Molten Earth and the origin of prebiological molecules

Evidence for the molten Earth at its accretion time has been accumulated through the geochemical investigations and the observations of the surfaces of planets by space probes such as Venera 8, Mariner 9, Surveyor, Luna, and Apollo. The primitive terrestrial atmosphere might have been derived from the volcanic gases, as suggested by Rubey, but of a higher temperature than so far assumed. A thermochemical calculation of the composition of the volcanic gas suggests the following possibilities:

1. Large amounts of H₂ and CO were present in the primitive atmosphere. This gives a theoretical basis for the HCN-production experiment by Abelson.
2. HCHO and NH₃ existed in the primitive oceans, of the amount comparable with the weight of the present biosphere.
3. Plenty of NO ₃ ⁻ , SO ₄ ⁻⁻ , and PO ₄ ⁻⁻⁻ were expected in the primitive oceans. The NO ₃ ⁻ ions might have been useful for the nitrate respiration advocated by Egami.

In an appendix, it is argued, on the basis of the observational evidence of the exospheric temperatures of planets by space probes, that a highly reducing atmosphere would (if it existed on the primitive Earth) have disappeared very quickly due to the thermal escape of hydrogen from its exosphere.     

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.     

Thermodynamic Constrains for Life Based on Non-Aqueous Polar Solvents on Free-Floating Planets

Free-floating planets (FFPs) might originate either around a star or in solitary fashion. These bodies can retain molecular gases atmospheres which, upon cooling, have basal pressures of tens of bars or more. Pressure-induced opacity of these gases prevents such a body from eliminating its internal radioactive heat and its surface temperature can exceed for a long term the melting temperature of a life-supporting solvent. In this paper two non-aqueous but still polar solvents are considered: hydrogen sulfide and ammonia. Thermodynamic requirements to be fulfilled by a hypothetic gas constituent of a life-supporting FFP’s atmosphere are studied. The three gases analyzed here (nitrogen, methane and ethane) are candidates. We show that bodies with ammonia oceans are possible in interstellar space. This may happen on FFPs of (significantly) smaller or larger mass than the Earth. Generally, in case of FFP smaller in size than the Earth, the atmosphere exhibits a convective layer near the surface and a radiative layer at higher altitudes while the atmosphere of FFPs larger in size than Earth does not exhibit a convective layer. The atmosphere mass of a life-hosting FFP of Earth size is two or three orders of magnitude larger than the mass of Earth atmosphere. For FFPs larger than the Earth and specific values of surface pressure and temperature, there are conditions for condensation (in the ethane atmosphere). Some arguments induce the conclusion than the associated surface pressures and temperatures should be treated with caution as appropriate life conditions.     

Prebiotic processes in planetary atmospheres

Within 40 years of experimental studies in prebiotic chemistry, most of the building blocks of the living systems have been synthesized in plausible conditions of the primitive Earth. The starting ingredients correspond to two complementary classes: volatile organics, and their non volatile oligomers. They may have been formed in the atmosphere on the primitive Earth and/or imported by extra-terrestrial sources. Organic chemistry is involved in meteorites, comets, in the giant planets and several of their satellites. Again this chemistry presents the two complementary aspects. In particular, with a dense reduced atmosphere rich in organic compounds in gas and aerosol phases, Titan appears as a natural laboratory for studying prebiotic chemistry at a planetary scale.     

The geological setting of the earliest life forms

Summary Life on Earth may have begun about 4×10⁹ years (4 Ga) ago. Plate tectonics probably operated in the early Archaean, with rapid spreading at mid-ocean ridges, a komatiitic (magnesium-rich) oceanic crust, active volcanic arcs and the development of extensional basins on continental crust. Shallow water environments would have been more restricted and probably shorter-lived than in later geological times; however, extensive shallow seas existed in the later phases of the development of extensional basins. Bacterial communities-presumably photosynthetic-have probably existed in such shallow-water settings and probably at shallow depths in the oceans for at least 3.5 Ga. Because the mid-ocean ridges were probably subaqueous, hydrothermal systems would have been very vigorous and would have offered suitable habitats for early chemo-autotrophic bacterial communities. Early life forms probably also occupied vesicles in lavas, pumice and volcanic breccias, and pores in soft sediments, living in the constant flux of fluid flushing through permeable strata. Other, similar habitats would have existed in volcanic island arcs and in extensional basins.     

