Extraterrestrial Organic Matter: A review

We review the nature of the widespread organic material present in the Milky Way Galaxy and in the Solar System. Attention is given to the links between these environments and between primitive Solar System objects and the early Earth, indicating the preservation of organic material as an interstellar cloud collapsed to form the Solar System and as the Earth accreted such material from asteroids, comets and interplanetary dust particles. In the interstellar medium of the Milky Way Galaxy more than 100 molecular species, the bulk of them organic, have been securely identified, primarily through spectroscopy at the highest radio frequencies. There is considerable evidence for significantly heavier organic molecules, particularly polycyclic aromatics, although precise identification of individual species has not yet been obtained. The so-called diffuse interstellar bands are probably important in this context. The low temperature kinetics in interstellar clouds leads to very large isotopic fractionation, particularly for hydrogen, and this signature is present in organic components preserved in carbonaceous chondritic meteorites. Outer belt asteroids are the probable parent bodies of the carbonaceous chondrites, which may contain as much as 5% organic material, including a rich variety of amino acids, purines, pyrimidines, and other species of potential prebiotic interest. Richer in volatiles and hence less thermally processed are the comets, whose organic matter is abundant and poorly characterized. Cometary volatiles, observed after sublimation into the coma, include many species also present in the interstellar medium. There is evidence that most of the Earth's volatiles may have been supplied by a late bombardment of comets and carbonaceous meteorites, scattered into the inner Solar System following the formation of the giant planets. How much in the way of intact organic molecules of potential prebiotic interest survived delivery to the Earth has become an increasingly debated topic over the last several years. The principal source for such intact organics was probably accretion of interplanetary dust particles of cometary origin.     

The role of cometary particle Coalescence in chemical evolution

Important prebiotic organic compounds might have been transported to Earth in dust or produced in vapor clouds resulting from atmospheric explosions or impacts of comets. These compounds coalesced in the upper atmosphere with particles ejected from craters formed by impacts of large objects. Coalescence during exposure to UV radiation concentrated organic monomers and enhanced formation of oligomers. Continuing coalescence added material to the growing particles and shielded prebiotic compounds from prolonged UV radiation. These particles settled into the lower atmosphere where they were scavenged by rain. Aqueous chemistry and evaporation of raindrops containing nomomers in high temperature regions near the Earth's surface also promoted continued formation of oligomers. Finally, these oligomers were deposited in the oceans where continued prebiotic evolution led to the most primitive cell. Results of our studies suggest that prebiotic chemical evolution may be an inevitable consequence of impacting comets during the late accretion of planets anywhere in the universe if oceans remained on those planetary surfaces.     

The cometary connection with prebiotic chemistry

Amino-acids, purines and pyrimidines may have been formed in space and brought down to Earth by comets during the final stage of the Earth's cold accretion from dust. Present-day comets seem to be the remnants of the building blocks of the early solar system, put for 4.6 billion years in parking orbits in the deep cold of space by the same process of orbital diffusion that brought a veneer of cometary material to the primitive Earth. The second part of the present review examines the chemical nature of comets as can be reconstructed from (so far) very incomplete evidence.     

Serpentinite and the dawn of life

Submarine hydrothermal vents above serpentinite produce chemical potential gradients of aqueous and ionic hydrogen, thus providing a very attractive venue for the origin of life. This environment was most favourable before Earth's massive CO(2) atmosphere was subducted into the mantle, which occurred tens to approximately 100 Myr after the moon-forming impact; thermophile to clement conditions persisted for several million years while atmospheric pCO(2) dropped from approximately 25 bar to below 1 bar. The ocean was weakly acid (pH ～ 6), and a large pH gradient existed for nascent life with pH 9-11 fluids venting from serpentinite on the seafloor. Total CO(2) in water was significant so the vent environment was not carbon limited. Biologically important phosphate and Fe(II) were somewhat soluble during this period, which occurred well before the earliest record of preserved surface rocks approximately 3.8 billion years ago (Ga) when photosynthetic life teemed on the Earth and the oceanic pH was the modern value of approximately 8. Serpentinite existed by 3.9 Ga, but older rocks that might retain evidence of its presence have not been found. Earth's sequesters extensive evidence of Archaean and younger subducted biological material, but has yet to be exploited for the Hadean record.     

