitive Earth and on the outer planets show that HCN (hydro- gen cyanide) and H2CO, which are important precursors in the synthesis of more complex organic compounds, can be produced with relatively high efficiencies from gas mixtures of H2O, CH4, and NH3. More work on the effects of solar flare irradiation and high-temperature shock chemistry on the biogenic elements and their compounds in a nebular environment is desirable to explore these attractive possibilities. It is necessary to do theoretical modeling of nonequilibrium effects on important gas-solid and solid-solid reactions responsible for the retention of biogenic-element-bearing phases in planetary-forming materials. Perhaps the single most important class of reactions to be studied is that responsible for incorporating H2O into planetary-forming materials. The thermochemi- cal reactions responsible for the conversions of solid carbonaceous phases, "reduced" carbon-bearing gases, and "oxidized" carbon-bearing gases also deserve detailed quantitative modeling. Although sufficient basic data on some chemical reaction rates and pathways are currently available, in other instances new laboratory studies of chemical reaction rates are necessary to

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 41 obtain the date for theoretical modeling. Kinetic data are specifically needed for homogeneous gas-phase kinetics of the conversion of reduced and oxi- dized phosphorous compounds, and heterogeneously catalyzed kinetics for the conversion of reduced and oxidized carbon compounds. It is also important to use realistic laboratory simulation experiments and quantitative theoretical modeling to study the effects of photochemically pumped nonequilibrium chemistry on the biogenic elements and their com- pounds under pressure, temperature, composition, and photon flux condi- tions consistent with currently accepted models of the solar nebula. In this regard it would be particularly valuable to try to simulate the effects of the ultraviolet flux from nearby stars on the gas-solid distribution of the bio- genic elements carbon, nitrogen, sulfur, and phosphorus between a cold solar composition gas and the grains embedded in it. The use of different substrate types (e.g., "rock," metal, and carbonaceous or graphitic material) for the simulated grains is also recommended. These experiments may yield important insights into the chemical processes affecting the biogenic elements in the outer regions of the nebula where thermochemical reactions were (probably) unimportant. Finally, the use of realistic laboratory simulation experiments should be extended to the study of other nonequilibrium processes affecting the bio- genic elements and their compounds in the solar nebula. Such processes include the production of organic compounds by the rapid quenching of high-temperature shocked gas mixtures (as in corona discharges, lightning, or planetesimal impacts), the gamma radiolysis of CO CO2 H2 Fez+ mixtures, and Fischer-Tropsch reactions. If simulations under conditions of pressure, temperature, composition, and energy input consistent with cur- rently accepted models of the solar nebula are impractical, then every effort should be made to conduct experiments under conditions that permit ex- trapolations to model conditions with a high degree of confidence. OBJECTIVE 4: To determine how the formation and evolution of primi- tive bodies modified the distribution, structure, and composition of preex- isting compounds and solid phases containing the biogenic elements. GRAIN INTERACTIONS The earlier objectives discussed chemical processes in the gas and grains of the solar nebula. Here, the physical growth of these grains into large objects and the chemical changes corresponding to such growth are consid- ered. The formation and development of primitive bodies encompass a wide spectrum of processes from the gentle amalgamation of micron-sized dust particles into larger aggregates to the differentiation of metals, silicates, and

42 THE SEARCH FOR LIFE'S ORIGINS volatiles in asteroidal objects. Depending on the accretion conditions and the geological evolution of their host bodies, the records of attendant altera- tions in the distribution, structure, and composition of the gases and grains inherited from the solar nebula would have been preserved with varying degrees of integrity. Some processes would have given rise to new com- pounds and solid phases, and these may testify to the earliest analogues of prebiotic processes that occurred later in the first 700 million years on the terrestrial planets but for which no geological record is accessible. For present purposes it is convenient to consider three stages in the development of primitive bodies: (1) coagulation of nebular dust into centi- meter-sized aggregates, (2) formation of kilometer-sized planetesimals, and (3) accretion of planetoids tens to hundreds of kilometers in diameter (i.e., asteroid-sized objects). Very few observational or experimental data exist regarding the first two stages, although some evidence may be uncovered through studies of meteorites, asteroids, comets, and interplanetary dust particles (IDPs). In the first stage of this process, the complex interplay of grain-grain and gas-grain interactions would have established a balance between growth and destruction such that a significant number of aggregates in the range of 0.1 to 10 cm could have formed, even though most of the mass of dust would have remained in the micrometer range. During particle growth, adsorption and eventual trapping of volatiles (including noble gases) within the aggregates could have taken place, thus preserving a record of the gas composition of the solar nebula. Such en- trapment has been suggested to account for the noble gases in primitive meteorites, the bulk of which reside in carbonaceous grains. Chemical and isotopic fractionation also could have occurred as a result of the separation of dust and gas. For example, if the bulk of any of the biogenic elements resided in dust, then their concentrations would have been strongly en- hanced in the equatorial plane of the nebula, and they would have been preferentially incorporated into planetesimals. The growth of particles by accretion would have depended on their com- position and structure, other factors being equal. The sticking of particles to each other involves short-range van der Waals, electrostatic, or ferromag- netic forces, of which van der Waals forces are expected to be the most important for nonmetallic grains. In this regard, it has often been suggested that the "stickiness" of organic matter may have facilitated grain growth in the early solar system. In a similar vein, it may be expected that accretion would be less favorable in collisions between hard compact grains than in interactions between relatively soft and porous deformable ones. Both of these hypotheses imply a critical role for the biogenic elements in facilitat- ing the earliest stages of the formation of solid bodies, but neither has been tested by experimental observations.