Prebiotic Synthesis of Methionine and Other Sulfur-Containing Organic Compounds on the Primitive Earth: A Contemporary Reassessment Based on an Unpublished 1958 Stanley Miller Experiment

Original extracts from an unpublished 1958 experiment conducted by the late Stanley L. Miller were recently found and analyzed using modern state-of-the-art analytical methods. The extracts were produced by the action of an electric discharge on a mixture of methane (CH₄), hydrogen sulfide (H₂S), ammonia (NH₃), and carbon dioxide (CO₂). Racemic methionine was formed in significant yields, together with other sulfur-bearing organic compounds. The formation of methionine and other compounds from a model prebiotic atmosphere that contained H₂S suggests that this type of synthesis is robust under reducing conditions, which may have existed either in the global primitive atmosphere or in localized volcanic environments on the early Earth. The presence of a wide array of sulfur-containing organic compounds produced by the decomposition of methionine and cysteine indicates that in addition to abiotic synthetic processes, degradation of organic compounds on the primordial Earth could have been important in diversifying the inventory of molecules of biochemical significance not readily formed from other abiotic reactions, or derived from extraterrestrial delivery.     

The outer solar system: Perspectives for exobiology

The outer solar system contains many environments of interest for studies of the origin of life. Recent observations support the idea that Jupiter and Saturn have retained the mixture of elements originally present in the solar nebula. Subsequent low temperature chemistry has produced the expected array of simple molecules giving characteristic absorption bands in the spectra of these planets. Microwave and infrared observations show that the lower atmospheres are at temperatures above 300 K. Sources of energy for non-equilibrium chemistry seem available at least on Jupiter and the presence of an array of colored materials in the Jovian cloud belts has often been cited as evidence for the existence of complex abiogenic organic molecules. Further study of both planets in an exobiological context seems well worthwhile; potentially productive methods of investigation (including planned space missions) can be described and evaluated from this point of view. Uranus and Neptune are clearly deficient in light gases, but otherwise little is known with certainty about these distant planets. Again unusually high temperatures have been reported, but not above 273 K. Pluto and many of the outer planet satellites appear to represent a class of small bodies very unlike our neighbors in the inner solar system. Titan, Saturn's largest satellite, is especially interesting for our purposes because of its atmosphere. Methane and hydrogen are both present, and Titan's unusually reddish color again suggests the presence of organic compounds. The hydrogen-methane ratio is likely to be more similar to that of a primitive reducing terrestrial atmosphere than the ratios for Jupiter and Saturn, suggesting that in some respects this satellite may provide an even better model for early organic synthesis on the Earth. The problem of Titan's heat balance and atmospheric composition are currently under active investigation.     

The oxygenation of the atmosphere and oceans

The last 3.85 Gyr of Earth history have been divided into five stages. During stage 1 (3.85-2.45 Gyr ago (Ga)) the atmosphere was largely or entirely anoxic, as were the oceans, with the possible exception of oxygen oases in the shallow oceans. During stage 2 (2.45-1.85 Ga) atmospheric oxygen levels rose to values estimated to have been between 0.02 and 0.04 atm. The shallow oceans became mildly oxygenated, while the deep oceans continued anoxic. Stage 3 (1.85-0.85 Ga) was apparently rather 'boring'. Atmospheric oxygen levels did not change significantly. Most of the surface oceans were mildly oxygenated, as were the deep oceans. Stage 4 (0.85-0.54 Ga) saw a rise in atmospheric oxygen to values not much less than 0.2 atm. The shallow oceans followed suit, but the deep oceans were anoxic, at least during the intense Neoproterozoic ice ages. Atmospheric oxygen levels during stage 5 (0.54 Ga-present) probably rose to a maximum value of ca 0.3 atm during the Carboniferous before returning to its present value. The shallow oceans were oxygenated, while the oxygenation of the deep oceans fluctuated considerably, perhaps on rather geologically short time-scales.     