Extraterrestrial Flux of Potentially Prebiotic C, N, and P to the Early Earth

With growing evidence for a heavy bombardment period ending 4–3.8 billion years ago, meteorites and comets may have been an important source of prebiotic carbon, nitrogen, and phosphorus on the early Earth. Life may have originated shortly after the late-heavy bombardment, when concentrations of organic compounds and reactive phosphorus were enough to “kick life into gear”. This work quantifies the sources of potentially prebiotic, extraterrestrial C, N, and P and correlates these fluxes with a comparison to total Ir fluxes, and estimates the effect of atmosphere on the survival of material. We find (1) that carbonaceous chondrites were not a good source of organic compounds, but interplanetary dust particles provided a constant, steady flux of organic compounds to the surface of the Earth, (2) extraterrestrial metallic material was much more abundant on the early Earth, and delivered reactive P in the form of phosphide minerals to the Earth’s surface, and (3) large impacts provided substantial local enrichments of potentially prebiotic reagents. These results help elucidate the potential role of extraterrestrial matter in the origin of life.     

The fate of organic matter during planetary accretion: Preliminary studies of the organic chemistry of experimentally shocked murchison meteorite

It is possible that Earth's biologic precursors were delivered by late-impacting asteroids or comets, and it is possible that these objects were a source of Earth's volatile inventory. To understand the behavior of organic matter in carbonaceous meteorites during hypervelocity impact (1–2 km s^–1), three samples of the Murchison (CM2) carbonaceous chondrite were shocked to 19, 20 and 36 GPa and analyzed by very sensitive thermal-desorption photoionization mass spectrometry (SALI). Thermal-desorption (25–800 °C) SALI mass spectra of unshocked Murchison reveal indigenous aliphatic, aromatic, sulfur and organosulfur compounds. Samples shocked to 20 GPa exhibit little or no loss of organic matter relative to the unshocked material. This is consistent with the earlier work of Tyburczyet al. (1986) which showed that incipient devolatilization of Murchison occurs at peak shock pressures near 20 GPa. The small amount of organic matter lost appears to have occurred by volatilization of elemental sulfur, amines and aliphatic compounds. In the sample shocked to 36 GPa, approximately 70% of the organic matter was volatilized as a result of impact. The residual organic matter desorbed at somewhat higher temperatures and displayed a different chemical signature. In particular, the shocked material has a lower alkene/alkane ratio than that of the starting material. The preliminary data suggest that it is unlikely that the indigenous organic matter in carbonaceous chondrite-like planetesimals could have survived impact on the Earth in the later stages of Earth's accretion. However, chemical reactions that produce organic compounds with greater thermal stabilities may occur during impact or subsequent to impact by condensation of the impact-produced vapor plume.     

Comets and the formation of biochemical compounds on the primitive Earth--a review.

Thirty years ago it was suggested that comets impacting on the primitive Earth may have represented a significant source of terrestrial volatiles, including some important precursors for prebiotic synthesis (Oró, 1961, Nature 190: 389). This possibility is strongly supported not only by models of the collisional history of the early Earth, but also by astronomical evidence that suggests that frequent collisions of comet-like bodies from the circumstellar disk around the star beta Pictoris are taking place. Although a significant fraction of the complex organic compounds that appear to be present in cometary nuclei were probably destroyed during impact, it is argued that cometary collisions with the primitive Earth represented an important source of both free-energy and volatiles, and may have created transient, gaseous environments in which prebiotic synthesis may have taken place.     

Hcn and Hnc in Comets C/2000 Wm1 (Linear) and C/2002 C1 (Ikeya-Zhang)

Comets have been suggested as a possibly significant source of organic molecules to the early Earth. Hydrogen cyanide (HCN) is important in models of prebiotic chemistry, but may be difficult to form in the early terrestrial environment, while hydrogen isocyanide (HNC) is a `classical' tracer of interstellar ion-molecule chemistry. We have observed both HCN and HNC in 2 recent comets, bringing the number of comets with published measurements of the HNC/HCN abundance ratio to 6. The HNC/HCN ratio in comet Ikeya-Zhang appears to increase with decreasing heliocentric distance, as was previously observed for comet Hale-Bopp, indicating that the HNC is produced at least in part by processes in the cometary coma (atmosphere) and is not simply a constituent of the nuclear ices. Both comets C/2000 WM1 (Linear) and C/2002 C1 (Ikeya-Zhang) exhibit values of the HNC/HCN ratio that appear to be too large (0.09–0.19) tobe matched by current models of coma chemistry. Cometary HNC maybe a photodissociation product of organic grains or large organic polymers stored in the nucleus. We have also set a limit on the emission from the NO radical in comet WM1.     

d-Amino acids in molecular evolution in space – Absolute asymmetric photolysis and synthesis of amino acids by circularly polarized light