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 43 Relics of kilometer-sized planetesimals formed in the second stage of development may still be preserved as small comets in the Oort cloud, and it has been suggested that the geomorphology of Comet Halley shows signs of formation through impact accretion of cometesimals in this size range. Similarly, evidence of planetesimals formed closer to the protosun than Jupiter may be found in the asteroid belt, and variations in their chemical composition with heliocentric distance may reflect the distribution of bio- genic elements in planetesimals during this stage. Based on modeling studies, the formation of planetoid-sized primitive bodies began with the relatively gentle collisional aggregation of planetesi- mals and smaller objects in nearly circular orbits. As some bodies grew to planet size and became large enough to perturb the trajectories of smaller objects in their vicinity, the remaining planetoids would have acquired more eccentric orbits and larger collisional velocities. Thus, accretion would have changed from a low-energy accumulation stage, which produced rela- tively homogeneous bodies, to one of higher energy involving a balance between shattering and accumulation, which mixed materials from a wide range of orbits and formation environments. Evidence of impacts is pre- served throughout the solar system in the cratered surfaces of planets and their satellites, including the moons of Mars (Phobos and Deimos). Repeated cycles of accretion, breakup, and continued growth would have produced surface regolith environments tens to hundreds of meters thick. Cooling times within thick regolith blankets could have been as long as hundreds of years. These processes would have mixed into the same body organic and inorganic materials from a variety of sources, including other bodies that had experienced separate evolutionary histories. Thus, materi- als oxidized and reduced, pristine and highly altered, and both rich and depleted in the biogenic elements may have been coaccreted. Such a diver- sity of materials -and, by implication, sources is indeed found in carbon- aceous chondrites, wherein, for instance, igneous mineral inclusions coexist with amino acids. The possible fates of compounds and phases containing the biogenic elements in this stage of planetoid formation are many and diverse. To varying degrees of intensity, impacts could have caused pyrolytic decompo- sition of heat-sensitive organic matter to form both gaseous and refractory products, thermal and aqueous alteration of minerals and carbonaceous grains, melting, near-surface volatile transport, and loss of volatiles to transient atmospheres from either the target or the projectile. Ample observational evidence from the mineralogy of meteorites strongly suggests that virtually no parent body has escaped the effects of thermal metamorphism. Moreover, the suite of hydrous minerals found in the volatile-rich carbo- naceous chondrites has been shown to result from aqueous alteration of preexisting anhydrous assemblages in a regolith environment. How water,