Cometary origin of carbon,nitrogen and water on the Earth

Two independent assumptions are substantiated; firstly, that the Earth accreted from dust particles that were hot enough not to contain any volatiles; secondly, that after the accretion was finished, all the volatiles of the biosphere, including the atmosphere and the oceans, were brought by a cometary bombardment.The first assumption is based on the empirical evidence that the planets originated from minor bodies. These minor bodies were generated by accumulation of fine dust particles, which sedimented from the gas of the solar nebula. We will demonstrate that, when the particles from the Earth's zone were separated from the nebular gas, they were close to 1000 K and at a thermochemical equilibrium with this gas. This implies that almost all carbon, nitrogen and water remained in the gas phase, respectively as CO, N₂ and steam. Since there was no volatile left in the minor bodies, they could produce neither atmosphere nor oceans.The second assumption is based on the existence of the giant planets in the outer reaches of the solar system. Over there the solar nebula was very cold; the minor bodies were generated by accumulation of frosty particles and became cometary nuclei containing a large amount of ice and volatile stuff. When the giant planets' embryos reached a mass of 10 to 20 terrestrial masses, the orbits of billions of minor icy bodies were perturbed enough to send some of them to the inner solar system. A model shows that the icy bodies which hit the Earth are more than enough to explain the whole biosphere, including the atmosphere and the oceans.     

Pathways to Earth-Like Atmospheres

We discuss the evolution of the atmosphere of early Earth and of terrestrial exoplanets which may be capable of sustaining liquid water oceans and continents where life may originate. The formation age of a terrestrial planet, its mass and size, as well as the lifetime in the EUV-saturated early phase of its host star play a significant role in its atmosphere evolution. We show that planets even in orbits within the habitable zone of their host stars might not lose nebular- or catastrophically outgassed initial protoatmospheres completely and could end up as water worlds with CO₂ and hydrogen- or oxygen-rich upper atmospheres. If an atmosphere of a terrestrial planet evolves to an N₂-rich atmosphere too early in its lifetime, the atmosphere may be lost. We show that the initial conditions set up by the formation of a terrestrial planet and by the evolution of the host star’s EUV and plasma environment are very important factors owing to which a planet may evolve to a habitable world. Finally we present a method for studying the discussed atmosphere evolution hypotheses by future UV transit observations of terrestrial exoplanets.     

Delivery of extraterrestrial amino acids to the primitive Earth. Exposure experiments in Earth orbit.

A large collection of micrometeorites has been recently extracted from Antarctic old blue ice. In the 50 to 100 micrometers size range, the carbonaceous micrometeorites represent 80% of the samples and contain 2% of carbon. They might have brought more carbon to the surface of the primitive Earth than that involved in the present surficial biomass. Amino acids such as "-amino isobutyric acid have been identified in these Antarctic micrometeorites. Enantiomeric excesses of L-amino acids have been detected in the Murchison meteorite. A large fraction of homochiral amino acids might have been delivered to the primitive Earth via meteorites and micrometeorites. Space technology in Earth orbit offers a unique opportunity to study the behaviour of amino acids required for the development of primitive life when they are exposed to space conditions, either free or associated with tiny mineral grains mimicking the micrometeorites. Our objectives are to demonstrate that porous mineral material protects amino acids in space from photolysis and racemization (the conversion of L-amino acids into a mixture of L- and D-molecules) and to test whether photosensitive amino acids derivatives can polymerize in mineral grains under space conditions. The results obtained in BIOPAN-1 and BIOPAN-2 exposure experiments on board unmanned satellite FOTON are presented.     