Living organisms on the Earth almost exclusively use l-amino acids for the molecular architecture of proteins. The biological occurrence of d-amino acids is rare, although their functions in various organisms are being gradually understood. A possible explanation for the origin of biomolecular homochirality is the delivery of enantioenriched molecules via extraterrestrial bodies, such as asteroids and comets on early Earth. For the asymmetric formation of amino acids and their precursor molecules in interstellar environments, the interaction with circularly polarized photons is considered to have played a potential role in causing chiral asymmetry. In this review, we summarize recent progress in the investigation of chirality transfer from chiral photons to amino acids involving the two major processes of asymmetric photolysis and asymmetric synthesis. We will discuss analytical data on cometary and meteoritic amino acids and their potential impact delivery to the early Earth. The ongoing and future ambitious space missions, Hayabusa2, OSIRIS-REx, ExoMars 2020, and MMX, are scheduled to provide new insights into the chirality of extraterrestrial organic molecules and their potential relation to the terrestrial homochirality. This article is part of a Special Issue entitled: d-Amino acids: biology in the mirror, edited by Dr. Loredano Pollegioni, Dr. Jean-Pierre Mothet and Dr. Molla Gianluca.     

Chemical Evolution and Meteorites: An Update

Carbonaceous chondrites are a primitive group of meteorites, which contain abundant organic material and provide a unique natural record of prebiotic chemical evolution. This material comprises a varied suite of soluble organic compounds that are similar, sometimes identical, to those found in the biosphere, such as amino acids, carboxylic acids, and sugar derivatives. Some amino acids of this suite also show L-enantiomeric excesses, and suggest the possibility they may have contributed to terrestrial homochirality by direct input of meteoritic material to the early Earth. This optical activity appears to be limited to the subgroup of alpha-methyl amino acids which, although not common in the extant biosphere, would have been well suited to provide the early earth with both enantiomeric excesses and means for their amplification by subsequent chemical evolution. We can also envision this exogenous delivery of carbonaceous material by meteorites and comets as having coincided with the endogenous formation of prebiotic precursors and influenced their evolution by complementary reactions or catalysis.     

Comets and the formation of biochemical compounds on the primitive Earth – A review

Thirty years ago it was suggested that comets impacting on the primitive Earth may have represented a significant source of terrestrial volatiles, including some important precursors for prebiotic synthesis (Oró, 1961,Nature 190: 389). This possibility is strongly supported not only by models of the collisional history of the early Earth, but also by astronomical evidence that suggests that frequent collisions of comet-like bodies from the circumstellar disk around the star Pictoris are taking place. Although a significant fraction of the complex organic compounds that appear to be present in cometary nuclei were probably destroyed during impact, it is argued that cometary collisions with the primitive Earth represented an important source of both free-energy and volatiles, and may have created transient, gaseous environments in which prebiotic synthesis may have taken place.     

Origins of life: A comparison of theories and application to Mars

The field of study that deals with the origins of life does not have a consensus for a theory of life's origin. An analysis of the range of theories offered shows that they share some common features that may be reliable predictors when considering the possible origins of life on another planet. The fundamental datum dealing with the origins of life is that life appeared early in the history of the Earth, probably before 3.5 Ga and possibly before 3.8 Ga. What might be called the standard theory (the Oparin-Haldane theory) posits the production of organic molecules on the early Earth followed by chemical reactions that produced increased organic complexity leading eventually to organic life capable of reproduction, mutation, and selection using organic material as nutrients. A distinct class of other theories (panspermia theories) suggests that life was carried to Earth from elsewhere — these theories receive some support from recent work on planetary impact processes. Other alternatives to the standard model suggest that life arose as an inorganic (clay) form and/or that the initial energy source was not organic material but chemical energy or sunlight. We find that the entire range of current theories suggests that liquid water is the quintessential environmental criterion for both the origin and sustenance of life. It is therefore of interest that during the time that life appeared on Earth we have evidence for liquid water present on the surface of Mars.     

Two Different Sources of Water for the Early Solar Nebula

Water is essential for life. This is a trivial fact but has profound implications since the forming of life on the early Earth required water. The sources of water and the related amount of delivery depend not only on the conditions on the early Earth itself but also on the evolutionary history of the solar system. Thus we ask where and when water formed in the solar nebula-the precursor of the solar system. In this paper we explore the chemical mechanics for water formation and its expected abundance. This is achieved by studying the parental cloud core of the solar nebula and its gravitational collapse. We have identified two different sources of water for the region of Earth's accretion. The first being the sublimation of the icy mantles of dust grains formed in the parental cloud. The second source is located in the inner region of the collapsing cloud core - the so-called hot corino with a temperature of several hundred Kelvin. There, water is produced efficiently in the gas phase by reactions between neutral molecules. Additionally, we analyse the dependence of the production of water on the initial abundance ratio between carbon and oxygen.     