44 THE SEARCH FOR LIFE'S ORIGINS carbon dioxide, and other volatiles were mobilized to accomplish this trans- formation is not known. In sharp contrast to the amount of evidence point- ing to alteration effects on minerals, very little is known about what imprint these effects left on preexisting organic matter that accreted onto the parent bodies of carbonaceous and unequilibrated chondrites. Depletions in bulk abundances of hydrogen, carbon, and nitrogen in some ordinary chondrites have been attributed to thermal metamorphism; however, evidence also suggests that volatile elements were already depleted in the nebular dust that accreted to form the chondrites. It is especially noteworthy that conditions could have existed within the regoliths or in transient atmospheres that were conducive to de nova synthe- sis of organic compounds and phases from the degradation products of preexisting material. Evidence of such synthesis is of the utmost impor- tance because analogous processes undoubtedly occurred in planetary envi- ronments, and important insights into the prebiotic mechanisms of synthesis may be obtained through study of the organic matter in meteorites. A few measurements of the isotopic composition of carbon, hydrogen, and nitro- gen in meteoritic hydrocarbons, amino acids, and carboxylic acids are con- sistent with parent body origins, but the data base must be enlarged to establish which compounds were produced in planetoid as distinct from presolar or nebular environments. A comparable situation holds for the high molecular weight insoluble organic matter that contains the bulk of the carbon and nitrogen in primitive meteorites. This chemically heterogeneous material contains small amounts of isotonically anomalous hydrogen, carbon, nitrogen, and noble gases at- tributable to presolar origins, but the amount and nature of the material that may have been affected by alteration or synthesized on the parent bodies are poorly understood. In contrast to the thermal regimes of near-surface environments, the inte- rior temperatures of the planetoids are expected to have been affected in only a minor way by discrete accretionary events. If the overall time scale of accretion was short, however, the decay of surviving 26Al 730,000-year half-life) could have melted objects as small as 1 km in diameter; over longer time scales, the decay of 40K and the actinides (~109-year half-lives) would have heated the interiors. The actual heat sources responsible for the mobilization of fluids required for aqueous alteration, internal metamor- phism, and igneous differentiation of planetoids in the early history of the solar system are unknown. Maximum temperatures within the parent bodies of chondritic meteorites may not have exceeded 1000 to 1300 K, and the composition of metal alloys in these meteorites indicates parent body slow cooling rates on the order of 1 to 100 K per 106 years. Under these conditions, preexisting

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 45 organic compounds would have been destroyed and carbonaceous grains would have been converted to graphite. Indeed, these expectations are largely borne out: metamorphosed ordinary chondrites lack organic com- pounds but do contain graphite. Perhaps the most important outcome of internal metamorphisms in the parent bodies would have been the expulsion and delivery of volatiles through overlying layers to near-surface regions by diffusion or volcanic activity. Such outgassing or transport of fluids could have been accompanied by mineral-catalyzed synthesis of organic com- pounds. Future Investigations Little is known about how the physical structure and chemical composi- tion of individual grains influence their growth under putative nebular con- ditions. To fill this knowledge gap, several types of investigations should be carried out. Calculations should be conducted to determine how the rates of formation or destruction of grain aggregates vary with particle hardness, porosity, and composition for metallic, silicate, organic, and icy grains. Theoretical studies should be complemented by laboratory experi- ments, some of which might be appropriate to carry out under microgravity conditions on the Space Station. From simulations of grain collisions under nebular conditions it should be possible to determine the relative "sticking efficiencies" of materials composed of the biogenic elements as compared with those of the rock-forming elements. The structures of aggregates pro- duced in these investigations will provide useful models against which to compare grain aggregates obtained from meteorites, IDPs, and comets. For the experimental studies, facilities capable of accelerating small particles to a range of pertinent velocities would be very valuable. Experiments should be conducted in which organic compounds and grains within inorganic matrices are subjected to laboratory simulations of phe- nomena presumed to have occurred on planetoids. For the biogenic com- pounds and phases used as starting materials in these experiments, modifi- cations of physical, chemical, and isotopic properties as a function of envi- ronmental conditions must be determined. Deeper understanding of the conditions of aqueous alteration, the identi- ties of the precursor phases, and the nature of the resulting hydrous phases should be sought in petrographic and mineral-chemical studies of carbona- ceous chondrites and IDPs. The fact that prebiotic compounds such as carboxylic acids and amino acids appear to occur only in these altered objects is particularly noteworthy, and elucidating the relationship between the origins of these inorganic and organic components is a research problem of high priority.

46 THE SEARCH FOR f IFE' S ORIGINS OBJECTIVE 5: To determine the distribution, structure, and composi- tion of presolar and nebular products in existing primitive materials in the solar system. Previous sections have considered, more or less chronologically, the evolution of chemical complexity in interstellar clouds, in the solar nebula that resulted from the collapse of such a cloud, and in solid objects that were formed in this nebula. Some end products of this evolution continue to exist today in asteroids, meteorites, comets, and IDPs and may be studied to elucidate this overall process. ASTEROIDS The asteroids are a large collection of small bodies that orbit the Sun, predominantly at distances of 2 to 3.5 AU in the "main belt" between Mars and Jupiter, residing in a transition region between the rocky terrestrial planets and the gas-rich outer planets. Dynamical calculations of asteroid orbits suggest that most of the asteroids have remained near their present relative positions in the solar system since their formation. Thus, one of the most important reasons for studying the asteroids is that they might pre- serve valuable information about the chemical and physical processes (e.g., condensation and accretion) operating in this transition region during the formation and early evolution of the solar system. Our present knowledge of asteroids is based primarily on determination of their orbits and study of the temporal variability and spectral distribution of the reflected and emitted radiation from unresolved starlike images. Spec- troscopic observations show that the asteroids vary in their surface mineral- ogical compositions and fall into broad classes that parallel, in a general fashion, some of the meteorite classes. The primitive nature of the bulk of asteroidal material is reflected by the predominance (by mass) of dark car- bonaceous material (C-type asteroids) in the main belt. Likewise, Ceres, which is the largest asteroid and contains approximately one-third of the total mass in the main belt, has a density of 2.6 + 0.7 g/cm3. This low density suggests that Ceres is far more volatile-rich than any of the terrestrial planets. Similar densities are in fact observed for the CI and CM2 types of carbonaceous chondrites; these meteorites are generally thought to be some of the most primitive early solar-system materials for which we have samples. The density of Ceres is also consistent with the predicted density of nebular condensates forming in the region of 300 K. The study of primitive material in meteorites has provided valuable in- formation about the chemical composition of the solar system and the chemi- cal and physical processes operating in the solar nebula and early solar system. However, the enormous advantage in studying primitive asteroidal