Vacant habitats in the Universe

The search for life on other planets usually makes the assumption that where there is a habitat, it will contain life. On the present-day Earth, uninhabited habitats (or vacant habitats) are rare, but might occur, for example, in subsurface oils or impact craters that have been thermally sterilized in the past. Beyond Earth, vacant habitats might similarly exist on inhabited planets or on uninhabited planets, for example on a habitable planet where life never originated. The hypothesis that vacant habitats are abundant in the Universe is testable by studying other planets. In this review, I discuss how the study of vacant habitats might ultimately inform an understanding of how life has influenced geochemical conditions on Earth.     

Heteropolypeptides on Titan?

Since hydrogen cyanide is a component of Titan's hazy atmosphere, HCN polymers might also be present by way of a low energy pathway leading initially to the synthesis of polyaminomalonitrile. Subsequent reactions of HCN with the activated nitrile groups of this HCN homopolymer would then yield heteropolyamidines, readily converted to heteropolypeptides following contact with frozen water on the surface of Titan.Similar HCN polymers in the reducing atmospheres of Jupiter and Saturn could be major contributors to the yellow-brown-orange appearance of these giant planets.Any detection of such HCN chemistry by the Voyager missions or the pending Galileo probe would constitute evidence for the hypothesis that heteropolypeptides on the primitive Earth were synthesized directly from hydrogen cyanide and water without the intervening formation of -amino acids.Paper presented at the 6th College Park Colloquium, October 1981.     

From interstellar amino acids to prebiotic catalytic peptides: a review

Amino acids were most likely available on the primitive Earth, produced in the primitive atmosphere or in hydrothermal vents. Import of extraterrestrial amino acids may have represented the major supply, as suggested by micrometeorite collections and simulation experiments in space and in the laboratory. Selective condensation of amino acids in water has been achieved via N-carboxy anydrides. Homochiral peptides with an alternating sequence of hydrophobic and hydrophilic amino acids adopt stereoselective and thermostable beta-pleated sheet structures. Some of the homochiral beta-sheets strongly accelerate the hydrolysis of oligoribonucleotides. The beta-sheet-forming peptides have also been shown to protect their amino acids from racemization. Even if peptides are not able to self-replicate, i.e., to replicate a complete sequence from the mixture of amino acids, the accumulation of chemically active peptides on the primitive Earth appears plausible via thermostable and stereoselective beta-sheets made of alternating sequences.     

The Effects of Ferrous and other Ions on the Abiotic Formation of Biomolecules using Aqueous Aerosols and Spark Discharges

It has been postulated that the oceans on early Earth had a salinity of 1.5 to 2 times the modern value and a pH between 4 and 10. Moreover, the presence of the banded iron formations shows that Fe⁺² was present in significant concentrations in the primitive oceans. Assuming the hypotheses above, in this work we explore the effects of Fe⁺² and other ions in the generation of biomolecules in prebiotic simulation experiments using spark discharges and aqueous aerosols. These aerosols have been prepared using different sources of Fe⁺², such as FeS, FeCl₂ and FeCO₃, and other salts (alkaline and alkaline earth chlorides and sodium bicarbonate at pH = 5.8). In all these experiments, we observed the formation of some amino acids, carboxylic acids and heterocycles, involved in biological processes. An interesting consequence of the presence of soluble Fe⁺² was the formation of Prussian Blue, Fe₄[Fe(CN)₆]₃, which has been suggested as a possible reservoir of HCN in the initial prebiotic conditions on the Earth.     

Aliens at home?