Contributions of Icy Planetesimals to the Earth's Early Atmosphere

Laboratory experiments on the trapping of gases by ice forming at low temperatures implicate comets as major carriers of theheavy noble gases to the inner planets. These icy planetesimals may also have brought the nitrogen compounds that ultimately produced atmospheric N₂. However, if the sample of three comets analyzed so far is typical, the Earth's oceans cannot have been produced by comets alone, they require an additionalsource of water with low D/H. The highly fractionated neon inthe Earth's atmosphere may also indicate the importance of non-icy carriers of volatiles. The most important additional carrieris probably the rocky material comprising the bulk of the mass of these planets. Venus may require a contribution from icy planetesimals formed at the low temperatures characteristic of the Kuiper Belt.     

Thinking of biology: asteroid impacts, microbes, and the cooling of the atmosphere

The authors examine the cooling of the Earth's surface from 3.75 to 1 billion years ago. Three effects of the bombardment of Earth by asteroids and comets that may have delayed surface cooling include time to form continents, volatilization of carbonate rocks which released carbon dioxide into the atmosphere, and inability of microbes to inhabit land masses during large impact events. Continental microbes may have helped reduce high temperatures from 3.75 to 3.5 billion years ago. If so, the evolutionary sequence of microbes is proposed to be anaerobic heterotrophs, chemoautotrophs, and then photoautotrophs.     

prebiotic phosphorus chemistry reconsidered

The available evidence indicates that the origin of life on Earth certainly occurred earlier than 3.5 billion years ago and perhaps substantially earlier. The time available for the chemical evolution which must have preceded this event is more difficult to estimate. Both endogenic and exogenic contributions to chemical evolution have been considered; i.e., from chemical reactions in a primitive atmosphere, or by introduction in the interiors of comets and/or meteorites. It is argued, however, that the phosphorus chemistry of Earth's earliest hydrosphere, whether primarily exogenic or endogenic in origin, was most likely dominated by compounds less oxidized than phosphoric acid and its esters. A scenario is presented for the early production of a suite of reactive phosphonic acid derivatives, the properties of which may have foreshadowed the later appearance of biophosphates.     

The possible origin of the first cell biosystem in the thermal subsurface environment of the earth.

Bacteria are the simplest living biosystems or organisms that exhibit all the characteristics of life. As such, they are excellent models to examine the cell as the basic unit of life and the cell theory which states that all organisms are composed of one or more similar cells. In this article I examine the hypothesis that the primordial soup so often referred to in science was possibly an oil/water interface and/or emulsion in the Earth's, warm, anaerobic subsurface. This warm subsurface location, protected from surface radiation, could have been a favourable location for the assembly of the first bacterial cells on the Earth capable of growth and controlled division or the first biosystem.     

Mineral Radioactivity in Sands as a Mechanism for Fixation of Organic Carbon on the Early Earth

Irradiation of organic molecules by mineral radioactivity is a feasible alternative to cosmic irradiation to precipitate solid organic carbon-rich matter on the early Earth. Radioactive (uranium- and thorium-rich) minerals have been concentrated at the Earth's surface, and accumulated accretionary coatings of carbon due to irradiation, since early Archean times. The organic accretion process could have occurred at the surface or in the sub-surface, and is independent of a terrestrial or extraterrestrial source for the carbon.     

IS EXTRATERRESTRIAL ORGANIC MATTER RELEVANT TO THE ORIGIN OF LIFE ON EARTH?

I review the relative importance of internal and external sources of prebiotic molecules on Earth at the time of life's origin 3.7Gyr ago. The efficiency ofsynthesis in the Earth's atmosphere was critically dependent on its oxidation state. If the early atmosphere was non-reducing and CO2-dominated, external delivery might havebeen the dominant source. Interplanetary dust grains and micrometeorites currently deliver carbonaceous matter to the Earth's surface at a rate of 3 × 10⁵kg/yr(equivalent to a biomass in 2Gyr), but this may havebeen as high as 5 × 10⁷kg/yr (a biomass in only10Myr) during the epoch of late bombardment. Much ofthe incoming material is in the form of chemically inactive kerogens and amorphous carbon; but if the Earth once had a dense (10-bar) atmosphere, small comets rich in avariety of prebiotic molecules may have been sufficiently air-braked to land non-destructively. Lingering uncertainties regarding the impact history of the Earth and the density and composition of its early atmosphere limit our ability to draw firm conclusions.     

Formation and stability of complex organic compounds in space environments.

Complex organic compounds have been found in extraterrestrial bodies such as meteorites and comets. We confirmed the formation of complex organic compounds that contained amino acid precursors from a mixture of carbon monoxide (or methanol), ammonia and water by radiation or UV. Molecular weights of the complex organics were several thousands. Stability of the complex precursors was studied. When free amino acids were irradiated with gamma rays or synchrotron radiation, they easily decomposed. The complex precursors were, however, much more stable than free amino acid against irradiation. We propose to examine the formation and alteration of amino acid precursors in space by using exposed facility of ISS.