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 47 materials is that the observed properties can be identified with a specific location in the solar system. Future Investigations Determination of the chemical composition of primitive asteroidal mate- rial with sufficient accuracy to make meaningful comparisons with the chemi- cal composition of meteoritic material is of prime importance. If such a direct link can be made, then the large number of meteorite samples can be used as probes of the main belt region and of specific locations in the solar nebula. To this end the committee endorses the recommendation made by COMPLEX (Committee on Planetary and Lunar Exploration, Strategy for the Exploration of Primitive Solar-System Bodies Asteroids, Comets, and Meteoroids: 1980-1990, SSB, 1980) that "the principal chemical elements present in asteroids to more than 1 percent abundance by atom be measured to an accuracy of about 0.5 atom percent. It is expected that these will include the elements H. C, O. Na, Al, Si, S. Ca, Ti, Fe, and Nil" The recommended measurement accuracies should be sufficient to permit infor- mative comparisons with the known meteorite classes, to determine the oxidation state of major elements and to assess the degree of hydration of surface minerals. Measurement of these elements should be made at one location on the surface at least; however, it is very desirable to make measurements at different locations to determine the scale and extent of surficial heterogene- ity. Similarly it is also of interest to determine the scale and extent of radial heterogeneity by making measurements at depth or around craters where samples of the interior may have been exposed. Another important endeavor is determination of the bulk content and the chemical form of the major biogenic elements (H. C, N. O. P. and S). These may be present in a variety of molecular components that would be diagnostic of the primitive nature and degree of subsequent alteration of the asteroid. The distribution of carbon among various carbon-bearing volatiles (CO, CO2, CH4), carbon- ates, graphite, and organic polymers is of particular interest in these mea- surements. A third area of investigation, which may take a longer time for imple- mentation, is the measurement of the D/H, i3C/~2C, ~sN/~4N, 180/~60, and 170/ i60 isotopic ratios on at least one sample of an asteroid. The carbon iso- topic ratios are of interest because of the carbonaceous nature of many asteroids and the observed variability of ~3C/~2C ratios in primitive meteorite components, whereas the oxygen isotopic ratios are important for compari- son with the ratios in various meteorite classes. Different types of scientific instrumentation and different means of in- vestigation and research will have to be involved in these investigations.

48 THE SEARCH FOR LIFE'S ORIGINS Two useful techniques are X-ray fluorescence and gamma-ray spectros- copy. X rays are excited in surficial materials by solar radiation and pro- vide information on the light elements (e.g., Mg, Al, and Si) in the topmost few micrometers of a surface. Gamma rays are emitted by long-lived natu- ral radionuclides such as potassium, thorium, and uranium and also by shorter- lived nuclides formed by cosmic-ray and solar particle interactions with the surface. Both X and gamma rays can provide qualitative and semiquantita- tive analyses for a large number of elements. Both nondestructive mapping techniques and destructive analytical tech- niques may be required to measure the abundances and chemical forms of the major biogenic elements. Spectral reflectance measurements in the ultraviolet, visible, and near-infrared region can be used to determine the mineralogy and composition of surficial materials and to map the spatial extent of different classes of materials (e.g., carbonaceous matter, hydrated phases). Thermal emission spectroscopy in the mid-range of the infrared region has similar applications. Because these two techniques are sensitive to different mineral phases present on the surface, they provide information complementary to the elemental analysis techniques, which are not sensi- tive to different phases. Detailed characterization of the various molecular components in which the biogenic elements might be present will be considerably more difficult. Pyrolysis or combustion of carbonaceous material with analysis of the evolved vapors by gas chromatography/mass spectrometry has been used for meteor- ite samples and may also be used on a soft-lander. Morphological charac- terization of carbonaceous phases can be made by scanning electron micros- copy; this would be possible on a returned sample or in situ by using a specially developed instrument for spaceflight. Finally, the committee notes the suggestion that the Martian moons Pho- bos and Deimos may be captured asteroids, so their characterization is di- rectly relevant to this objective. METEORITES Meteorites are interplanetary objects that survive passage through the terrestrial atmosphere as discrete bodies or associated fragments. Ranging in size from a few grams to several tons, meteorites are grouped into two broad categories, depending on whether they are undifferentiated or differ- entiated. The undifferentiated meteorites, or chondrites, have generally not been melted; consist of a mixture of small spheroidal objects (chondrules) and finer-grained, heterogeneous material (matrix); and have close resem- blance in elemental abundances to the Sun. In fact, the nonvolatile ele- ments are generally present in solar proportions, whereas the volatile ele-