If we ponder how alien life might look like on other planets, we don''t have to go far, Simon Conway Morris argues, since life forms on Earth have already pushed life to the limits.When in 1609 Galileo first saw the moons of Jupiter, he must have been spellbound. I was certainly so enrapt when I saw Europa and her three companions strung like a line of jewels. Galileo may have appreciated the irony that my guide was a Jesuit priest, and the somewhat antiquated telescope we used was but a few yards from the Papal summer residence in Castel Gandolfo. Galileo prized open the door and before long, scientific imagination was fired by the prospect of innumerable inhabited worlds. As the centuries progressed, imagination raced ahead of facts, with the Moon optimistically colonized by Selenites, and Mars transformed by immense canals to supply the parched regions of a planet plunging into desertification. From this dying planet H.G. Wells propelled his aliens to terrorize southern England with immense tripods housing sinister octopoids.Now we might be closer to knowing if Wells was in any sense on the right track. The spectacular success in detecting extrasolar planets has produced a roster in excess of 450, and this technology potentially allows us to detect Earth-like planets. Even if many of the known planets are too large to be habitable and lie, for the most part, beyond the inferred ‘habitable zones'', before long we will get some clues as to how densely our galaxy is inhabited. The consensus points in two directions. First, life is a universal. Second, our biosphere will be of almost no use when it comes to comparisons. Let me draw your attention to a remarkably unappreciated fact: if you want to understand aliens, stay at home.Am I serious? After all it is already clear that extrasolar planetary systems are vastly different to our Solar System. Immense planets orbit their suns every few days, their surfaces far more torrid than that of Venus. Other planets most likely possess giant oceans, hundreds of kilometres deep. The diversity of moons and planets in our Solar System is a reminder of what may await us light years from Earth. Even among our neighbours, a case can be made for possible life in the clouds of Venus and Jupiter, the oceans of Europa and hydrocarbon lakes of Titan, and—with perennial optimism—in the permafrost of Mars. We might assume, therefore, that the range of environments available to life, its ‘habitation box'', is gigantic, and that Earth''s biosphere just nestles in one tiny corner. Oddly enough the evidence is exactly the opposite. Life on Earth has reached the limits of what is possible—anywhere.Temperature? The current limit on Earth is 122 °C. Plunging in the opposite direction the evidence is just as remarkable. At temperatures well below freezing, life carries on cheerfully. Even far beyond the eutectic, in which free water cannot form, organisms remain in a state of suspended animation with rates of damage and repair almost precisely matched. What of extreme desiccation? Evidently life has reached the limits of water activity. Entertainingly some of the hardiest forms are fungi that inhabit the weird alien world of Blue Stilton cheese. So, too, the bright colouration of salt pans is a familiar sight, and these osmotic extremes not only host rich microbial faunas but life that can flourish in the most bitter of brines. What of the extremes of pH—bleach versus battery acid? Once again, alkaliphiles and acidophiles disport themselves in ponds and streams that would have the Health and Safety officers in a state of panic. Pressure, either crushingly high or extremely attenuated? Life, of course, exists in the deepest oceanic trenches, but how much deeper might be viable? The weakest link seems to be the pressure sensitivity of the phospholipid membranes, suggesting that even on planets with titanic oceans life won''t survive much deeper than in the Mariana Trench. The same argument applies to the deep crust: at about 5 km the crushingly high pressures also coincide with the thermal limits imposed by the geothermal gradient. Shall we look to the skies? Clouds carry bacteria, but even at quite modest heights it seems to be accidental freight rather than a nebulous ecosystem.Terrestrial life has conquered nearly all of the ‘habitation box'' and its evolution begs so many questions. Are some forms, such as the hyperthermophiles, survivors from the Earth''s apocalyptic beginnings? Maybe, but most have clearly been reinvented several times. Getting to the limits of life isn''t that difficult, but how do extremophiles not only survive but flourish in these environments? Often the adaptations seem minor, which merely means they are more subtle than we might realize. What of the future? So far as the Earth is concerned it must cope with ever increasing solar luminosity: the last men will long predecease the last microbe. Possibly long before, we will engage in the first great galactic diaspora; but wherever our biologists journey they may find that life ‘out there'' got no further than the blue jewel that is Earth.     