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 49 meets are depleted to variable extents. The most primitive of the chondrites are the carbonaceous chondrites. On the other hand, the differentiated meteorites, which include the irons, stony-irons, and chondrites, have been subjected to melting and fractiona- tion events, do not consist of the simple chondrule-matrix duplex structure, and do not closely resemble the chemistry of the undifferentiated meteorites or the Sun. In many instances, the compositions of the differentiated mete- orites (e.g., the chondrites) suggest chemical fractionations similar to those produced by igneous activity on the Earth and Moon. However, unlike the continuing igneous activity on the Earth, isotopic dating shows that most of the igneous fractionations reflected in the differentiated meteorites occurred 4.5 billion years ago, shortly after the formation of the solar system. A1- though the differentiated meteorites are important sources of information about the thermal histories of small planetesimals in the early solar system, they provide much less information than do the chondrites on presolar and nebular phases in primitive materials. The carbonaceous chondrites, which are generally thought to be among the most primitive early solar-system materials for which samples exist, are the best candidates for preserving presolar and nebular phases or their sig- natures (e.g., "fossil" elemental abundance patterns or isotopic anomalies). Indeed, rubidium-strontium (Rb-Sr) dating of the CAIs in the allende carbo- naceous chondrite has identified some of these inclusions as the oldest known solids in the solar system. The antiquity of the CAIs, and their resemblance (at least to a first approximation) to the chemistry and mineral- ogy of solid assemblages predicted as vapor-solid condensates at high tem- peratures from a solar composition gas, have led to intensive study of CAIs in the allende and other carbonaceous chondrites. However, to date no pristine nebular phases (i.e., vapor-solid condensates) have been identified unambiguously in any components of the chondritic meteorites. A similar situation prevails in the search for presolar phases in primitive meteorites. The canonical model for the formation of the solar nebula envisioned a homogeneous, totally vaporized swirling cloud of gas that became a mixture of gas and dust upon cooling. In this scenario, a well- defined sequence of mineral phases, which became progressively more vola- tile-rich, formed from this homogeneous cloud with decreasing temperature. The end products of this sequence were postulated to be the oxidized iron- and H2O-rich minerals observed in the carbonaceous chondrites. However, the discovery of non-mass-dependent isotopic anomalies for oxygen and subsequently for titanium in CAIs showed that this viewpoint was fundamentally incorrect. A wide range of other non-mass-dependent and mass-dependent isotopic anomalies in refractory elements (Mg, Si, Ca, Cr. Ba, Nd, Sm) have since been observed in CAIs. Although the non-

so THE SEARCH FOR LIFE'S ORIGINS mass-dependent isotopic anomalies have been interpreted in terms of mate- rial from different nucleosynthetic sources, no presolar grains have been unambiguously identified in the CAIs. Widespread isotopic anomalies are also observed in the biogenic elements hydrogen, carbon, and nitrogen and in the noble gases neon, krypton, and xenon. The observed isotopic anomalies in the biogenic elements reinforce the notion from the refractory element isotopic anomalies that presolar material from a variety of environments was incorporated into chondritic meteorites relatively unaltered and without being thoroughly homogenized in the solar nebula. Large deuterium enrichments are observed in the insoluble organic matter that forms the bulk (70 to 80 percent) of all carbon in the CI and CM2 carbonaceous chondrites. These enrichments, which cannot plausibly be explained by mass fractionation in the solar nebula, are believed to indicate that these meteorites contain remnants of material from dark inter- stellar clouds. Isotopically heavy carbon found in CM2 chondrites may indicate the incorporation of carbon grains from red giant stars into these meteorites. Isotopically light nitrogen in components of the Allende mete- orite may indicate incorporation of almost pure ON into this meteorite. At present, the complex picture described by the collective isotopic variations is incompletely understood but strongly suggests the preservation of pre- solar material from different nucleosynthetic sources and a variety of astro- physical environments. Future Investigations Observational studies of meteorites can be expected to continue to yield important results and to influence thinking on the chemical and physical processes responsible for shaping our solar system. In its 1980 report Strategy for the Exploration of Primitive Solar-System Bodies Asteroids, Comets, and Meteoroids: 1980-1990 (SSB, 1980), COMPLEX recommended that "a vigorous program of laboratory and theoretical investigations of meteorites be maintained" and also stated that "to realize the full promise of meteorite research it is necessary to maintain laboratory capabilities at the highest level of evolving technology and to encourage the development of even more sophisticated analytical methods." The committee endorses both these statements. In addition, a range of complementary studies should be pursued. Some topics are exceedingly important. Laboratory studies are required of the molecular and isotopic compositions and yields of organic molecules produced by ion-molecule reactions, ultraviolet-pumped photochemical re- actions, and high-temperature nucleation-condensation processes in a vari- ety of astrophysical environments such as dark molecular clouds and cool stellar outflows. It is of utmost importance to conduct simulation experi-

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 51 meets under realistic conditions of pressure, temperature, composition, and energy flux or to perform the experiments in such a fashion as to permit meaningful extrapolations to these conditions. Laboratory studies should also be made of the survivability of artificially induced and natural isotopic anomalies in refractory carbonaceous materials such as the insoluble organic polymer found in carbonaceous chondrites. Of particular interest is the change in a deuterium-enriched sample during heating in a solar composition gas for varying time periods. The resistance of t3C-enriched graphitic grains to pyrolysis and isotopic exchange during heating in Hz-CO gas mixtures with solar '3C/~2C ratios is also of interest. Such studies should be designed to provide kinetic data that can be applied to solar nebular models of the survivability of infalling interstellar grains. Concerted observational studies of primitive meteorites should be made to determine unambiguously the nature, amount, and distribution of deu- terium-enriched carrier phases. The use of in situ techniques such as the ion microprobe should be exploited fully in these efforts. Although the selective chemical dissolution techniques used in studies of noble gas and deuterium, TIC, or ON carrier phases have provided invaluable information, these techniques are ultimately limited by their destructive nature, which renders observation of the carrier phases in the host meteorite impossible. COMETS AND INTERPLANETARY DUST PARTICLES Comets Comets occupy a special place in the cosmic history of the biogenic elements and compounds: they hold promise of containing the most vola- tile-rich relics of processes that occurred in stars, interstellar clouds, and the protosolar nebula, while at the same time bearing evidence of their own formation and evolution as building blocks of planetary materials. Not only are they thought to contain grains and gas inherited from the interstellar cloud that spawned the solar system, they are also expected to have ac- creted both refractory and volatile material formed in cold regions of the protosolar nebula. In addition, a role as carriers of volatile and biogenic elements to the terrestrial planets where, at least on Earth, life arose and evolved is attributed to them. These expectations arise from theories that comets formed by cold accre- tion of interstellar dust and gas or solar nebular condensates, or mixtures of these materials, into small planetesimals whose size, composition, and or- bital distance from the Sun precluded subsequent differentiation. In turn, the theories are based on estimates of the relative abundances of the major elements in comets as inferred from a long history of ground-based and airborne observations of species in their comae and tails and from in situ