CHEMICAL EVOLUTION ON TITAN: COMPARISONS TO THE PREBIOTIC EARTH

Models for the origin of Titan's atmosphere, the processing of the atmosphere and surface and its exobiological role are reviewed. Titan has gained widespread acceptance in the origin of life field as a model for the types of evolutionary processes that could have occurred on prebiotic Earth. Both Titan and Earth possess significant atmospheres ( 1 atm) composed mainly of molecular nitrogen with smaller amounts of more reactive species. Both of these atmospheres are processed primarily by solar ultraviolet light with high energy particles interactions contributing to a lesser extent. The products of these reactions condense or are dissolved in other atmospheric species (aerosols/clouds) and fall to the surface. There these products may have been further processed on Titan and the primitive Earth by impacting comets and meteorites. While the low temperatures on Titan ( 72–180 K) preclude the presence of permanent liquid water on the surface, it has been suggested that tectonic activity or impacts by meteors and comets could produce liquid water pools on the surface for thousands of years. Hydrolysis and oligomerization reactions in these pools might form chemicals of prebiological significance. Other direct comparisons between the conditions on present day Titan and those proposed for prebiotic Earth are also presented.     

ultraviolet radiation from F and K stars and implications for planetary habitability

Now that extrasolar planets have been found, it is timely to ask whether some of them might be suitable for life. Climatic constraints on planetary habitability indicate that a reasonably wide habitable zone exists around main sequence stars with spectral types in the early-F to mid-K range. However, it has not been demonstrated that planets orbiting such stars would be habitable when biologically-damaging energetic radiation is also considered. The large amounts of UV radiation emitted by early-type stars have been suggested to pose a problem for evolving life in their vicinity. But one might also argue that the real problem lies with late-type stars, which emit proportionally less radiation at the short wavelengths ( < 200 nm) required to split O2 and initiate ozone formation. We show here that neither of these concerns is necessarily fatal to the evolution of advanced life: Earth-like planets orbiting F and K stars may well receive less harmful UV radiation at their surfaces than does the Earth itself.     

Sulfur,ultraviolet radiation,and the early evolution of life

The present biosphere is shielded from harmful solar near ultraviolet (UV) radiation by atmospheric ozone. We suggest here that elemental sulfur vapor could have played a similar role in an anoxic, ozone-free, primitive atmosphere. Sulfur vapor would have been produced photochemically from volcanogenic SO₂ and H₂S. It is composed of ring molecules, primarily S₈, that absorb strongly throughout the near UV, yet are expected to be relatively stable against photolysis and chemical attack. It is also insoluble in water and would thus have been immune to rainout or surface deposition over the oceans. The concentration of S₈ in the primitive atmosphere would have been limited by its saturation vapor pressure, which is a strong function of temperature. Hence, it would have depended on the magnitude of the atmospheric greenhouse effect. Surface temperatures of 45 °C or higher, corresponding to carbon dioxide partial pressures exceeding 2 bars, are required to sustain an effective UV screen. Two additional requirements are that the ocean was saturated with sulfite and bisulfite, and that linear S₈ chains must tend to reform rings faster than they are destroyed by photolysis. A warm, sulfur-rich, primitive atmosphere is consistent with inferences drawn from molecular phylogeny, which suggest that some of the earliest organisms were thermophilic bacteria that metabolized elemental sulfur.     

Estimates of the maximum time required to originate life

Fossils of the oldest microorganisms exist in 3.5 billion year old rocks and there is indirect evidence that life may have existed 3.8 billion years ago (3.8 Ga). Impacts able to destroy life or interrupt prebiotic chemistry may have occurred after 3.5 Ga. If large impactors vaporized the oceans, sterilized the planets, and interfered with the origination of life, life must have originated in the time interval between these impacts which increased with geologic time. Therefore, the maximum time required for the origination of life is the time that occurred between sterilizing impacts just before 3.8 Ga or 3.5 Ga, depending upon when life first appeared on Earth. If life first originated 3.5 Ga, and impacts with kinetic energies between 2×10³⁴ and 2×10³⁵ were able to vaporize the oceans, using the most probable impact flux, we find that the maximum time required to originate life would have been 67 to 133 million years (My). If life first originated 3.8 Ga, the maximum time to originate life was 2.5 to 11 My. Using a more conservative estimate for the flux of impacting objects before 3.8 Ga, we find a maximum time of 25 My for the same range of impactor kinetic energies. The impact model suggests that it is possible that life may have originated more than once.