52 TlIE SEARCH FOR LIFE'S ORIGINS studies of Comet Halley. The relatively high ratio of volatile (e.g., water) to involatile (e.g., silicates) substances observed in comets signifies that they were accreted at great distances from the Sun and then never heated for long to temperatures much above the sublimation point of water ice in space. Although resembling primitive carbonaceous chondrites in exhibit- ing approximately solar atomic ratios of the metallic elements, comets more closely approximate the Sun and interstellar frost in the relative abundances of the volatile elements. These abundances, coupled with the putative lack of internal differentiation, place comets among the most primitive solid objects in the solar system and the likeliest to have preserved intact the gases and grains that accreted to form them. For these reasons, comets assume the highest priority among solar-system objects for study of the cosmic evolution of compounds and phases containing the biogenic ele- ments. Many major scientific questions can be addressed by the study of com- ets. These questions should be kept in mind during present and future inves- tigations. They include the following: possible relationships among bio- genic compounds and phases in cometary, meteoritic, and interstellar mat- ter; similarities between cometary and interstellar organic chemistry; and the insertion into, and stability of, interstellar material in cometary nuclei. Prior to the return of Comet Halley, the nucleus of a comet had never been directly observed, and inferences about its composition relied on re- constructions based on the abundances of radicals, ions, and atoms ob- served in the coma and tail. Reconstructions of unobservable "parent" molecules in the nucleus from observable "daughter" species are fraught with uncertainties. Nonetheless, H2O and HCN had previously been identi- fied as parent molecules. Exciting new data pertinent to the gas phase have been obtained from Comet Halley by the Giotto and Vega spacecraft, as well as from related ground-based and airborne observations. Some of these new findings point to CO, CO2, and perhaps H2CO as additional parent molecules. In particu- lar, the gases released from the nucleus were composed of about 80 percent water, 10 to 20 percent CO, a few percent CO2, and smaller amounts of other gases. In addition, analyses of the coma gas phase by neutral and ion mass spectrometers revealed a surprising abundance of peaks attributable to hydrocarbons and other organic compounds. Although the identities of these compounds are presently controversial, their occurrence strongly underscores the complexity of the organic chemical content of comets. Other especially noteworthy findings were the discovery of jets of cyanide associated with the emission of dust from active regions of the nucleus and the observation that the source of much of the CO was extended in the coma. This raises the novel possibility that the dust may contribute species directly to the gas phase.

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AD COMPOUNDS 53 Perhaps the most significant and exciting new insights into comets arose from direct observations of the nucleus of Comet Halley and its solid dust component. Fine-grained dust composed of dark, apparently carbonaceous, matter was found covering inactive regions of the comet surface and ejected in plumes from active regions into the coma. Spacecraft analyses of dust grains in the coma by impact mass spectrometry revealed a variety of com- positional types. In addition to silicatelike particles and inorganic grains of chondritic composition, several populations were found to be composed of various combinations of the biogenic elements carbon, hydrogen, oxygen, and nitrogen exclusively, as well as mixed with inorganic elements. The size and composition of the particles are consistent with our knowledge of interstellar dust, but no conclusions can yet be drawn about their origin. Clearly these particles and their counterparts or analogues in meteorites and IDPs provide fascinating new targets for study. In principle, the isotopic composition of hydrogen, carbon, nitrogen, sul- fur, and other elements in comets could provide clues to their origin. Iso- topic measurements obtained at Comet Halley for carbon, nitrogen, and sulfur, although still imprecise, appear to fall within the range of solar- system materials. Similarly, the bulk ratio of deuterium to hydrogen is compatible with that of terrestrial materials and bulk meteorites. A detailed study of dust at Comet Halley to probe the possible existence of inclusions with large D/H ratios was not possible. Interplanetary Dust Particles Interplanetary dust particles (IDPs) are extraterrestrial particles, typi- cally less than 1 mm in diameter, that survive entry into the upper atmos- phere and are currently collected by high-flying aircraft. Their contents of solar wind noble gases and cosmic-ray tracks attest to their extraterrestrial origin. Among the variety of particle types that have been identified, the most common ones exhibit the solar pattern of relative abundances for ma- jor and minor elements that typifies primitive, chemically unfractionated, chondritic materials. Often called "cosmic dust," these IDPs constitute a unique collection of samples that complement meteorites as "fossils" of the earliest history of the solar system. Some may be of interstellar origin, but the bulk are presumably cometary or asteroidal. Most of the chondritic particles that have been examined are in the 5- to 50-,um size range. They are typically black, and semiquantitative analyses show them to contain 2 to 5 weight percent, or higher, of carbon. Abun- dances of hydrogen and nitrogen have not yet been measured. Two popula- tions make up these particles: one contains only anhydrous phases; the other is composed largely of hydrated minerals, among which the most abundant are layer lattice silicates (clays).

54 THE SEARCH FOR LIFE'S ORIGINS The anhydrous particles are unique in several distinctive ways. They contain much larger amounts of carbon than comparably anhydrous meteor- ite samples. Their extreme porosity suggests previous filling by ice and structural fragility, the latter being consistent with physical properties of materials in cometary meteors. They are composed of extremely small grains, ranging from micrometers down to tens of angstroms in size, as- sembled in a highly porous, three-dimensional structure. Especially note- worthy among the minerals found as grains are carbides, graphite, and sul- fides, along with olivine and enstatite. Carbonaceous material appears to be ubiquitous as amorphous coatings and clumps and as a medium for the embedment of other inorganic grains. The lack of any counterpart for materials with these characteristics in the meteorite collections argues strongly for a different, probably cometary, . . Orlgln. Recent measurements performed on individual IDPs with the ion micro- probe revealed anomalously high D/H ratios associated with organic carbo- naceous material. Similar findings were obtained on both anhydrous and hydrous IDPs. In the case of carbonaceous chondrites, such high ratios have been interpreted as indicating the presence of interstellar organic matter. The commonality of this organic matter among several types of primitive materials may reflect a common interstellar source. Some of the IDPs composed of hydrous phases may also be related to comets. Although the clay minerals in some cases closely resemble those of carbonaceous chondrites, in other cases they are distinctly different. The degree of compactness exhibited by these particles may reflect the influence of liquid water on the origin of the hydrous phases. If such were the case, and if the particles were determined to be cometary based on other criteria, the implications for cometary thermal evolution, physical properties, and solution-phase organic chemistry would be far-reaching. Future Investigations For the foreseeable future, IDPs will provide the only prospect for direct study of comet samples. Therefore, a vigorous program of ground-based studies should be pursued to characterize them according to physical prop- erties and chemical, isotopic, and mineralogical composition, with primary emphasis on the phases and structures containing the biogenic elements. Furthermore, to expand the size of the existing inventory and perhaps ob- tain particles not captured in the stratosphere, opportunities should be ex- ploited to collect IDPs in relatively unaltered form in low Earth orbit, as for example on the Space Station. The so-called primitive IDPs appear to have no analogues in the meteor- ite collections and, therefore, are most likely to be cometary in origin. In

THE COSMIC HISTORY OF THE BIOGENIC ELEMENTS AND COMPOUNDS 55 contrast, those "chondritic" particles that contain layer lattice silicates grossly resemble samples of carbonaceous chondrites whose chemistry and mineral- ogy have been altered by liquid water, but the detailed similarities that would confirm a meteoritic rather than a cometary origin remain to be established. For this reason, the latter particles must be included along with the "primitive" ones in future investigations, and parallel studies at very high spatial resolution of the finest-grained material in carbonaceous and unequilibrated ordinary chondrites must be exploited to establish the neces- sary comparative data base. For comets, an approach is needed to address via in situ investiga- tions scientific questions about the elemental, isotopic, molecular, and mineral composition of the comet nucleus, as well as its physical properties and geological characteristics. Included in any mission package should be instruments designed to determine (1) the identities and abundances of the volatile organic compounds at depth in the nucleus as well as in the gas and dust of the coma, (2) the physical structure of the coma dust, (3) the abun- dances of the biogenic elements in the dust, and (4) the isotopic composi- tions of the biogenic elements in the gas phase. The proposed Comet Rendezvous Asteroid Flyby (CRAP) mission would provide such an instru- mental complement and would thus be the next major advance in our scien- tific understanding of comets. Furthermore, this mission would serve as a necessary precursor to a comet nucleus sample return mission (Strategy for the Exploration of Primitive Solar-System Bodies—Asteroids, Comets, and Meteoroids: 1980-1990, SSB, 1980; A Strategy for Exploration of the Outer Planets: 1986-1996, SSB, 1986b). Over this same time frame, returning short-period comets and new com- ets will provide occasions for ground-based and airborne observations. These opportunities should be exploited to address new questions raised by the recent studies of Comet Halley. For the longer term, however, highest priority for the study of the cosmic evolution of the biogenic compounds and phases must be given to the return of a comet nucleus sample. Under carefully controlled laboratory condi- tions, the full range of state-of-the-art analytical instruments and techniques could be brought to bear. Perhaps most important, the ingenuity of an international community of scientists would be released from the constraints of preprogrammed experimental approaches imposed by the requirements of remote analyses. With the expectation that such a sample will be available some time near the turn of the century, it is timely now to begin developing the analytical and sample manipulation techniques required to operate at subambient temperatures on a micrometer scale on samples likely to be dominated by ices and volatile components. The committee strongly en- dorses the recommendation for a comet sample return mission in Space Science in the Twenty-First Century (SSB, 1988a,b).

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The field of planetary biology and chemical evolution draws together experts in astronomy, paleobiology, biochemistry, and space science who work together to understand the evolution of living systems.

This field has made exciting discoveries that shed light on how organic compounds came together to form self-replicating molecules--the origin of life.

This volume updates that progress and offers recommendations on research programs--including an ambitious effort centered on Mars--to advance the field over the next 10 to 15 years.

The book presents a wide range of data and research results on these and other issues:

  • The biogenic elements and their interaction in the interstellar clouds and in solar nebulae.
  • Early planetary environments and the conditions that lead to the origin of life.
  • The evolution of cellular and multicellular life.
  • The search for life outside the solar system.

This volume will become required reading for anyone involved in the search for life's beginnings--including exobiologists, geoscientists, planetary scientists, and U.S. space and science policymakers.

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